NCD980729602_19910901_Jadco-Hughes_FRBCERCLA RD_Sampling Analysis Plan - Remedial Design Work Plan Submittal B-OCR

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SAMPLING AND ANA YLSIS PLAN
REMEDIAL DESIGN WORK PLAN
SUBMITTAL B
Jadco-Hughes Site
Gaston County, North Carolina
I SEPTEMBER 1991
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REF. NO. 3669 (4) CONESTOGA-ROVERS & ASSOOATES
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TABLE OF CONTENTS
Page
1.0 INTRODUCTION ...................................................................................................... 1
2.0 PROJECT DESCRIPTION .......................................................................................... 3
2.1 GENERAL ........................................................................................................ 3
2.2 RD INVESTIGATIVE ACTIVITIES .......................................................... .4
2.2.1 Groundwater Sampling and Analysis ...................................................... .4
2.2.2 Monitoring Well and Piezometer Installations ...................................... 5
2.2.3 Bedrock Monitoring Well Installations .................................................... 6
2.2.4 Geophysical Survey ....................................................................................... 7
2.2.5 Other Investigative Activities ..................................................................... 7
3.0 SAMPLE COLLECTION AND ANALYSIS PROTOCOLS ................................. 8
3.1 GENERAL SAMPLING PROTOCOLS ....................................................... 8
3.2 MONITORING WELL INSTALLATION ................................................. 9
3.2.1 Overburden Monitoring Wells .................................................................. 9
3.2.2 Bedrock Monitoring Wells .......................................................................... 10
3.2.2.1 Overburden Drilling .................................................................................. 11
3.2.2.2 Bedrock Coring ............................................................................................ 12
3.2.3 Monitoring Well Installation Procedure .................................................. 14
3.3 PIEZOMETER INSTALLATION ................................................................. 17
3.4 MONITORING WELL SAMPLING ........................................................... 18
3.4.1 Well Development.. ...................................................................................... 18
3.4.2 In Situ Monitoring Well Hydraulic Conductivity ................................. 20
3.4.3 Well Purging ................................................................................................... 20
3.4.4 Monitoring Well Sampling Procedure ..................................................... 22
3.5 GAS MONITORING ..................................................................................... 25
3.5.1 SVE Exhaust Gas Monitoring ...................................................................... 25
3.5.2 Soil Gas Monitoring ...................................................................................... 26
3.6 SAMPLE LABELING AND CONTROL ..................................................... 28
3.6.1 Initial Labeling of Samples .......................................................................... 28
3.6.2 Sample Shipment .......................................................................................... 29
3.6.3 Chain-of-Custody-Records ................................................................... : ....... 30
3.7 ANALYTICAL PROTOCOLS ....................................................................... 30
3.7.1 Scope ................................................................................................................. 30
3.7.2 Sample Analysis ............................................................................................. 31
3.7.3 Data Quality Assessment.. ............................................................................ 31
3.7.3.1 Laboratory Data Assessment. .................................................................... 31
3.7.3.2 CRA Data Assessment ............................................................................... 31
4.0 EQUIPMENT CLEANING PROTOCOLS .............................................................. 33
CONESTOGA-ROVERS & ASSOCIATES
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I TABLE OF CONTENTS
Page
I 5.0 WASTE MATERIAL HANDLING ........................................................................ 35
I 6.0 ON-SITE HEALTH AND SAFETY PLAN ............................................................ 36 ,, 7.0 REFERENCES ............................................................................................................. 37
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I CONESTOGA-ROVERS & ASSOCIATES
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I LIST OF FIGURES
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Page
I FIGURE 1.1 SITE LOCATION 1
FIGURE 1.2 SOIL TREATMENT TARGET AREA 1
I FIGURE 2.1 MONITORING WELL LOCATIONS 4
I FIGURE 2.2 MAGNETOMETER SURVEY PLAN 7
FIGURE 3.1 SPLIT SPOON SAMPLE SELECTION DETAIL 10
I FIGURE 3.2 TYPICAL MONITORING WELL NEST DETAIL 17
I FIGURE 3.3 TYPICAL CHAIN-OF-CUSTODY FORM 30
I LIST OF TABLES
I TABLE 2.1 PROPOSED WELL CONSTRUCTION DETAILS 5
,I TABLE 3.1 FIELD QUALITY CONTROL PROCEDURES 25
I TABLE 3.2 SAMPLE COLLECTIONS, PRESERVATION AND
SHIPPING PROTOCOL SUMMARY 29
I TABLE 3.3 TCL VOCs 30
TABLE 3.4 TCL BNAs 30
I TABLE 3.5 INORGANIC ANALYTES 30
I TABLE 3.6 SAMPLING SUMMARY 30
I LIST OF APPENDICES
I APPENDIX A ROCK QUALITY DESIGNATION PROCEDURE
I APPENDIX B QUALITY ASSURANCE PROJECT PLAN
I CONESTOGA-ROVERS & ASSOCIATES
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1.0 INTRODUCTION
This Sampling and Analysis Plan (SAP) has been prepared
as part of the Remedial Design (RD) Work Plan for the Jadco-Hughes Site
located in Gaston County, North Carolina. Figure 1. 1 shows the location of
the Site. The pre-RD and RD design activities consists of:
1) installation of a soil vapor extraction (SVE) system to remove volatile
organic compounds (VOC:s) and base/neutral/acid extractables (BNAs)
compounds in soils from the identified soil treatment target area (see
Figure 1.2) -RD activity;
2) SVE off-gas treatment using vapor-phase carbon-RD activity;
3) installation of five additional monitoring wells and six additional
piezometers - a pre-RD activity;
4) one round groundwater sampling of new and existing monitoring
wells - a pre-RD activity;
5) a geophysical survey of the northern portion of the Site - a pre-RD
activity; and
6) sampling of up to three residential wells downgradient of the Site, if
requested by USEP A and if access is granted to collect the samples.
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CONESTOGA-ROVERS II. ASSOCIATES
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figure 1.1
SITE LOCATION
JADCO-HUGHES SITE
Gaston County. North Carolina
3669-19/06/91-4--0
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~ SOIL TREATMENT TARGET AREA
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figure 1.2
SOIL TREATMENT TARGET AREA
JAOCO-HUGHES SITE
Gaston County, North Carolina
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This report presents protocols that will be followed during
the RD activities which are described in the RD Work Plan. These protocols
will insure that the analytical results are accurate and representative of field .
conditions.
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CONESTOGA-ROVERS 8, ASSOCIATES
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2.0 PROJECT DESCRIPTION
2.1 GENERAL
The objective of this SAP is to verify the effectiveness of
the remedial action technologies contemplated for use in treatment of the soil
and groundwater contamination at the Site. The SAP includes the following
activities:
1) completion of soil borings;
2) collection of soil samples from selected soil borings for chemical
analyses;
3) installation of five new monitoring wells and six piezometers;
4) development and slug testing of new monitoring wells and
piezometers;
5) collection of one round of groundwater samples from monitoring
wells for chemical analyses;
6) collection of gas samples from the SVE pilot system for chemical
analyses;
7) analyses of soil, gas and groundwater samples;
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CONESTOGA-ROVERS 11 ASSOCIATES
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8) a geophysical survey in the northern portion of the Site; and
9) collection and analyses of up to three samples from residential wells
downgradient of the Site, if requested by USEPA and if access is granted·
to collect the samples.
The procedures and protocols for collecting and analyzing
samples and performing all related field activities are described in the
following sections with the following exception:
• installation of the SVE pilot system is described in Section 3.0 of the
Treatability Study Work Plan.
2.2 RD INVESTIGATIVE ACTIVITIES
2.2.1 Groundwater Sampling and Analysis
As a part of the pre-design activities, all existing
monitoring wells shown on Figure 2.1 will be sampled once for volatile
organic compounds (VOCs) and metals analyses. In order to assess the impact
of silts and sediments in groundwater samples on the analytical results for
metals, the pre-design sampling will include the collection of filtered samples
for metals analyses from the following monitoring wells shown on
Figure 2.1: MWl; MW2D; MW3D; MWSD and MW6S.
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(APPROXIMATE LOC"TION)
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PROPERTY LINE
FENCE LINE
■ EXISTING PLUME t.lONITORING v.£ll
EXISTING SENTRY t.lONITORJNG WELl
e EXISTING PIEZOUETER
6 EXISTING PUMP v.£1...1..
@ PROPOSED SENTRY MONITORING WELl
@ PROPOSED PIEZOMETER
0 I.IANHOI..£ CUL\IERT
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50 100ft
MW501 MW5S
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figure 2.1
MONITORING WELL LOCATIONS
JADCO-HUGHES SITE
Gaston County. North Carolina
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The data from the analyses of filtered metals samples will
be compared with the unfiltered samples to determine if there is a statistical
difference between the results. This comparison will develop data for the
evaluation of background metals concentrations. Upon completion of the
installation of the new monitoring wells (see Section 2.2.2) groundwater will
be sampled and analyzed for VOCs,BNAs and metals.
2.2.2 Monitoring Well and Piezometer Installations
Additional monitoring wells and piezometers will be
installed as part of the pre-design activities. The locations of the proposed
monitoring wells and piezometers are shown on Figure 2.1. The proposed
installation details of the monitoring wells are shown in Table 2.1. The
purpose of each of the proposed installations is as follows:
• MWSDD -to evaluate the vertical extent of groundwater contamination at
this location;
• MW14S and 14D -to evaluate the vertical and horizontal extent of
groundwater contamination downgradient of Tributary A and to provide
a sentry monitoring post at the downgradient property limit;
• MW15S and 15D -to evaluate the vertical and horizontal extent of
groundwater contamination on the east side of Tributary B and to provide
a sentry monitoring post at this location; and
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TABLE 2.1
PROPOSED WELL CONSTRUCTION DETAILS
JADCO -HUGHES RD
Approximate Screen
Depth Length
Well Number (1) (Ft. BGS) (Ft.)
MW5DD 95 5
MW14S 12 5
MW14D 30 10
MW15S 16.5 10
MW15D 35 10
PZ8S 16 5
PZ8O 35 10
PZ9S 16.5 10
PZ9D 35 10
PZlOS 15 5
PZlOD 30 10
Notes:
(1) See Figure 2.1 for monitoring well locations
(2) Actual screened interval will be determined after well installation is completed.
Ft. BGS -Feet below ground surface
Ft AMSL -Feet above mean sea level
Proposed
Screened
Interval
(Ft.AMSL)
565 to 560
637 to 632
628 to 618
646 to 636
626 to 616
640 to 635
626 to 616
646 to 636
626 to 616
637 to 632
628 to 618
CONESTOGA-ROVERS & ASSOCIATES
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• PZ85, 8D, 95, 9D, 105 and lOD -to provide an assessment of the
pieziometric surface upgradient of the tributary and to provide for future
monitoring of the performance of the groundwater extraction system.
2.2.3 Bedrock Monitoring Well Installations
Bedrock monitoring wells were not installed during the
RI because there were no groundwater data to support the hypothesis that
groundwater contamination had migrated to the bedrock. Further, positive
vertical hydraulic gradients in the areas of elevated contaminant
concentration would not support the downward movement of contaminants.
Bedrock monitoring wells are not proposed to be installed
during the RD unless groundwater data demonstrate a significant increase in
contaminant concentration in deep overburden groundwater. Data from the
analysis of samples collected from existing monitoring wells MWlOD and
MW13D and proposed monitoring well MWSDD will be evaluated to
determine if a statistically significant increase in contaminant concentrations
has occurred. If such an increase is observed, then one to three bedrock
monitoring wells will be installed at a location(s) to be determined based on
the data.
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2.2.4 Geophysical Survey
A magnetometer survey will be conducted as part of the
remedial action activities. The survey will be performed over the northern
portion of the Site where extensive subsurface investigations have not been
completed. The area to be investigated (the northern portion of the Site) is
illustrated on Figure 2.2. The survey will be conducted on a 50 foot grid
spacing over the Site. The grid spacing will be surveyed by CRA or a
subcontractor using existing surveyed installations as reference points.
A magnetometer (Unimag II Portable Proton
Magnetometer Model G-846 or equivalent) will be used for the survey. A
magnetometer is capable of accurately detecting magnetic objects, such as
buried drums or large bodies of ore which alter the earth's magnetic field by
measuring this change in the magnetic field.
All geophysical abnormalities detected during the survey
will be documented in the field and surveyed in reference to the SO-grid
locations.
2.2.5 Other Investigative Activities
All other field investigative activities which are part of
the RD are related to the proposed treatability studies and are discussed in
Section 3.5 and the Treatability Study Work Plan (Submittal C to the RD
Work Plan).
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1,~,-c·;i:·r1 MAGNETOMETER SUR\'EY AREA
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figure 2.2
MAGNETOMETER SURVEY PLAN
JADCO-HUGHES SITE
Gaston County, North Carolina
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3.0 SAMPLE COLLECTION AND ANALYSIS PROTOCOLS
3.1 GENERAL SAMPLING PROTOCOLS
The following protocols will be employed during all
sampling throughout this RD program:
1) all sampling activities will be conducted in accordance with the Health
and Safety Plan (Submittal A to the RD Work Plan);
2) prior to drilling or excavating, at the initial and all subsequent
locations, the drilling rig and all drilling equipment or excavation
equipment will be cleaned according to the protocols established in
Section 4.0;
3) all sampling instruments and equipment used in collecting samples for
chemical analysis will be cleaned in accordance with the protocols
presented in Section 4.0 prior to sampling at each location; and
4) a new pair of disposable latex gloves will be used at each sampling
location. Additional glove changes will be undertaken as conditions
warrant.
Additional protocols specific to each sampling method are
presented in the following sections.
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3.2 MONITORING WELL INST ALVA TION
3.2.1 Overburden Monitoring Wells \
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All overburden mon'itoring well boreholes will be
I advance to specified depths, using 4-1/4 inch inside diameter (ID) [8-inch
outside diameter (OD)] hollow stem aug~rs. The locations of the proposed
new monitoring wells are shown on FiJure 2.1.
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Soil samples will be lollected continuously during
augering to identify and classify soil maJerials.
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I All soil samples will be collected using a split spoon
sampler as described by the standard peJetration test method (ASTM 1586-84)
or a continuous sampling system should soil conditions allow its use.
Soil sampling equipment will be cleaned between samples
as per Section 4.0. All soil samples collecJed will be described and classified
according to the Unified Soil ClassificatiJn System (USCS) and then stored in
glass jars for geologic record. All sampleJ retained for geologic record will be
stored on Site. Soil samples will also be Jollected for chemical analysis at each
new well nest location at 5-foot intervals !until the upper limit of the water
table is encountered.
Split-spoon soil sampils collected for chemical analysis
will be obtained and prepared in the follJwing .manner:
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a)
b)
c)
The split-spoon sampler will be removed to a sample preservation
station and opened. I
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Using a clean cutting tool (stainle~s steel knife) a thin section will be
removed from the top and bottoJ of the core and discarded, as shown
on Figure 3.1.
The remaining core will be cut in half longitudinally. From the centre
of the core a continuous soil sample will be taken using a clean spatula.
I The sample will be placed into a 250-mL glass jar with teflon lid liner
for subsequent chemical analysis.
During sampling, photoionization detector (HNu)
readings of soil samples will be taken frJm the open split spoon and will be
recorded, as an indication of the volatile organic contamination as soon as
possible after collection. HNu readings are considered as survey values
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which provide relative concentrations of volatile organic concentrations
present in soil. All soil cuttings will be s~read on polyethylene sheeting near
the borehole and subsequently transferreh into 55-gallon drums. The drums
will be relocated to the temporary drum itaging area for treatment with the
I remainder of Site soils in the final remedy.
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3.2.2 Bedrock Monitoring Wells
I The protocols for the installation of bedrock monitoring
I wells are included herein so that scheduling delays are not encountered in
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a
TYPICAL SOIL CORE
SPLIT
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3669-11/09/91-4-0 (D-06)
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PORi:lON OF SAMPLE FOR CHEMICAL ANALYSIS
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-CONTACT WllH UNSTERIUZED MATERIALS IS I
NOT ACCEPTABLE
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-srORAGE -REFRIGERATED ( 4"C)
-SHIPPING -ON ICE BY COURIER TO DESIGNATED LAB
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PORTION OF SAMPLE TO BE RETAINED
' FOR GEOLOGIC RECORDS
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-CONTACT WllH UNSTERIUZED MATERIALS IS
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NOT A PROBLEM
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-CONTAINER: -CLEAN GLASS JAR
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-CLEAR GLASS IS SUITABLE
-STIORAGE -IN STANDARD SHIPPING CARTON
-NO REFRIGERATION REQUIRED
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PORTION OF SAMPLE TO BE DISCARDED
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-DISCARDED WllHIN 55 GALLON DRUM
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MAINTAINED ON-SITE
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figure 3.1
SAMPLE SELECTION DETAIL
JADCO-HUGHES SITE
Goston County, NC
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the unlikely event that the pre-RD data demonstrate that a bedrock
monitoring well(s) are required. Bedrock monitoring wells are not proposed
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to be installed during the RD, as was discussed in Section 2.2.3.
3.2.2.1 Overburden Drilling
At each bedrock well location, if such a well(s) are
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required, the overburden portion of each bedrock monitoring well will be
I advanced using 4-1/4-inch ID (8-inch OD) hollow stern augers until competent
bedrock is encountered. Soil sampling Jrotocols, as described in Section 3.2.1,
will remain in effect during the overbu)den drilling of the bedrock wells.
Upon auger refusal, the hollow-stem augers will be
removed from the borehole. The borehole will be reamed to 10 inches in
diameter using a tricone bit and wet-rotkry drilling methods. Wet rotary
methods utilize water or drilling mud (~ornrnonly a bentonite slurry) as a
I drilling fluid to carry cuttings to surface! The 10-inch hole will be advanced
I two feet into competent bedrock.
A 6-inch diameter st~el protective casing complete with
I centralizers, will be installed in the borehole, two feet into bedrock, where it
will be grouted into place.
Grout will consist of a cernent/bentonite slurry and will
have a mixture ratio of 6.5 gallons of water per 94-pound bag of normal
portland cement, producing a slurry weiiht of 15.6 lb/gal. Approximately
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four pounds of bentonite per sack of cement will be added to the slurry. · The
amount of bentonite will not exceed five percent of the mixed slurry to avoid
excessive shrinkage of the cement.
The grout will be pumped into the annular space through
a tremie pipe/packer assembly located in the protective casing near the
bottom of the boring. The discharge end of the grout rod will be fitted with a
ball valve to reduce the infiltration of grout into the protective casing. The
pumping of grout will continue until undiluted grout returns through the
annulus to the ground surface. The casing will then be pushed into the
bedrock to further seal the annulus. The grout will be allowed to set for a
minimum period of 24 hours before bedrock coring commences.
All fluids generated during drilling will be contained and
analyzed to determine final disposition. All containment drums will be
labeled as to the date, time and contents. An inventory of all drums will be
maintained by CRA's on-Site personnel.
3.2.2.2 Bedrock Coring
The bedrock portion of each bedrock monitoring well will
be completed by coring techniques. All coring will be performed in
accordance with AS1M D2113-83, using clear, potable water as the circulation
medium. A sample of the potable water used in the drilling and coring
operations will be collected and analyzed for Target Compound List (TCL)
VOCs. A record of water used for drilling will be kept. This record will
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include the date, time, borehole, water source, additives, purpose and the
amount not recovered from the borehole. The corehole will be advanced
using an "N" size corebarrel (1.88-inch diameter core and 2.98-inch diameter
hole) .
The borehole will be cored continuously, in IO-foot
intervals, for the entire depth. The corehole will extend a minimum of
15 feet below the bedrock surface and 15 feet into a water-bearing fracture
zone.
Each core run will be laid in core boxes in accordance with
the above noted ASTM standard and visually inspected by a qualified
geologist in the field. The geologist will complete a geologic log of the core
with particular attention being noted of fractures, aperture size, orientation,
spacing, filling, roughness and discontinuity type. Rock quality designation
(RQD) tests will be conducted over the length of the core. The procedure for
applying the RQD is presented in Appendix A. During drilling the water loss
and gains will be closely monitored to identify fracture zones. The geologist
will also note any staining or secondary mineralization with the fractures.
Upon reaching the final depth, the drilling fluid will be
circulated to remove rock cutting from the borehole walls which remain after
the drilling and reaming operations. All fluids generated during coring will
be contained and analyzed to determine final disposition.
All core boxes will be clearly labeled to indicate the
following: job name, job number, hole number, run number, run interval
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and date. All core boxes will be covered in plastic and placed in a secure area
on a Site once they are logged and sealed.
3.2.3 Monitoring Well Installation Procedure
Overburden monitoring wells will be completed in the
saprolite/overburden, to the required depths, in the following manner. The
borehole will be advanced using 4-1/4-inch ID (8 inch OD) hollow stern augers
to the required screened interval.
The augers will be fitted with a plug to prevent soil from
entering the augers during advancement of the borehole. The drill plug and
rods will be removed so that the augers act as temporary casings.
Filter sand will be placed in the borehole and the augers
will be retracted so that approximately one foot of filter sand is in the bottom
of the hole.
A 2-inch diameter, Type 304, No. 15 slot, 5 or 10-foot long
stainless steel well screen attached to 2-inch diameter, Schedule 5, Type 304
stainless steel riser will be installed. No lubricants other than water will be
used.
Augers will be raised in 2-foot increments as the filter
sand pack is installed to a level of two feet above the well screen. The length
of sand pack will be confirmed by measurement.
14
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A two foot bentonite pellet seal will be placed and tamped
in place with 3/4-inch·rod. The thickness of seal will be confirmed by
measurement and will be allowed to set prior to placement of grout. Then a
6-inch diameter, Schedule 40, lockable protective casing will be installed.
Next, grout will be pumped into the borehole until undiluted grout returns
to the ground surface. After the grout has set overnight, the remaining
portion of the borehole will be filled with cement/bentonite to within one
foot of the ground surface.
Well installations which are not completed at the end of a
workday will be temporarily secured by placing the drilling auger head over
the hole or installing a temporary fence around the drilling area.
Upon completion of the monitoring wells, each protective
surface casing will be fitted with a permanent lockable cap. The lockable cap
will be two to four inches above the top of riser and a vented cap will be
placed on the riser. A lock will be placed on the well for securement. A weep
hole will be drilled in the casing to facilitate drainage after development and
purging. A concrete protection collar measuring three feet by two feet by
one foot in depth will be placed around the protective casing. The collar will
be sloped such that it promotes the drainage of surface waters away from the
protective casing.
Any necessary bedrock well will be completed as a 2-inch
diameter monitoring well in the following manner. The geologic log of the
core will be examined to locate fracture zones. Based on the observed
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distribution of fracture (based on water losses or gains), fracture staining,
secondary mineralization and RQD, a preferred monitoring interval will be
selected. If the bedrock proves to be competent, no well screen will be
installed and the well will be completed as an open borehole in bedrock. The
hole will be cored as described in Section 3.2.2.2.
The corehole will then be reamed (if necessary) using wet
rotary drilling techniques to a 6-inch diameter to the desired depth. A 2-inch
diameter, Type 304, No. 15 slot stainless steel well screen of predetermined
length (maximum 10 feet) attached to 2-inch diameter, Schedule 5, Type 304
stainless steel riser will be installed through the protective casing to the
desired depth. No lubricants other than potable water will be used in the
assembly of the well screen and riser.
An inert sandpack (20-40 mesh) will be placed in the
annulus space to a height of approximately two feet above the well screen and
will be confirmed by measurement. A 2-foot thick bentonite pellet seal will
be placed above the sand pack and will be tamped in place using a 3 / 4-inch
rod. Bentonite pellets will be tested prior to use to determine swelling time.
The bentonite seal will be allowed to set prior to placing the grout.
A tremie pipe will be lowered into the borehole and
cement/bentonite grout will be introduced to the annular space between the
riser and protective casing. Pumping of grout will continue until undiluted
grout returns to the ground surface. After the grout has set overnight, the
remaining portion of the borehole will be filled with cement/bentonite to
within one foot of the ground surface.
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A copy of each monitoring well key will be provided to
the United States Environmental Protection Agency (USEPA).
Each monitoring well will be clearly labeled with its own
unique identification number in an area where it is protected from possible
vandalism. A label will be placed stating that the well is a monitoring well
and should not be used for drinking or irrigation.
Completion details for typical overburden and bedrock
wells (not proposed to be installed during the RD, presented as contingency
wells only) are shown on Figure 3.2.
3.3 PIEZOMETER INSTALLATION
Piezometers will be installed at locations as shown on
Figure 2.1 to the specified depths (see Table 2.1). Piezometers will be advanced
into the overburden material by the same methods described for monitoring
well installations. The well screen and riser of the piezometers will be 1-inch
diameter PVC pipe.
All piezometer well screens and risers will be cleaned,
according to protocols described in Section 4.0 for sampling equipment, prior
to installation.
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BEDROCK WELL OVERBURDEN WELL
APPROX.
15'
(VARIES) 2 FT
CRA
3669-19 /06/91-4-0
s•• PROTECTIVE
CASING 1'11TH
LOCKABLE CAP
2•• STAINLESS STEEL
TYPE 304
SCH 5 RISER
WEEP HOLE
CONCRETE
SECURITY
COUAR
ANNUL.AR SPACE
MIN. 25 FT
~fflt---Fill.ED 1'11TH ----.;; VARIES
CEMENT /BENTONITE
GROUT
10•111 BORING
GROUTED 1'11TH
CEMENT /BENTONITE
MIXTURE
BENTONITE SEAL
"I---5•111 STEEL CASING
2·111x1 o·
NO. 15 SLOT
STAINLESS STEEL
WELL SCREEN
GRADED SILICA _ _,,..
SANDPACK
2•111 X 5'
NO. 15 SLOT
STAINLESS STEEL
WELL SCREEN
-~---GRADED SILICA .==.¥,-,.. SANDPACK
_i2 FT =r2 FT
( BEDROCKJ
figure 3.2
TYPICAL MONITORING WELL NEST DETAIL
JADCO-HUGHES SITE
Goston County, North Carolina
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Piezometer installation methods will follow the
procedures utilized for monitoring well installations (i.e. sandpack, bentonite
grout, etc.). Since the piezometers will be used only for water level
measurements, soil sampling will not be performed during piezometer
installation because sufficient sampling will be performed during monitoring
well construction.
3.4 MONITORING WELL SAMPLING
3.4.1 Well Development
All monitoring wells will be developed prior to sampling
in accordance with the following protocols:
1) water levels in all wells will be measured to ±0.01 foot prior to
development;
2) all wells will be developed to a silt-free condition, if possible, following
installation, by one of the following techniques:
a) bailing with a bottom loading stainless steel/ teflon bailer
attached to a nylon rope;
b) pumping using a stainless steel bladder pump with teflon
bladder and discharge tubing and polyethylene air supply line
attached to a nylon rope;
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3)
4)
c) peristaltic pump with teflon discharge tubing. For development
the small length of silicon within the pump will not be replaced;
or
d) two-inch submersible stainless steel pump attached to reinforced
PVC discharge tubing.
Discharge tubing, if used, will be dedicated to each well. New
polyethylene air tubing and nylon rope, where applicable, will be used
at each well location;
during development, sediment within the well will be placed into
suspension by surging with the bottom loading bailer or agitation of
the discharge tubing;
after each well volume is removed, a sample will be collected and
analyzed for pH, temperature and conductivity. Development will
continue until three consecutive and consistent readings of pH,
temperature and conductivity are obtained. Readings will be
considered consistent if all three conductivity values are within
ten percent of the average value and all pH values are within +0.1 pH
unit of the average value over the last three volumes. In the event
that these field measurements are not consistent, well development
will continue to a silt free condition, if possible, or until a maximum of
ten well volumes have been removed;
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CONESTOGA·ROVERS & ASSOCIATES
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5) in wells where recharge is insufficient to conduct the development
protocol described above, the well will be pumped/bailed to dryness on
three consecutive working days. Wells which are developed to dryness
will not be subject to the above stabilization criteria. The three
consecutive days can be split to allow for a break for the weekend; and
6) all development water will be handled in accordance with the
protocols specified in Section 5.0.
3.4.2 In Situ Monitoring Well Hydraulic Conductivity
The in-situ horizontal hydraulic conductivity for
monitoring wells will be determined using one of the following methods:
Hvorslev (1951); Cooper et al (1967); Papadopulos et al (1973); or, Bouwer and
Rice (1976).
3.4.3 Well Purging
Prior to sample collection, all monitoring wells will be
purged in accordance with the following protocols:
1) water levels in all wells will be measured to ±0.01 foot prior to purging,
unless development and purging occur on the same day. In that case, a
static water level will have been taken prior to development;
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2)
3)
4)
all wells will be purged by one of the following techniques:
a) bailing with a bottom loading stainless steel/ teflon bailer
attached to a nylon rope;
b) a teflon bladder stainless steel pump fitted with teflon discharge
and polyethylene air supply lines attached to a nylon rope;
c) a peristaltic pump with a teflon discharge line; or
d) a two-inch submersible pump.
Discharge tubing, if used, will be dedicated to each ~ell. The small
length of silicon tubing within the peristaltic pump will not be replaced
between wells. New nylon rope and polyethylene tubing, where
applicable, will be used at each well location;
purging will be conducted until a minimum of three well volumes are
evacuated. After each well volume is evacuated, a sample will be
collected and analyzed for pH, temperature and conductivity;
in the event that recharge is insufficient to conduct the purging
protocol described above, the well will be pumped/bailed to dryness
and allowed to sufficiently recharge prior to sampling. Wells which
are purged to dryness will not be subject to the above purging criteria;
and
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5) all purge water will be handled in accordance with the protocols
specified in Section 5.0.
3.4.4 Monitoring Well Sampling Procedure
Following well purging, monitoring well sampling will be
carried out according to the following protocols:
1) water samples will be collected for chemical analysis using one of the
following techniques:
a) a bottom loading stainless steel/ teflon bailer attached to a nylon
rope; or
b) a teflon bladder stainless steel pump fitted with teflon discharge
tubing and polyethylene air supply lines attached to a nylon
rope.
Prior to use in any monitoring well, the sampling equipment will be
precleaned as described in Section 4.0. New nylon rope and
polyethylene tubing, where applicable, will be used at each well
location;
2) in the event that the groundwater is still turbid following purging,
additional purging and/or appropriate sampling techniques (i.e. low
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3)
4)
pumping rate) shall be implemented to collect sedimentsfree samples
or samples that are as sediment-free as possible;
in the event that a well is purged dry, sample collection will commence
on the following day and continue for up to four consecutive days to
obtain the required sample volume. Sampling may commence on the
day of purging if the water level recovers to static water level within
four hours after completion of purging. A well shall be deemed dry for
sampling purposes if the volume of water collected over four days is
not sufficient for the required analysis. The above procedure may
require four consecutive days for slow recovering wells;
sufficient groundwater will be collected for chemical analysis of TCL
VOCs, TCL BNAs and Target Analyte List (TAL) Metals and Cyanide
(see Section 3.7). Groundwater samples collected for TCL VOC analysis
will be collected in 3 x 40 mL glass septum cap vials each preserved
with four drops of HCL. TCL BNA groundwater samples will be
collected in 1-litre amber glass bottles. Duplicate groundwater samples
(filtered and unfiltered) collected for TAL Metals analysis will be
collected in 500 mL polyethylene bottles and preserved with 50% HN03
to pH <2. The filtered sampled will be collected using a Whatman #40
filter paper. The samples collected for analysis of total cyanide will be
collected in 1-litre polyethylene or glass bottles and preserved with
NaOH to pH >12.
Sample containers will be ICH-EM 300 series or equivalent to ensure
containers are analyte free. Sample containers will be shipped to the
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CONESTOGA·.~OVERS 11. ASSOCIATES
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5)
6)
7)
site in sealed containers from a single lot of prepared bottles. A trip
blank will be included for all aqueous VOC sampling events. The trip
blank will be prepared, in duplicate, in the laboratory, and will consist
of two sets of bottles from the same lot of bottles as the sample bottles,
filled with distilled/ deionized water. One set will be retained in the lab
and the second set will be sent with the sample bottles. Both sets will
be analyzed using the same protocols as those used for water sample
analysis;
field measurements of pH (using a Fisher Model MDL-107 pH meter or
equivalent), conductivity and temperature (using a YSI Model 33 SCT
meter or equivalent) will be taken after well purging, prior to sample
collection. Calibration of field instruments will be undertaken daily in
accordance with manufacturer's specifications;
a blind field duplicate sample will be collected per set of samples per
matrix (a set of samples is defined as the samples collected in a matrix
for a specific sampling event, for example a groundwater sampling
round) or at a minimum frequency of one in ten locations per matrix;
and
a rinsate sample will be collected per set of samples or at a minimum
frequency of one in ten locations. The rinsate sample will consist of
deionized/distilled water poured into, and then sampled out of, a
bailer/pump cleaned under the protocol specified for sampling
equipment. The rinsate blank collected for metals will be in duplicate
(filtered and unfiltered).
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Table 3.1 presents a summary of field quality control
procedures established for both water and soil matrices. Quality control
protocols are presented in the Quality Assurance Project Plan (QAPP), which
is presented in Appendix B.
3.5 GAS MONITORING
3.5.1 SVE Exhaust Gas Monitoring
The SVE pilot study exhaust gas samples will be collected
from the exhaust side of the SVE vacuum blower, upstream from the
treatment unit. The samples will be collected in accordance with the
following protocols:
1) the samples will be collected by attaching a pre-evacuated, 6-liter
Summa® gas canister to the sampling port using Swageloc®
compression tube connectors;
2) the samples will be collected while the vacuum blower is operating at
its nominal flow rate and pressure by opening both the sample port
valve and the Summa® canister valve;
3) the valves will be left open until the pressure on the canister has
equilibrated with that on the SVE exhaust line as indicator by a
pressure gauge on the intake of the canister;
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TABLE 3.1
FIELD QUALITY CONTROL PROCEDURES
REMEDIAL DESIGN
JADCO-HUGHES SITE
Trip Blank Rinsate Sample
one per set of samples one per set of samples
or a minimum of
one per set of samples
1 in 10 investigatory
sampling locations
Field Duplicate
one per set of samples
or a minimum of
1 in 10 investigatory
sampling locations
one per set of samples
or a minimum of
1 in 10 investigatory
sampling locations
Matrix Spike/
Matrix Spike
Duplicates (1)
one per set of samples
or a minimum of
1 in 20 investigatory
sampling locations
one per set of samples
or a minimum of
1 in 20 investigatory
sampling locations
I Note:
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(1) Additional sample (three times the designated value) will be collected for matrix
spike/matrix spike duplicate analyses.
CONESTOGA-ROVERS & ASSOCIATES
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4) the valve on the canister will be closed and then the valve on the
exhaust port will be closed;
5) the canister will be labeled with the location, time, date, sampler name,
initial and exhaust pressure as specified in the QAPP. QA/QC samples
(duplicates, trip blanks) will be collected as specified in the QAPP; and
6) the samples will be shipped to the laboratory within 24 hours of
collection.
3.5.2 Soil Gas Monitoring
Soil gas samples will be collected from the permanent
monitoring probes which would be placed in the former landfill pursuant to
the Soil Vapor Extraction Treatability Study Work Plan according to the
following protocols:
1) samples will be collected after the SVE system has been shut-off at least
48 hours;
2) samples will be collected by attaching a pre-evacuated, 6-liter Summa®
gas canister and portable vacuum pump with a T-connector to the
probe with the valves on the probe and canister closed;
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3)
4)
5)
6)
7)
8)
the probe will be evacuated for a sufficient time to remove three probe
volumes of gas at standard temperature and pressure. The probe
evacuation volume will be calculated based on the volume of the
tubing leading to the sampling interval and the approximate pore
volume of the sand pack in the sampling interval;
after purging is complete but prior to shutting off the vacuum pump,
the valve between the pump and the T-connector will be closed. The
vacuum pump will then be shut off;
with the probe valve open and the canister valve shut, the probe will
be allowed to equilibrate to ambient pressure;
after the vacuum gauge on the probe has read zero vacuum for one
minute, the valve on the Summa® canister will be opened to collect
the sample. Sampling will be complete after the vacuum gauge on the
probe has read zero vacuum for one minute and the valves on the
canister and the probe will be closed;
the canister will be labeled with the location, time, date and sampler
name as specified in the QAPP. QA/()!: samples (duplicates) will be
collected as specified in the QAPP; and
the samples will be shipped to the laboratory within 24 hours of
collection.
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3.6 SAMPLE LABELING AND CONTROL
Sample labeling and control will be consistent with
USEPA requirements and CRA procedures. These procedures are discussed
below.
3.6.1 Initial Labeling of Samples
A unique numbering system will be used to identify each
collected sample. This system will provide a tracking number to allow
retrieval and cross-referencing of sample information. A listing of the
sample identification numbers with written descriptions of sample location,
type, time and date will be maintained by CRA's on-Site personnel. The
sample number system to be used is described as follows:
Example:
where:
w
YYMMDD
AA
xxxx
W-YYMMDD-AA-XXXX
-designates sample type
(W -water, G -gas, 5-soil)
-date of collection (year, month, day)
-sampler initials
-sequential number starting with 0001
Quality Control samples will also be numbered with a unique location
number using this numbering system.
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CRA's on-Site personnel will be responsible for recording
the sampling activities for each day and will record in the log book the
following with respect to each sample:
1) unique sample identification number;
2) sampling location identification;
3) date/ time of sample collection; and
4) sampling data/remarks.
3.6.2 Sample Shipment
All water and soil samples will be placed in laboratory
supplied coolers and iced to 4°C (±2°C) after collection and labeling. Summa®
canisters will be placed in the original shipping cartons. All samples will be
delivered to the laboratory within 48 hours of sample collection by
commercial courier.
Individual sample bottles will not be sealed; however,
each cooler will be sealed with a transportation security seal containing the
sampler's initials. The cooler will then be sealed with packing tape.
Table 3.2 presents a summary of sample collection,
preservation and shipping requirements.
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CONESTOGA-ROVERS 11 ASSOCIATES
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0 0 2 rn (/)
--l 0
,:;i
]>
::0 0 < m
::0 (/)
"" )>
(J) en 0
0
)> -I m (J)
Matrix
Ground water
Soil
Air
Note:
TABLE 3.2
SAMPLE COLLECTION, PRESERVATION AND SHIPPING PROTOCOL SUMMARY
REMEDIAL DESIGN
JADCO-HUGHES SITE
Parameter Bottles/Jars Preservatives Holding Time (1) Shipping
TCLVOCs 3 x 40 ml glass iced to 4 °C (±2°C) 60 days Federal Express
septum vials preserved with Priority 1
four drops of HCl
topH<2
TCLBNAs 1-litre amber glass iced to 4 °C (±2°C) 7 days until Federal Express
bottle extraction, Priority 1
40 days after
extraction
Total Metals 500 ml polyethylene iced to 4 °C (±2°C) 6 months Federal Express
bottle preserved with 50% (Mercury 28 days) Priority 1
HNO3topH<2
Total Cyanide 1-litre polyethylene iced to 4°C (±2°C) -14 days Federal Express
or glass bottle preserved with Priority 1
NaOH to pH> 12
TCLVOCs 250 ml glass -iced to 4 °C (±2°C) -14 days Federal Express
TCLBNAs jar with teflon Priority 1
lid
TCLVOCs Summa® canister -none -30 days Federal Express
Priority 1
(1) Sample holding time will be calculated from the time of sample collection to sample analysis.
Packaging
Cooler, Cushioning
(i.e. bubble pack,
foam)
Cooler, Cushioning
(i.e. bubble pack,
foam)
Cooler, Cushioning
(i.e. bubble pack,
foam)
Cooler, Cushioning
(i.e. bubble pack,
foam)
Cooler, Cushioning
(i.e. bubble pack,
foam)
packing carton
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3.6.3 Chain-of-Custody-Records
CRA chain-of-custody records will be used to track all
samples from the time of sampling to the arrival of samples at the laboratory.
Three original copies of the chain-of-custody record will accompany the
sample shipment to the laboratory and will be signed and retained by the
receiving laboratory's sample custodian. A copy of the chain-of-custody
record will be retained by the shipper. Two completed copies will be returned
to CRA by the laboratory. A typical chain-of-custody form is presented on
Figure 3.3.
3.7 ANALYTICAL PROTOCOLS
3.7.1 Scope
Samples collected for chemical analysis as described in the
previous sections will be analyzed for TCL VOCs, TCL BNAs, Total Metals
and cyanide. Table 3.3 and 3.4 presents the TCL VOCs and TCL BNAs,
respectively. Table 3.5 presents a list of inorganic analyses. A sampling
summary is presented on Table 3.6. All analytical work will be completed
using approved USEP A methodologies as specified in the following sections.
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CRA SHIPPED TO (Laboratory name):
CONESTOGA-ROVERS & ASSOCIATES
CHAIN OF CUSTODY PROJECT ""'' PROJECT NAME:
RECORD
"' SAMPLER'S SIGNA TIJRE 15 SAMPLE , ..... i TYPE i!!l! REMARKS
!:~ SEQ. SAMPLE ""'· DATE TIME SAMPLE LOCATION ""'·
/ " // .
\. \.,. './ -\. ' ,, >
\. \.. ' r/
TOT AL NUMBER .0F .CC lifAltlERS / >
ANTICIPATED CHEMICAL HAZARDS: A \V) V
RELINQUISHED BY: '~\\~v RECEIVED BY:
[I] (SON) ® (SON) -'' RELINQUISHED BY: ,~ ~~ 11ME RECEIVED BY: -'--._ I @ ,2 (SIGNy > \ \ .... (SON) -
RELINQUISHED BY: I~\( DATE/11ME RECEIVED BY:
3 (S I I r I © (SON)
RELINQUISHED BY: ~ DATE/TIME RECEIVED BY:
Iii (SON) I ® (SON)
RELINQUISHED BY: DATE/11ME RECEIVED BY:
[ID (SON) I ® (SIGN)
RELINQUISHED BY: DATE/TIME RECEIVED BY:
[ID (SON) I (2) (SON)
RELINQUISHED BY: DATE/TIME RECEIVED BY:
CT] (SON) I ® (SON)
METiiOD OF SHIPMENT: SHIPPED BY: RECEIVED FOR LABOR A TORY BY: DATE/TIME
(SON) I
CONDITION OF SEAL UPON RECEIPT: COOLER OPENED BY: DATE/TIME
GENERAL CONDITION OF COOLER:
(SON) I
-CRA OFflCE COPY \\HITE
YELLOW
PINK
GOLDENROD
-RECEIVING LABORATORY COPY figure 3.3
TYPICAL CHAIN OF CUSTODY FORM
JADCO-HUGHES SITE
Goston County, North Carolina
-CRA LABORATORY COPY
-SHIPPERS
3669-19/06/91-4--0
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TABLE 3.3
TCL voes
REMEDIAL DESIGN
JADCO-HUGHES SITE
CAS No.
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-34-3
156-60-5
67-66-3
107-06-2
78-93-3
71-55-6
56-23-5
75-27-4
78-87-5
10061-02-6
71-01-6
71-43-2
124-48-1
79-00-5
10061-01-05
75-25-2
591-78-6
127-18-4
79-34-5
108-88-3
108-90-7
100-41-4
108-10-1
108-42-5
1330-20-7
Compound
chloromethane
bromomethane
vinyl chloride
chloroethane
methylene chloride
acetone
carbon disulfide
1, 1-dichloroethene
1, 1-dichloroethane
1,2-dichloroethene (total)
chloroform
1,2-dichloroethane
butanone
1, 1, 1-trichloroethane
carbon tetrachloride
bromodichloromethane
1,2-dichloropropane
trans-1,3-dichloropropene
trichloroethene
benzene
dibromochloromethane
1, 1,2-trichloroethane
cis-1,3-dichloropropene
bromoform
2-hexanone
tetrachloroethene
1, 1,2,2-tetrachloroethane
toluene
chlorobenzene
eth y 1 benzene
4-methyl-2-pentanone
styrene
total xylenes
CONESYOG/.\·ROVERS & ASSOCIATES
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CAS No.
111-44-4
108-95-2
95-57-8
541-73-1
106-46-7
95-50-1
39638-32-9
95-48-7
67-72-1
621-64-7
98-95-3
106-44-5
78-59-1
88-75-5
105-67-9
111-91-1
120-83-2
120-82-1
91-20-3
106-47-8
87-68-3
91-57-6
59-50-7
77-47-4
95-95-4
88-06-2
91-58-7
208-96-8
131-11-3
606-20-2
83-32-9
99-09-2
132-64-9
51-28-5
121-14-2
86-73-7
TABLE 3.4
TCL BNAs
REMEDIAL DESIGN
JADCO-HUGHES SITE
Compound
bis(2-chloroethyl)ether
phenol
2-chlorophenol
1,3-dichlorobenzene
1,4-dichloro benzene
1,2-dichlorobenzene
bis(2-chloroisopropyl)ether
2-methylphenol
hexachloroethane
Page 1 of 2
N-ni troso-di-n-di propy !amine
nitrobenzene
4-methylphenol
isophorone
2-nitrophenol
2,4-dimeth y I phenol
bis(2-chloroethoxy)methane
2,4-dichlorophenol
1,2,4-trichlorobenzene
naphthalene
4-chloroaniline
hexachlorobutadiene
2-methylnaphthalene
4-chloro-3-methylphenol
hexachlorocyclopentadiene
2,4,5-trichlorophenol
2,4,6-trichlorophenol
2-chlorona p h thalene
acenaphthylene
dimethylphthalate
2,6-dinitrotoluene
acenaphthene
3-nitroaniline
dibenzofuran
2,4-dini trop henol
2,4-dinitrotoluene
fluorene
CONESTOGA-ROVERS 8 ASSOCIATES
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CAS No.
100-02-7
7005-72-3
84-66-2
534-52-1
86-30-6
100-01-6
101-55-3
118-74-1
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
218-01-9
56-55-3
117-81-7
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
91-94-1
88-74-4
86-74-18
TABLE 3.4
TCL BNAs
REMEDIAL DESIGN
JADCO-HUGHES SITE
Page 2 of 2
Compound
4-ni trophenol
4-chlorophenyl phenyl ether
diethyl phthalate
4,6-dini tro-2-meth y I phenol
N-ni trosodi phen ylamine
4-nitroaniline
4-bromophenyl phenyl ether
hexachlorobenzene
pentachlorophenol
phenanthrene
anthracene
di-n-bu tylph thalate
fluoranthene
pyrene
butylbenzylphthalate
chrysene
benzo(a)anthracene
bis(2-ethylhexyl)phthalate
di-n-octyl phthalate
benzo(b) fl uoran thene
benzo(k)fluoranthene
benzo(a)pyrene
indeno(l,2,3-cd)pyrene
dibenz(a,h)anthracene
benzo(g,h,i)perylene
3 ,3' -dichloro benzidine
2-nitroaniline
carbazole
CO~i:STOGP.-ROVERS il J.l.SSOCIATES
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I TABLE 3.5
INORGANIC ANAL YTES
I REMEDIAL DESIGN
JADCO-HUGHES SITE
I
aluminum
I antimony
arsenic
I barium
beryllium
I cadmium
calcium
I chromium
cobalt
copper
I iron
lead
I magnesium
manganese
I mercury
nickel
I potassium
selenium
silver
I sodium
thallium
I vanadium
zinc
I total cyanide
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I CONES"iOGA·ROVERS !h ASSOCIATES
-------------------
Task
Soil Sampling
Soil Gas Sampling
SVE System Sampling
Groundwater Quality
Sampling
Locations
New Monitoring Wells
Former Landfill
SVE Exhaust Gas
TABLE 3.6
SAMPLING SUMMARY
REMEDIAL DESIGN
JADCO-HUGHES SITE
Frequency
Installation (5' intervals)
Weekly during SVE pilot study
Weekly during SVE pilot study
Existing and New Wells One Round
Parameters
TCL VCX::s and TCL BNAs
TCL VCX::s and TCL BNAs
TCL VCX::s and TCL BNAs
TCL VCX::s, TCL BNAs and
Total Metals
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3.7.2 Sample Analysis
All samples collected for chemical analysis will be
analyzed using approved analytical methods as outlined in the QAPP.
Practical Quantification Limits (PQLs) for water and soil/sediment are also
presented in the QAPP. PQLs are highly matrix dependent, thus, the PQLs are
provided for guidance and may not always be achievable.
3.7.3 Data Quality Assessment
3.7.3.1 Laboratory Data Assessment
The laboratory quality assurance officer will review data
and identify results where additional work is required. This additional work
may take the form of re-analysis or resampling and analysis.
Internal quality control tests will be conducted by the
laboratory in accordance with their standard operating procedures and the
individual method requirements.
3.7.3.2 CRA Data Assessment
This step is carried out by the CRA Quality Assurance
Officer-Analytical Activities to evaluate the quality and utility of the data, as a
31
COi\;:CSTOC'P.·ROVERS t ASSOC;ATES
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level of quality assurance beyond that provided by the laboratory. The
analytical data will be evaluated based on criteria outlined in the QAPP.
The quality and acceptability or unacceptability of the data
will be determined following the reporting of the laboratory analysis. The
data will be examined for the acceptability of trip blanks, rinsate samples, field
duplicate samples, percent recoveries of MS/MSD analyses, surrogate
compounds and control samples. In the event that data are deemed
unacceptable, a decision will be made by CRA regarding the appropriate
corrective action. The corrective action may include resampling, reanalysis or
data qualification.
32
CON:CS'iOC'-1·ROVERS ll /\SSOCit'.TES
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4.0 EQUIPMENT CLEANING PROTOCOLS
Prior to mobilization, the drilling rig and all associated
excavation equipment will be thoroughly cleaned to remove oil, grease, mud
and other foreign matter. In addition, before initiating drilling or excavating
at each location, the augers, cutting bits, samplers, drill steel and associated
equipment will be thoroughly cleaned, at the Decontamination Area (see
Health and Safety Plan), to prevent potential cross-contamination from the
previous drilling location. The equipment will be inspected by the CRA's
on-Site personnel after cleaning and prior to initiation of drilling. Cleaning
will be accomplished by flushing and wiping the components to remove all
visible sediments followed by a thorough high-pressure steam wash and
rinsing. Special attention will be given to the threaded sections of the drill
rods and split spoon samplers.
All equipment used for the collection of samples for
chemical analysis including bailers, pumps and trowels or split-spoons will be
cleaned between each sampling location/interval according to the following
protocols;
1) wash with detergent (Alconox);
2) rinse with deionized water;
3) rinse twice with isopropanol;
4) rinse with deionized water; and
5) allow to air dry.
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The above rinse sequence does not include a hexane rinse.
This rinse has been deleted due to concerns related to worker exposure to
hexane during decontamination operations.
The bottom three feet of the water level measuring
equipment will be cleaned prior to use in each well with an isopropanol and
deionized water rinse.
Equipment will be protected from all forms of chemical
contact between final rinse and initial use.
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5.0 WASTE MATERIAL HANDLING
All sampling generated wastes, soil cuttings,
development/purge water, disposed personal protection equipment and
decontamination fluids will be collected and contained in separate
DOT-approved 55-gallon drums. The drums will be temporarily stored on
the concrete pad in the Former Operations Area with other drums or similar
material generated during the RI. In addition, soil excavated during the
installation of the SVE pilot system will be stockpiled on 6-mil polyethylene
sheeting and covered with polyethylene sheeting. The liner shall be secured
over the stockpile so as to prevent infiltration of water. Once the SVE pilot
system is installed, the excavated soils will be backfilled into the former
landfill and treated by the SVE system. Excess soils will be contained in
55-gallons drums, if appropriate, until the final soil remediation system is
installed at the Site.
Final disposition of the drummed soils, purge waters and
wastes will be addressed during the final remediation.
35
COil!c:STOG'-\-ROVERS & ASSOCIATES
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6.0 ON-SITE HEAL TH AND SAFETY PLAN
The sampling plan described in Section 3.0 involves the
collection of soil, gas and groundwater samples at the Jadco-Hughes Site in
Gaston County, North Carolina. During the program personnel may come in
contact with materials that contain VOCs and BNAs.
During the program, provisions for health and safety will
be implemented which are designed to ensure:
1) personnel working on Site are not adversely exposed to Site
contaminants;
2) the health and safety of the general public and the environment is not
compromised by off-Site migration of contaminated materials; and
3) compliance with applicable governmental and non-governmental
(American Conference of Governmental Industrial Hygienists)
regulations and guidelines.
The proposed environmental Health and Safety Plan
under which this work will be completed is presented in the document
entitled "Health and Safety Plan, Remedial Design Work Plan, Submittal A,
Jadco-Hughes Site, Gaston County, North Carolina".
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2.
3.
4.
5.
6.
7.
"Remedial Investigation Report, Jadco-Hughes Site, Gaston County,
North Carolina", CRA, July 1990.
"Feasibility Study Report, Jadco-Hughes Site, Gaston County,
North Carolina", CRA, July 1990.
"Environmental Compliance Branch Standard Operating Procedures
and Quality Assurance Manual", USEPA Region IV, February 1, 1991.
"Laboratory Operating and Quality Control Manual", USEP A
Region IV, September 1990.
"Data Quality Objectives for Remedial Response Activities",
USEPA/540/G-87 /003, March 1987.
"Test Methods for Evaluating Solid Waste Physical/Chemical
Methods", USEPA SW-846, Third Edition, Revision I, December 1987.
"Supplement of EPA/600/4-84/041: Compendum of Methods for the
Determination of Toxic Organic Compounds in Ambient Air",
USEPA/600/487 /006, September 1986.
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APPENDIX A
ROCK QUALITY DESIGNATION PROCEDURE
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ROCK QUALITY DESIGNATION (ROD)
In order to provide a simple and direct means of
indicating rock-mass properties, the Rock Quality Designation (RQD) will be
used. The RQD is based on a modified core recovery procedure which, in
turn, is based indirectly on the number of fractures and the amount of
softening or alternation in the rock mass as observed in the rock cores from
the borehole. Core recovery is the ratio of the length of core recovered to the
length drilled (i.e. no recovery = 0 and full recovery = 100). Instead of
counting the fractures, an indirect measure is obtained by summing the total
length of core recovered by counting only those pieces of hard and sound core
which are 10 centimeters (cm) (four inches) or greater in length and dividing
that sum by the total length of that run.
RQD should not be applied to core less than 5.4 cm
(two inches) in diameter as a false RQD may be obtained because smaller cores
can be frequently broken during the coring operation.
Care must be taken when removing the core from the
core barrel. If a core is broken by handling or during drilling, the fresh broken
pieces are fitted together and counted as one piece.
Some judgement is necessary in the case of thinly bedded
sedimentary rocks and foliated metamorphic rocks. The method is not so
exact in these cases as it is for igneous rock, thick bedded limestone,
sandstones, etc. However, this procedure has been applied successfully even
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for shales, although it is necessary to log the core immediately upon
removing them from the core barrel before air-slaking and cracking can occur.
This procedure obviously penalizes the rock where
recovery is poor. This is appropriate because poor recovery usually reflects
poor quality rock. However, poor drilling techniques and equipment can also
cause poor recovery. It is for this reason, that proper equipment and
procedure along with competent supervision of the drilling procedure are
imperative.
As simple as the procedure appears, it has been found that
as an indicator of general quality of rock for engineering purposes, the
numerical value of the RQD is more sensitive and consistent than gross
percentage core recovery.
A simple example of using RQD is illustrated on the
following page.
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Modified Core Recovery as an Index of Rock Quality
Core Modified Core
Recovery Recovery
(cm) (cm)
25 25
12 12
5 0
8 0
8 0
8 0
10 10
7 0
13 13
15 15
8 0
12 12
10 10
20 20
15 15
176 cm 132 cm
185 cm = length of run
Core Recover = 176/185 = 95%
Rock Quality
Designation
(ROD)
0-25
25-50
50 -75
75 -90
90 -100
Description of
Rock Quality
very poor
poor
fair
good
excellent
RQD = 132 = 71
therefore, RQD is fair
In this case, the core barrel was advanced 185 cm with a total
recovery of 176 cm. However, due to fractures, soft zones, etc., the modified
recovery was 132 cm. This translates to RQD of 71, which can be used as a modifier
in the geologic description of the rock, which in this case would be "Fair".
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APPENDIX B
QUALITY ASSURANCE PROJECT PLAN
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TABLE OF CONTENTS
Page
B.1.0 INTRODUCTION .................................................................................................. B-1
B.2.0 QUALITY ASSURANCE
OBJECTIVES FOR MEASUREMENT DATA ................................................... B-3
B.2.1 LEVEL OF QA EFFORT ............................................................................. B-4
B.2.2 ACCURACY, SENSITIVITY AND PRECISION OF ANALYSIS ..... B-6
B.2.3 COMPLETENESS, REPRESENTATIVENESS
AND COMPARABILITY .......................................................................... B-6
B.2.4 FIELD MEASUREMENTS ........................................................................ B-7
B.2.5 GEOTECHNICAL TESTING QA ............................................................. B-8
B.3.0 SAMPLING PROCEDURES ................................................................................. B-10
B.4.0 SAMPLE CUSTODY AND DOCUMENT CONTROL .................................... B-11
B.4.1 FIELD CUSTODY PROCEDURES ........................................................... B-11
B.4.2 SAMPLE LABELS ....................................................................................... B-11
B.4.3 CHAIN-OF-CUSTODY .............................................................................. B-11
B.4.4 SAMPLE DOCUMENTATION IN THE LABORATORY .................. B-12
B.4.5 STORAGE OF SAMPLES .......................................................................... B-13
B.4.6 SAMPLE DOCUMENTATION -CRA ................................................... B-14
B.5.0 CALIBRATION PROCEDURES AND FREQUENCY ..................................... B-15
B.5.1 LABORATORY INSTRUMENT PERFORMANCE ............................ B-15
B.5.1.1 Organic Analyses ..................................................................................... B-15
B.5.2 LABORATORY CALIBRATION ............................................................ B-16
B.5.2.1 Calibration Check .................................................................................... B-16
B.5.3 FIELD INSTRUMENT CALIBRATION ................................................ B-16
B.5.3.2 pH Meter ................................................................................................... B-17
B.5.3.2 Cond ucti vi ty Meter ................................................................................ B-18
B.5.3.3 HNU Meter .............................................................................................. B-18
B.6.0 ANALYTICAL PROCEDURES ............................................................................ B-20
B.6.1 OVERVIEW ................................................................................................ B-20
B.6.2 IDENTIFICATION ..................................................................................... B-21
B.6.3 QUANTIFICATION .................................................................................. B-22
B.6.4 DETECTION LIMIT AND QUANTITATION LIMIT ......................... B-22
B.7.0 DATA REDUCTION, VALIDATION I ASSESSMENT AND REPORTING .................................................................... B-23
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TABLE OF CONTENTS
B.8.0 INTERNAL QUALITY CONTROL
CHECKS AND FREQUENCY .............................................................................. B-25
B.8.1 FIELD QC ...................................................................................................... B-25
B.8.2 LABORATORY QC .................................................................................... B-25
B.8.2.1 Method Blank Samples ......................................................................... B-25
B.8.2.2 Matrix Spike/Matrix Spike Duplicates (MS/MSD) Analyses ........ B-26
B.8.2.3 Surrogate Compounds ........................................................................... B-26
B.8.2.4 Control Samples ...................................................................................... B-27
B.9.0 PERFORMANCE AND SYSTEM AUDITS AND FREQUENCY ................. B-28
B.10.0 PREVENTIVE MAINTENANCE .................................................................... B-30
B.11.0 SPECIFIC ROUTINE PROCEDURES USED TO ASSESS
DATA PRECISION, ACCURACY AND COMPLETENESS .......................... B-32
B.11.1 QA MEASUREMENT QUALITY INDICATORS ............................. B-32
B.11.1.1 Precision ................................................................................................. B-32
B.11.1.2 Accuracy ................................................................................................. B-32
B.11.1.3 Outliers ................................................................................................... B-32
B.12.0 CORRECTIVE ACTION ..................................................................................... B-33
B.13.0 QUALITY ASSURANCE REPORT TO MANAGEMENT ......................... B-34
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I LIST OF FIGURES
Following
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FIGURE B.4.1 TYPICAL SAMPLE LABEL B-11
I FIGURE B.4.2 TYPICAL CHAIN OF CUSTODY FORM B-11
I FIGURE B.7.1 ANALYTICAL DATA FLOW B-23
I LIST OF TABLES
I Following
Page
I TABLE B.2.1 SUMMARY OF SAMPLING AND ANALYSIS
I PROGRAM B-6
TABLE B.2.2 TARGETED QUANTITATION LIMITS
I (ORGANIC ANALYSES/WATER AND SOIL) B-6
TABLE B.2.3 TARGETED QUANTITATION LIMITS
I (INORGANIC ANALYSES/WATER AND SOIL) B-6
TABLE B.2.4 TARGETED QUANTITATION LIMITS
I (VOC ANALYSES/ AIR) B-6
TABLE B.8.1 SURROGATE COMPOUND RECOVERY LIMITS B-27
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I LIST OF ATTACHMENTS
I ATTACHMENT B-1 LA BORA TORY CUSTODY PROCEDURES
i I ATTACHMENT B-2 LABORATORY STANDARD OPERATING
PROCEDURES
I ATTACHMENT B-3 DATA REDUCTION, VALIDATION AND
REPORTING
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B.1.0 INTRODUCTION
Procedures presented within this document shall be used
for sample collection and laboratory analyses in support of the RD/RA. This
QAPP is consistent with "Environmental Compliance Branch Standard
Operating Procedures and Quality Assurance Manual", USEPA Region IV,
February 1, 1991 and "Laboratory Operating and Quality Control Manual",
USEPA Region IV, September 1990.
The Steering Committee has contracted analytical services
to ENSECO Laboratories, as discussed in the RD Work Plan. ENSECO's key
project personnel are listed below:
Project Manager -Pat Mcisaac (ENSECO)
-Ensures all laboratory resources are available on an as-required basis
-Overviews final analytical report
-Oversees all laboratory's activities
Operations Managers -Steven D. Harris (Air Toxics)
and Gary Tort (Rocky Mountain)
-Coordinate laboratory analyses
-Supervises in-house chain-of-custody
-Schedule sample analyses
-Oversees data review
-Prepares analytical reports
B-1
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-Approves final analytical reports prior to submission to CRA.
Quality Assurance Officers
-Overviews laboratory quality assurance
-Overviews QA/QC documentation
-Conducts detailed data review
-Decides laboratory corrective actions, if required
-Technical representation of laboratory QA procedures
Sample Custodians
-Receives and inspects the incoming sample containers
-Records the condition of the incoming sample containers
-Signs appropriate documents
-Verifies chain-of-custody and its correctness
-Notifies laboratory manager and laboratory supervisor of sample receipt
and inspection
Assigns a unique identification number and customer number and enters
each into the sample receiving log
Initiates sample transfers to appropriate lab sections with the help of the
laboratory manager
-Controls and monitors access/storage of samples and extracts
B-2
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OBJECTIVES FOR MEASUREMENT DATA
The overall QA objective is to develop and implement
procedures for field sampling, chain-of-custody, laboratory analyses and
reporting which provide accurate and precise data. Specific procedures to be
used for sampling, chain-of-custody, calibration, laboratory analysis,
reporting, quality control, audits, preventive maintenance and corrective
actions are presented in other sections of this QAPP.
Data quality objectives (DQO) have been established in
accordance with the USEPA guidance document entitled "Data Quality
Objectives for Remedial Response Activities", EPA/540/G-87/003, March
1987, dated March 25, 1986, to ensure that the database developed during the
Site investigation meets the objectives and quality necessary for its intended
use, namely, evaluation of the RD/RA system.
DQOs can be classified for measurement data by defining
the level of analytical support assigned to each type of measurement data. In
general, all groundwater, surface water, soil and sediment analyses will
require level III analytical support.
The level III support for the analyses will require that all
organics and inorganics are analyzed using SW-846, third edition, revision I,
December 1987 (SW-846) methods. Data deliverables will consist of a full data
package deliverables as described in Section B.7.0.
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Field screening activities such as determining of pH,
specific conductance, temperature and VOC concentration (HNu) will require
level I analytical support.
The use of the analytical support levels defined above will
ensure that the overall objectives for the RD/RA will be completed.
B.2.1 LEVEL OF OA EFFORT
To assess the quality of data resulting from the field
sampling program, field duplicate samples, rinsate samples (bailer rinse, etc.)
trip blank samples, and matrix spike/matrix spike duplicate (MS/MSD)
samples will be taken (where appropriate) and submitted to the analytical
laboratory.
For all field samples collected, field duplicate samples will
be collected at a frequency of 1 per 10 or at least one per day of sampling
activity. One MS/MSD sample will be analyzed per 20 investigative samples
per matrix, excluding air. One matrix spike and one duplicate will be
performed per 20 investigative samples, for air samples.
Rinsate blank samples will be submitted at a frequency of
1 per 10 well purgings/sampling equipment cleanings or at least once per day
of well purging/sampling equipment cleanings. Rinsate blanks will be
collected by routing deionized, distilled water through decontaminated
sampling equipment.
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Trip blank samples for VOC analyses (prepared by the
laboratory and consisting of organic-free water poured into the sample vials)
will be shipped with each shipment container of VOC sample vials by the
laboratory. Trip blanks samples will be handled in a manner consistent with
actual field sample handling and will be shipped back to the laboratory each
day with the daily field samples. The trip blanks samples will provide a
measure of potential cross contamination of samples during shipment and
handling. Trip blanks will not be opened in the field.
Blank samples will be analyzed to check procedural
contamination and/or ambient conditions and/or sample container
contamination that may be responsible for sample contamination.
If blank samples are found to contain any of the target
analytes, the following procedure will be followed. First, contamination will
be verified by examining the associated investigative samples and method
blanks. If the contamination can be traced to an isolated source, e.g. a highly
contaminated sample, the data remain unqualified. Otherwise, the data will
be examined to determine the extent of contamination and all associated data
will be qualified according to the data validation guidelines given in
Section B.7.0.
Field duplicate samples will be analyzed to check for
sampling and matrix heterogeneity. Field duplicate samples are to be used as
a measure of precision throughout the sampling event. Comparison of field
duplicate samples will be based upon the target analytes, both non-detected
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and detected, and the relative percent differences (RPD) of each analyte's
concentrations. The parameters which do not meet the criteria may only be
used as qualitative measurements. Professional judgement shall determine
the RPD limits on a sample-to-sample basis.
The sampling and analysis program is summarized in
Table B.2.1, which lists the specific parameters to be measured, the number
and frequency of sampling and the level of QA effort required for each matrix.
B.2.2 ACCURACY, SENSITIVITY AND PRECISION OF ANALYSIS
The fundamental QA objective with respect to the
accuracy, sensitivity, and precision of analytical data is to achieve the QC
acceptance criteria of each analytical protocol. The sensitivities required for
these organic analyses will be at least the targeted quantitation limits listed in
Tables B.2.2 through B.2.4. These tables present targeted quantitation limits
for all target analytes. Lower method quantitation limits, if achieved by the
laboratory, will be substituted for the targeted quantitation limits in the final
report.
B.2.3 COMPLETENESS, REPRESENTATIVENESS
AND COMP ARABILITY
It is expected that all analyses conducted in accordance
with USEPA methods will provide data meeting QC acceptance criteria for 80
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Sample
Matrix
Soil/Sediment/
Waste
Water
Air (6)
Notes:
TABLE B.2.1
SUMMARY OF SAMPLING AND ANALYSIS PROGRAM (1)
JADCO-HUGHES REMEDIAL DESIGN
Quali!:Jl Assurance Sam(!_les !21
Field Laboratory Field Trip
Parameters Parameters Duplicates Rinsate Blanks (3)
TCLVOC 1 1 0
TCLBNA 1 1 0
TAL Metals 1 1 0
Cyanide 1 1 0
pH, TCLVOC 1 1 1
Conductivity TCLBNA 1 1 0
Temperature TAL Metals 1 1 0
Cyanide 1 1 0
Atmospheric TCLVOC 1
Pressure,
Temperature
MS/
MSD (4) (5)
1
1
1
1
1
1
1
1
1
(1) Table 3.6 of the FSAP lists the Sampling Summary. Table B2.1 lists the necessary QA/QC samples per
sampling event.
(2) Entries reflect number of QA samples per ten samples or number of QA samples per day of sampling
events.
(3) Trip blank samples are used when aqueous VOC samples are collected.
(4) Matrix spike/matrix spike duplicate sample.
(5) Entries reflect number of QA samples per 20 samples.
(6) MS/MSD Samples are replaced with duplicate and spiked analyses. Spike compounds will be added
using a cryrogenic trap.
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TABLE B.2.2
TARGETED QUANTITATION LIMITS 1,
ANALYTICAL METHODS OF ANALYSIS AND
MATRIX SPIKFJMATRIX SPIKE DUPUCATE ANALYSES
RECOVERYCONIROLLIMITS
FOR WATER AND SOIL ORGANIC ANALYSES
JADCO-HUGHES REMEDIAL DESIGN
Page 1 of 4
MSIMSD3 Recovery
Iarg&.t&.d. Qu.autitatiau Limia Control Limits4
Compound Cas No. Water Soi12
(µg/L) (µglkg) Water Soil
VOLATI..E ORGANIC COMPOUNDS
Analytical Method5: 8260
Chloromethane 74-87-3 10 10
Bromomethane 74-83-9 10 10
Vinyl Chloride 75-01-4 2 10
Chloroethane 75-00-3 10 10
Methylene Chloride 75-09-2 5 5
Acetone 67-64-1 10 10
Carbon Disulfide 75-15-0 5 5
1, 1-dichloroethene 75-35-4 5 5 61-145(14) 59-172(22)
l, 1-dichloroethane 75-34-3 5 5
1,2-dichloroethene (Total) 40-59-0 5 5
Chloroform 67-66-3 5 5
1,2-dichloroethane 107-06-2 5 5
Butanone 78-93-3 10 10
1, 1, 1-Trichloroethane 71-55-6 5 5
Carbon Tetrachloride 56-23-5 5 5
Bromodichloromethane 75-27-4 5 5
1,2-dichloropropane 78-87-5 5 5
cis-1,3-dichloropropene 10061-01-5 5 5
Trichloroethene 79-01-6 5 5 71-120(14) 62-137(24)
Dibromochloromethane 124-48-1 5 5
1, 1,2-Trichloroethane 79-00-5 5 5
Benzene 71-43-2 5 5 76-127(11) 66-142(21)
lrans-1,3-dichloropropene 10061-02-6 5 5
Bromoform 75-25-2 5 5
4-methyl-2-pentanone 108-10-1 10 10
2-hexanone 591-78-6 10 10
Tetrachloroethene 127-18-4 5 5
Toluene 108-88-3 5 5 76-125(13) 59-139(21)
1, 1,2,2-tetrachloroethane 78-34-5 5 5
Chlorobenzene 108-90-7 5 5 75-130(13) 60-133(21)
Ethylbenzene 100-41-4 5 5
Styrene 100-42-5 5 5
Xylenes (Total) 1330-20-7 5 5
I Page 2 of 4
TABLE B.2.2
I TARGETED QUANTITATION LIMITS1,
ANAL YfICAL METHODS OF ANALYSIS AND
MA TRIX SPIKE/MA TRIX SPIKE DUPLICATE ANALYSES
I RECOVERY CONTROL LIMITS
FOR WATER AND SOIL ORGANIC ANALYSES
JADCO-HUGHES REMEDIAL DESIGN
m MSIMSD3 Recovery
u Iargt.tJ:.d Quautitatiau L,imib. Control Limits4
Compound Cas No. Water Soil2
(µg!L) (µglkg) Water Soil
u BASE NEUTRAL AND ACID EXTRACTABLE COMPOUNDS
Analytical Method: 8270
I Extraction Method: 3520 (Water)
3550 (Soil)
0 Phenol 108-95-2 10 330 12-110(42) 26-90(35)
Bis(2-chloroethyl )ether 111-44-4 10 330
2-chlorophenol 95-57-8 10 330 27-123(40) 25-102(50)
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1,3-dichlorobenzene 541-73-1 10 330
1,4-dichlorobenzene 106-46-7 10 330 36-97(28) 28-104(27)
1,2-dichlorobenzene 95-50-1 10 330
2-methylphenol 95-48-7 10 330
m Bis(2-chloroisopropyl)ether 108-60-1 10 330
4-methylphenol 106-44-5 10 330
N-Nitroso-di-n-dipropylamine 621-64-7 10 330 41-116(38) 41-126(38)
E Hexachloroethane 67-72-1 10 330
Nitrobenzene 98-95-3 10 330
Isophorone 78-59-1 10 330
2-nitrophenol 88-75-5 10 330 I 2,4-dimethylphenol 105-67-9 10 330
Bis(2-chloroethoxy)methane 111-91-1 10 330
2,4-dichlorophenol 120-83-2 10 330
I 1,2,4-trichlorobenzene 120-82-1 10 330 39-98(28) 38-107(23)
Naphthalene 92-20-3 10 330
4-chloroaniline 106-47-8 10 330
I Hexachlorobutadiene 87-68-3 10 330
4-chloro-3-methylphenol
(para-chloro-meta-creso I) 59-50-7 10 330 23-97(42) 26-103(33)
2-methylnaphthalene 91-57-6 10 330 I Hexachlorocyclopentadiene 77-47-4 10 330
2,4,6-trichlorophenol 88-06-2 10 330
2,4,5-trichlorophenol 95-95-4 50 1600
I 2-chloronaphthalene 91-58-7 10 330
2-nitroaniline 88-74-4 50 1600
Dimethylphthalate 131-11-3 10 330
I Acenaphthylene 208-96-8 10 330
2,6-dinitrotoluene 606-20-2 10 330
3-nitroaniline 99-09-2 50 1600
Acenaphthene 83-32-9 10 330 46-118(31) 31-137(19)
I 2,4-dinitrophenol 51-28-5 50 1600 24-96(38) 28-89(47)
4-nitrophenol 100-02-7 50 1600 10-80(50) 11-114(50)
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TABLEB.2.2
TARGETED QUAN1TIATIONLIMITS1,
ANALYTICAL METHODS OF ANALYSIS AND
MATRIX SPIKF/MATRIX SPIKE DUPLICATE ANALYSES
RECOVERY CONTROL LIMITS
FOR WATER AND SOIL ORGANICANALYSES
JADCO-HUGHES REMEDIAL DESIGN
Page 3 of 4
Tar.g.etcd Ouantitation Limits
MSIMSD3 Recovery
Control Limits4
Compound Cas No. Water Soil2
(µg/L) (µglkg) Water Soil
BASE NEUTRAL AND ACID EXTRACTABLE COMPOUNDS
Dibenzofuran 132-64-9 10 330
2,4-dinitrotoluene 121-14--2 10 330 24-96(38) 28-89(47)
Dielhylphlhala le 84-66-2 10 330
4-chlorophenylphenylelher 7005-72-3 10 330
Auorene 86-73-7 10 330
4-nitroaniline 100-01-6 50 1600
4,6-d ini lro-2-methy Ip henol 534-52-1 50 1600
N-Nitrosodiphenylamine 86-30-6 10 330
4-bromophenylphenylelher 101-55-3 10 330
Hexachlorobenzene 118-74-1 10 330
Penlachlorophenol 87-86-5 50 1600 9-103(50) 17-109(47)
Phenanlhrene 85-01-8 10 330
Anthracene 120-12-7 10 330
Di-n-butylphthala le 84-74-2 10 330
Auoranthene 206-44-0 10 330
Carbazole 86-74-18 10 330
Pyrene 129-00-0 10 330 26-127(31) 35-142(36)
Butylbenzylphthalate 85-68-7 10 330
3,3'-dichlorobenzidine 91-94-1 20 660
Benzo(a)anthracene 56-55-3 10 330
Chrysene 218-01-9 10 330
Bis(2-eth ylhexyl )phthala te 117-81-7 10 330
Di-n-octylphthala te 117-84-0 10 330
Benzo(b)fluoranthene 205-99-2 10 330
Benzo(k)fluoranthene 207-08-9 10 330
Benzo(a)pyrene 50-32-8 10 330
lndeno(l,2,3-cd)pyrene 193-39-5 10 330
Dibenzo(a,h)anthracene 53-70-3 10 330
Benzo(g,h,i)perylene 191-24-2 10 330
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Notes:
TABLE B.2.2
TARGETED QUANTITATIONLIMITS1,
ANALYTICAL METHODS OF ANALYSIS AND
MA TRIX SPIKF/MA TRIX SPIKE DUPLICATE ANALYSES
RECOVERY CONTROL LIMITS
FOR WATER AND SOIL ORGANIC ANALYSES
JADCO-HUGHES REMEDIAL DESIGN
Page4 of 4
1. Quantitation limits are provided for guidance purposes only as they may not always be technically
achievable due to such factors as elevated analyte concentrations, which would require sample dilution and
matrix interferences. In these cases, the laboratory quantitation limits will be submitted for the
quantitation detection limits in accordance with the method(s) protocols.
2. Soil targeted quantitation limits provided are based on wet weight results. Actual quantitation limits shall
be reported on a dry weight basis and, as such, quantitation limit will be higher.
3. MS/MSD -Matrix Spike/Matrix Spike Duplicate.
4. Values in parenthesis indicate maximum acceptable relative percent differences (RPO) between duplicate
spike analyses.
5. "Test Methods for Evaluating Solid Waste Physical/Chemical Methods", USEPA SW-846, Third Edition,
revision I, December 1987.
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Compound
TALMETALS
Analytical Method 5,
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
TABLEB.2.3
TARGETED QUANTITATIONLIMITS1,
ANALYTICAL METHOD OF ANALYSIS AND
MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSES
RECOVERY CONTROL LIMITS
FOR WATER AND SOIL INORGANIC ANALYSES
JADCO-HUGHES REMEDIAL DESIGN
Page 1 of2
MSIMSD3 Recovery
Iar:gf:.t:e.d. Quaatitatian Limit:z ContTol Limits4
Water Soil2
Cas No. (µg/l) (mglkg) Water Soil
6000/7000 Series
200 40 75-125 (20) 75-125 (35)
60 12 75-125 (20) 75-125 (35)
10 2 75-125 (20) 75-125 (35)
200 40 75-125 (20) 75-125 (35)
5 1 75-125 (20) 75-125 (35)
5 1 75-125 (20) 75-125 (35)
5000 1000 75-125 (20) 75-125 (35)
10 2 75-125 (20) 75-125 (35)
so 10 75-125 (20) 75-125 (35)
25 5 75-125 (20) 75-125 (35)
100 20 75-125 (20) 75-125 (35)
5 1 75-125 (20) 75-125 (35)
5000 1000 75-125 (20) 75-125 (35)
15 3 75-125 (20) 75-125 (35)
0.2 0.04 75-125 (20) 75-125 (35)
40 8 75-125 (20) 75-125 (35)
5000 1000 75-125 (20) 75-125 (35)
5 1 75-125 (20) 75-125 (35)
10 2 75-125 (20) 75-125 (35)
5000 1000 75-125 (20) 75-125 (35)
10 2 75-125 (20) 75-125 (35)
so 10 75-125 (20) 75-125 (35)
10 2 75-125 (20) 75-125 (35)
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TABLE B.2.3
TARGETED QUANIITATION LIMITS1,
ANALYTICAL METHOD OF ANALYSIS AND
MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSES
RECOVERY CONTROL LIMITS
FOR WATER AND SOIL INORGANIC ANALYSES
JADCO-HUGHES REMEDIAL DESIGN
Targeted Ouantitation Limits
Water Soi('
Page 2 of 2
MSIMSD3 Recovery
Control Limits4
Compound Cas No. (µg/1) (mg/kg) Water Soil
CYANIDE
Analytical Method: 9010
Cyanide 10 2 75-125 (20) 75-125 (35)
1.
2.
3.
4.
5.
Quantitation limits are provided for guidance purposes only as they may not always be technically
achievable due to such factors as elevated analyte concentrations, which would require sample
dilution and matrix interferences. In these cases, the laboratory quantitation limits will be
submitted for the quantitation limits in accordance with the method(s) protocols.
Soil targeted quantitation limits provided are based on wet weight results. Actual quantitation
limits shall be reported on a dry weight basis and, as such, quantitation limit will be higher.
MS/MSD -Matrix Spike/Matrix Spike Duplicate. Spike and duplicate analyses may be used in
place of MS/MSD analyses.
Values in parenthesis indicate maximum acceptable relative percent differences (RPO) between
duplicatee analyses.
"Test Methods for Evaluating Solid Waste Physical/Chemical Methods", USEPA SW-846, Third
Edition, revision I, December 1987.
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Compound
TABLE B.2.4
TARGETED QUANTITATIONLIMITS1,
ANALYTICAL METHOD OF ANALYSIS AND
MA1RIX SPIKE DUPLICATE ANALYSES
RECOVERYCONTROLLIMITS
FOR AIR SAMPLES
JADCO-HUGHES REMEDIAL DESIGN
Cas No.
Targeted
Quantitation
Limits (ppb: vlv>
VOLATLE ORGANIC COMPOUNDS
Analytical Method3: TO-14
Chloromethane 74-87-3 2.5
Bro mo methane 74-83-9 3
Vinyl Chloride 75-01-4 2.5
Chloroethane 75-00-3 5
Methylene Chloride 75-09-2 4
Acetone 67-64-1 10
Carbon Disulfide 75-15-0 10
1, 1-dichloroethene 75-35-4 2
1, 1-dichloroethane 75-34-3 2.5
1,2-dichloroethene (Total) 40-59-0 6
Chloroform 67-66-3 2
1,2-dichloroethane 107-06-2 2
Butanone 78-93-3 3
1, 1, 1-trichloroethane 71-55-6 2
Carbon Tetrachloride 56-23-5 2
Bromodichloromethane 75-27-4 2
1,2-dichloropropane 78-87-5 8
cis-1,3-dichloropropene 10061-01-5 3
Trichloroethene 79-01-6 2.5
Dibromochloromethane 124-48-1 2
1, 1,2-trichloroethane 79-00-5 3
Page 1 of2
MS/Duplicate
Recovery
Control Liwits2
80-115 (20)
80-115 (20)
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Compound
TABLE B.2.4
TARGETED QUANTITATIONLIMITS1,
ANALYTICAL METHOD OF ANALYSIS AND
MATRIX SPIKE DUPLICATE ANALYSES
RECOVERY CONTROL LIMITS
FOR AIR SAMPLES
JADCO-HUGHES REMEDIAL DESIGN
Cas No.
Targeted
Quantitation
Limits (,zpb: vlv>
VOLATLE ORGANIC COMPOUNDS
3 Analytical Method : TO-14
Benzene
trans-1,3-dichloropropene
Bromofonn
4-methyl-2-pentanone
2-hexanone
Tetrachloroethene
Toluene
1, 1,2,2-tetrachloroethane
Chlorobenzene
Ethylbenzene
Styrene
Xylenes (Total)
71-43-2
10061-02-6
75-25-2
108-10-1
591-78-6
127-18-4
108-88-3
78-34-5
108-90-7
100-41-4
100-42-5
1330-20-7
3
3
2
3
5
3
3
4
2.5
2.5
7
5
Page 2 of 2
MS/Duplicate
Recovery
Control Liwits2
80-115 (20)
80-115 (20)
1. Quantitation limits are provided for guidance purposes only as they may not always be technically
achievable due to such factors as elevated analyte concentrations, which would require sample
dilution and matrix interferences. In these cases, the laboratory quantitation limits will be
submitted for the quantitation limits in accordance with the method(s) protocols.
2. Matrix spike analytes will be added via cryogenic trap. Values in parenthesis indicate maximum
acceptable relative percent differences (RPO) between lab control sample/lab control duplicate
sample analyses.
3. "Supplement to EPA/600/4-84/041: Compendum of Methods for the Determination of Toxic Organic
Compounds in Ambient Air", EPA/ 600/ 487 /006, September 1986.
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percent of all samples tested. Any reasons for variances will be documented.
Corrective actions that will be taken if the completeness goals are not met are
described in Section B.12.0 of this QAPP.
The sampling networks have been designed to provide
data representative of site conditions. During development of these
networks, consideration was given to past disposal practices, existing data
from past studies completed for the Site, remedial activities to date and
physical setting. The extent to which existing and planned analytical data will
be comparable depends on the similarity of sampling and analytical methods.
The procedures used to obtain the planned analytical data are documented in
this QAPP. However, it may be necessary to verify similar documentation for
previous analytical data to adequately establish comparability. Comparability
of laboratory analyses will be ensured by the use of consistent units.
Following completion of data collection (during the RD), the existing database
will be evaluated for representativeness.
B.2.4 FIELD MEASUREMENTS
Measurement data will be generated in many field
activities. These activities include, but are not limited to, the following:
i) Documenting time and weather conditions;
ii) Determining pH, specific conductivity and temperature of water
samples;
iii) Determining depths in a well;
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iv) Verifying well development and presampling purge volumes;
v) Observing drill cuttings, sample appearance and other conditions;
vi) Measuring groundwater elevations in wells;
vii) Measuring soil and sediment samples depths; and
viii) Completing single well response tests.
The general QA objective for such measurement data is to
obtain reproducible and comparable measurements to a degree of accuracy
consistent with the use of standardized procedures.
B.2.5 GEOTECHNICAL TESTING QA
Laboratory QA for the geotechnical testing will require
that all equipment used to perform the analyses be calibrated no more than
six months prior to actual testing, that all solutions be no more than one
month old and that calculations be checked by a person other than the person
performing the actual testing. The geotechnical laboratory will also be
required to test one laboratory duplicate for each type of analyses, that is, to
repeat some tests using the same material used for the initial testing of that
sample. Geotechnical tests may include, but are not limited to, the following:
i) particle size analysis (as presented in ASTM D422-63);
ii) hydraulic conductivity (as presented in SW-846 Method 9100
U.S. Army Corps of Engineers, Appendix VII);
iii) soil sample description (ASTM D2216-80); and
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iv) standard penetration test and split-barrel sampling of soils (ASTM
D1586-84).
The geotechnical data will be considered accurate if the
QA criteria with respect to equipment, solutions and calculations are met, and
if adherence to appropriate methods can be documented. The precision of
these data will be assessed using the duplicate results, but no quantitative
control criteria have been established. The geotechnical data will be made
adequately sensitive through adherence to appropriate methods.
B-9
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B.3.0 SAMPLING PROCEDURES
The procedures and protocols for collecting samples and
for performing all related field activities are described in detail in the Field
Sampling and Analysis Plan (FSAP), Submittal B to the RD Work Plan.
B-10
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B.4.0 SAMPLE CUSTODY AND DOCUMENT CONTROL
This section details the procedures and protocols which
must be followed for the transport of samples from the Site.
B.4.1 FIELD CUSTODY PROCEDURES
Once samples are collected and placed in a cooler, limited
access will be enforced by keeping coolers in sight or restricting access to the
coolers (i.e. locking coolers in field office or vehicle).
B.4.2 SAMPLE LABELS
Sample labels will include sample number, place of
collection and date and time of collection. Corrections will require a single
line drawn through the incorrect entry above. Figure B.4.1 shows a typical
sample jar label. Samples will be placed in the shipping cooler immediately
after collection.
B.4.3 CHAIN-OF-CUSTODY
Each cooler being shipped to ENSECO will contain a
chain-of-custody form. Figure B.4.2 shows a typical chain-of-custody form
consisting of four copies which are distributed to the shipper, the receiving
B-11
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I CRA
3669-18/09/91-4-0
CAA Consulting Engineers
CONESTOGA-ROVERS & ASSOCIATES LIMITED
JOB NAME: __________ _
JOB NO: ____ __:DATE: ____ _
LOCATION: -----------RE MAR KS: ___________ _
NOTES:
1) SAMPLE LABELS 'MLL BE FIRMLY AmXED
TO SAMPLE CONTAINERS
2) ALL SAMPLE LABELS 'MLL BE COMPLETED
USING WATER INSOLUBLE INK
figure B.4.1
TYPICAL SAMPLE LABEL
JADCO-HUGHES SITE
Gaston County, NC
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CRA SHIPPED TO (Laboratory name):
CONESTOGA-ROVERS & ASSOCIATES
CHAIN OF CUSTODY PROJECT l'I': PROJECT NAME:
RECORD
SAMPLER'S SIGNATURE "' 15 SAMPLE (SIGN) lYPE 1!5~ REMARKS
SEQ. SAMPLE l'I'. DATE TIME SAMPLE LOCATION "~ 1-P.
., I\
./ ./ -'\ \., .,, _/
-'\ . ., ">
'\. '\ \ ~ ./
TOTAL NUMBER <= r, ~A'ltlE'l!S /) ~
ANTICIPATED CHEMICAL HAZARDS: A\V) V
RELINQUISHED BY: -~~\v RECEIVED BY:
[I] (SGN) (i) (SGN) -
RELINQUISHED BY: \~ ~-• TIME RECEIVED BY:
'-._,_ I @ (SGNv > \ \ ./ (SGN)
RELINQUISHED BY: ( c.... -, \ ( DATE/TIME RECEIVED BY:
I © cs-., ) I ,.. (SIGN)
RELINQUISHED BY: <::::/ DATE/TIME RECEIVED BY:
[ii (SGN) I ® (SIGN)
RELINQUISHED BY: DATE/TIME RECEIVED BY:
ml (SGN) I ® (SIGN)
RELINQUISHED BY: DATE/TIME RECEIVED BY:
(fil (SGN) I (!) (SGN)
RELINQUISHED BY: DATE/TIME RECEIVED BY:
I] (SGN) I @ (SIGN)
METHOD OF SHIPMENT: SHIPPED BY: RECEIVED FOR LABORATORY BY: DATE/TIME
(SIGN) I
CONDITION OF SEAL UPON RECEIPT: COOLER OPENED BY: DATE/TIME
GENERAL CONDITION OF COOLER: (SIGN) I
-CRA OFFICE COPY 1'.HITE
YELLOW
PINK
GOLDENROD
-RECEIVING LABDRA TORY COPY figure 8.4.2
TYPICAL CHAIN OF CUSTODY FORM
JADCO-HUGHES SITE
Goston County, North Carolina
-CRA LABORATORY COPY
-SHIPPERS
3669-19 /06 /91-4-0
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laboratory, the CRA laboratory and the CRA office file. Each sample number
of each sample shipped will be recorded on the sheet. The shipper will
maintain his copy while the other three copies are enclosed in a waterproof
envelope within the cooler with the samples. The container will then be
sealed for shipment. The laboratory, upon receiving the samples, will
complete the three remaining copies. The laboratory will maintain one copy
for their records. One copy will be returned to CRA upon receipt of the
samples by the laboratory. One copy will be returned to CRA with the data
deliverables package.
Upon receipt of the container at the laboratory, the
container will be inspected by the designated sample custodian. The
condition of the container will be noted on the chain-of-custody record sheet
by the sample custodian. The sample custodian will document the date and
time of receipt of the container and sign the form.
If damage or discrepancies are noticed, it will be recorded
in the remarks column of the record sheet, dated and signed. Any damage or
discrepancies will be reported to the laboratory supervisor who will inform
the lab manager and QA officer. The lab QA officer will then notify the CRA
QA Officer -Analytical Activities.
B.4.4 SAMPLE DOCUMENTATION IN THE LABORATORY
The sample custodian will assign a unique number to
each incoming sample for use in the laboratory. The unique number and
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customer number will then be entered into the laboratory information
management system and in the project file. The laboratory date of receipt will
also be noted.
ENSECO will be responsible for maintaining analytical log
books and laboratory data, as well as sample (on hand) inventory for
submittal to CRA on an "as required" basis. Samples will be maintained by
the laboratory for a period of 30 days following CRA's receipt of the respective
sample data under the conditions prescribed by the appropriate USEP A
methods for additional analyses, if necessary. Raw laboratory data files will be
inventoried and maintained by ENSECO for a period of five years at which
time CRA will advise ENSECO regarding the need for additional storage.
Laboratory custody procedures are documented in detail
in Attachment B-1.
B.4.5 STORAGE OF SAMPLES
After the sample custodian has prepared the log book, the
chain-of-custody will be checked to ensure that all samples are stored in the
appropriate locations. All soil and water samples will be stored within an
access controlled location and will be maintained at 4°C, ±2°C until
completion of all analytical work, but in any event for at least 30 days. Air
samples will be stored at 25°C, ±2°C.
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B.4.6 SAMPLE DOCUMENTATION -CRA
Evidentiary files for the entire project will be inventoried
and maintained by CRA and will consist of the following:
-Project Plan
-Project Logbooks
-Field Data Records
-Sample Identification Documents
-Chain-of-Custody Records
-Analytical Data Packages
-Correspondence
-Report Notes, Calculations, etc.
-References, Literature
-Miscellaneous -photos, maps, drawings, etc.
Final Report
The evidentiary file materials will be the responsibility of
the evidentiary file custodian with respect to maintenance and document
removal. Steve Quigley will be the evidentiary file custodian.
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B.5.0 CALIBRATION PROCEDURES AND FREQUENCY
The procedures indicated below will be performed for all
samples delivered for analysis to ENSECO. Specific instructions relevant to a
particular type of analysis are given in the pertinent analytical procedures for
this project, and are referenced in Section B.6.0 and Tables B.2.2 and B.2.3.
All quality control data and records produced from
calibration will be retained by the laboratory and will be made available to
CRA on an "as required" basis.
The following specific analytical quality control
procedures are related to each analytical batch.
B.5.1 LABORATORY INSTRUMENT PERFORMANCE
Prior to initiating analyses, the laboratory must establish
that all instruments will meet required specifications.
B.5.1.1 Organic Analyses
The following requirements will be applied to those
samples analyzed by gas chromatography (GC) and gas chromatography /mass
spectrometry (GC/MS). The calibration of each of these instruments will be
verified at frequencies specified in ENSECO's Standard Operating Procedures
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(SOPs). Where appropriate, a new standard curve may be prepared as
specified in the SOPs.
B.5.2 LABO RA TORY CALIBRATION
Prior to analysis, instruments will be calibrated using
standard procedures for organics, metal and cyanide analyses. Calibration
procedures are detailed in ENSECO's SOPs, which are provided in
Attachment B-2.
B.5.2.1 Calibration Check
Method mandated compounds will be used to check
calibration of the instrument being used. A calibration check will be
conducted prior to any batch analysis. Calibration check procedures are
detailed in ENSECO's SOPs.
B.5.3 FIELD INSTRUMENT CALIBRATION
Calibrating field instruments will be done prior to
collecting each water sample if well purging data indicate a change
(>±10 percent) in pH and/or conductivity from the last location sampled.
Calibration will be conducted at least daily during groundwater sampling.
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The field equipment will be maintained, calibrated and operated in a manner
consistent with the manufacturer's guidelines and USEPA standard methods.
However, since the majority of field measurements will
be limited to pH, conductivity, temperature and depth (water level), the
following minimum procedures will be observed.
B.5.3.2 pH Meter
The pH meter will be calibrated with commercially
obtained pH 4, 7 and 10 buffer solutions. The pH calibration will be
temperature compensated and will be performed immediately before
initiating a sampling event. Calibration checks will be performed with every
sample collected. In the event that the result fails to be within 0.1 pH units,
the meter must be recalibrated and all samples after the last calibration must
be remeasured.
Calibration will be performed in accordance with the
following procedure:
1. Rinse the probe in deionized water;
2. Insert probe in a fresh pH 7 buffer solution;
3. Slide battery compartment cover back to the first stop, exposing the
adjustment potentiometers;
4. Adjust the "CAL" potentiometer such that the display reads 7.00;
5. Remove the probe; rinse in deionized water;
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6. Insert probe in a fresh pH 4 or pH 10 buffer solution;
7. Adjust the slope potentiometer until the correct pH is displayed; and
8. Remove probe; rinse in deionized water.
B.5.3.2 Conductivity Meter
The specific conductivity meter is factory calibrated, but
the calibration should be checked periodically and the probe thoroughly
rinsed between samples. Calibrating the specific conductivity meter will be
performed as follows:
1. Rinse probe in deionized water;
2. Wipe probe and allow to dry, the conductivity displayed should be zero
in air;
3. Adjust the zero potentiometer if necessary;
4. Immerse the probe in a solution of known conductivity;
5. Adjust the "SPAN" potentiometer such that the correct conductivity is
displayed; and
6. Rinse probes thoroughly with deionized water and allow to dry.
B.5.3.3 HNU Meter
Calibration checks will be performed in accordance with
the following procedures:
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Connect the analyzer to the regulator and cylinder with a short piece
(butt connection) of tubing. The calibration gas in the cylinder consists
of a mixture of isobutylene and zero air. Isobutylene is non-toxic and
safe to use in confined areas. There are no listed exposure levels at any
concentration.
It is important that the tubing be clean since contaminated tubing will
affect the calibration reading. Do not use the cylinder below about
30 psig, as a reading below that level can deviate up to ten percent from
the rated value.
Safely discard the disposable cylinder when empty. Do no refill this
cylinder.
Set SPAN and function switches at the same positions as listed in the
Application Data Sheet or Calibration Report. Open the valve on the
cylinder until a steady reading is obtained. If the reading is the same as
the recorded data, the analyzer calibration for the original species of
interest is still correct.
If the reading has changed, adjust the SP AN setting until the reading is
the same.
Shut off the cylinder as soon as the reading is established.
Record and maintain this new SPAN setting.
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B.6.0 ANALYTICAL PROCEDURES
This section presents the analytical methods which will be
employed by ENSECO to complete all required analyses.
B.6.1 OVERVIEW
All sediments, soil, surface water and groundwater
samples collected for chemical analyses will be analyzed using SW-846, third
edition, revision I methods, which are presented on Table B.2.2 and B.2.3. Air
samples will be analyzed using method TO-14.
In addition, a library search will be executed for non-TCL
components during the first round of sampling for the purpose of tentative
identification. Up to ten substances of greatest apparent concentration for
VOC and 20 substances of greatest apparent concentration for the
base-neutral/acid (BNA) (10 acid, 10 base-neutral) extractable analyses will be
tentatively identified. via a forward search of the National Institute of
Standards and Technology (NIST) Mass Spectra Library.
Computer library search routines will not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of
sample spectra with the nearest library searches, will the mass spectral
interpretation specialist assign a tentative identification.
B-20
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B.6.2 IDENTIFICATION
Identification of all targeted analytes will be accomplished
with an authentic standard of the analyte. When authentic standards are not
available (i.e. for non-target compounds) identification will be considered
tentative.
For gas chromatographic determinations of specific
analytes, the relative retention time of the unknown will be compared with
that of an authentic standard. Since a true identification using GC is not
possible, an analytical run for compound confirmation will be performed
according to the specifications in the methods. Peaks must elute within daily
retention time windows established for each indicator parameter. to be
declared a tentative or confirmed identification. Retention time windows are
determined via a standard 72-hour study defined in each method. Results of
the study are to be filed in the laboratory and available for inspection during a
QC audit.
For gas chromatographic/mass spectrometric
determinations of specific analytes, the spectrum of the analyte will conform
to a literature representation of the spectrum or to a spectrum of the
authentic standard obtained after satisfactory tuning of the mass spectrometer.
The appropriate analytical methods will be consulted for specific criteria for
matching the mass spectra, relative response factors, and relative retention
times to those of authentic standards.
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B.6.3 QUANTIFICATION
The procedures for quantification of analytes are discussed
in the appropriate specific laboratory SOPs.
B.6.4 DETECTION LIMIT AND OUANTITATION LIMIT
The methods used will have quantitation limits that are
consistent with the appropriate USEPA methods.
The targeted quantitation limits for analyses are presented
on Tables B.2.2 through B.2.4. Specific quantitation limits are highly matrix
dependent. The quantitation limits are provided for guidance and may not
always be technically achievable.
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B.7.0 DATA REDUCTION, VALIDATION
ASSESSMENT AND REPORTING
ENSECO will perform analytical data reduction and
validation in-house under the direction of the laboratory QA officer. The
laboratory QA officer will be responsible for assessing data quality and
advising CRA's QA Officer -Analytical Activities of any data which were
rated "preliminary" or "unacceptable" or other qualifications. Figure B.7.1
illustrates the analytical data flow through the laboratory. Data reduction,
validation and reporting by the laboratory will be conducted as detailed in
Attachment B-3.
CRA's QA Officer -Analytical Activities will evaluate data
reduction and reporting. These evaluations will consider the finished data
sheets, rinsate data, field duplicate data, and recovery data for surrogate and
matrix spikes. The material will be checked for legibility, completeness,
correctness, and the presence of requisite dates, initials and signatures. The
results of these checks will be assessed and reported to the project managers
noting any discrepancies and their effect upon data acceptability. All
information garnered from QA/QC checks will be discussed in the Final
Remedial Design Report.
Analytical data validation will be performed by the CRA
QA Officer -Analytical Activities. Validation of analytical and field data will
include checks for data consistency by looking for comparability of duplicate
analyses, potential sample contamination as indicated by results of blank
sample analyses, laboratory QA procedures, adherence to accuracy and
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Samples received by
sample custodian, logged
in, worksheets generated
for each parameter
group and transmitted
to lob supervisor
Sample preparation
Sample analyses
Data processed and
transcribed onto
worksheets by onalyst
N
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Worksheets transferred
to independent analyst
for review
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CRA
3669-18/09/91-4-0 (C-01
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Corrective
Actions
N
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Final report to Project
Administrator for approval
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Report to CRA
figure 8. 7.1
ANALYTICAL DATA FLOW
ANALYTICAL SUBCONTRACTOR
JADCO-HUGHES SITE
Gaston County, NC
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precision criteria, transmittal errors, and anomalously high or low parameter
values. The results of data validations will be reported to the project
managers, noting any discrepancies and effects upon data acceptability.
Raw data from field measurements and sample collection
activities that are used in project reports will be appropriately identified and
appended to the report. Where data have been reduced or summarized, the
method of reduction will be documented in the report. In addition, field data
will be audited for abnormally high or low values that may appear to be
inconsistent with other data.
All analytical data packages will contain a summary of the
following:
chain of custody forms,
analytical methods,
-extraction and analysis dates,
-method blank samples,
-surrogate compound recoveries,
-MS/MSD analyses recoveries, and
-control sample recoveries.
A detailed case narrative summarizing analytical
difficulties and corrective actions will also be included with each data package.
If additional deliverables are required, these will conform to the current
USEPA Contract Laboratory Program (CLP) deliverables format, or equivalent.
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B.8.0 INTERNAL QUALITY CONTRqL
CHECKS AND FREQUENCY
B.8.1 FIELD 0C
Quality control procedures for field measurements will be
limited to checking the reproducibility of the measurement in the field by
obtaining multiple readings and by calibrating the instruments (where
appropriate).
Field quality control will involve collecting field duplicate
and rinsate samples in accordance with the applicable procedures described in
the FSAP.
B.8.2 LA BORA TORY OC
Specific procedures related to internal laboratory QC
samples (namely, matrix spikes, surrogate spikes, blanks, QC check samples
and matrix spike duplicates) are detailed in the following subsections.
B.8.2.1 Method Blank Samples
A method blank sample will be analyzed by the laboratory
at a frequency of one per twenty analyses or at least one per batch. The
method blank sample, an aliquot of analtye-free water or solvent, will be
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carried through the entire analytical procedure. All detected analyte
extractions must be less than twice the quantitation limits listed in
Tables B.2.2 and B.2.3.
B.8.2.2 Matrix Spike/Matrix Spike Duplicates (MS/MSD) Analyses
MS/MSD analyses will be analyzed at a frequency of 1 in
20 for each method per matrix, excluding air. For metals and cyanide, spiked
and duplicate analyses may be used in place of MS/MSD analyses. Acceptable
criteria and compounds that will be used for matrix spikes are identified in
the appropriate methods. Tables B.2.2 and B.2.3 present the compounds and
acceptable criteria. Percent spike recoveries will be used to evaluate analytical
accuracy while percent relative standard deviation or percent difference
between the spike and matrix spike duplicate recoveries will be used to assess
analytical precision.
For air analyses, one duplicate and one spike analyses will
be performed per batch. Table B.2.4 presents acceptable criteria for these
analyses.
B.8.2.3 Surrogate Compounds
Surrogate compounds are used in all organic analyses,
excluding air samples. Every blank, standard and environmental sample,
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includi!).g MS/MSD samples, will be spiked with surrogate compounds prior
to purging VOC or extracting BNA and PEST /PCB.
Surrogate compounds will be spiked into samples
according to the appropriate analytical methods. Surrogate compound
recoveries will fall within the control limits set by procedures specific in the
method for analytes falling within the quantification limits without dilution.
Diluting samples to bring the analyte concentration into the linear range of
calibration may dilute the surrogates below the quantification limit;
assessment of analytical quality in these cases will be based on the quality
control embodied in the check and MS/MSD samples.
Table B.8.1 presents a summary of the surrogate recovery
control limits as stated within the analytical methods.
B.8.2.4 Control Samples
Control samples are used to assess method accuracy. The
analytes contained in control samples will be a representative subset of the
target analytes. Percent recoveries shall be within limits specified by the
laboratory.
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TABLE B.8.1
SURROGATE COMPOUND RECOVERY LIMITS(%)
JADCO-HUGHES REMEDIAL DESIGN
Volatile Organic Compounds
Toluene-d8
Bromofluorobenzene
1,2-Dichloroethane-d 4
Base/Neutral and Acids
Nitrobenzene-d5
2-Fluorobiphenyl
Terpheny!-d14
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol
Percent Recoveries
Soil/
Water
88-110
86-115
76-114
10-110
43-116
33-141
10-94
21-100
10-123
Sediment
84-138
59-113
70-121
23-120
30-115
18-137
24-113
25-121
19-122
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B.9.0 PERFORMANCE AND SYSTEM AUDITS AND FREQUENCY
For the purpose of external evaluation, performance
evaluation check samples from the USEPA and various state agencies are
analyzed periodically by ENSECO.
Internally, data evaluation for these samples is done on a
continuing basis over the duration of a given project.
The CRA QA Officer -Analytical Activities may carry out
performance and/or systems audits to ensure that data of known and
defensible quality are consistently produced during a program.
System audits are qualitative evaluations of all
components of field and laboratory quality control measurement systems.
They determine if the measurement systems are being used appropriately.
The audits may be carried out before all systems are operational, during the
program, or after the completion of the program. Such audits typically
involve a comparison of the activities given in the QA/QC plan described
herein, with activities actually scheduled or performed. A special type of
system audit is the data management audit. This audit addresses only data
collection and management activities.
The performance audit is a quantitative evaluation of the
measurement system used for a monitoring program. It requires testing the
measurement systems with samples of known composition or behavior to
evaluate precision and accuracy. A performance/system audit may be carried
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out by or under the auspices of the USEP A Region IV Central Regional
Laboratory, without the knowledge of the analyst during each sampling event
for this program. The scheduling of performance evaluation (PE) audits will
be at the discretion of the USEP A.
In addition, one external QA audit may be conducted by
CRA prior to analysis of any investigatory samples. It should be noted,
however, that any additional external QA audits will only be performed if
deemed necessary by either the PRP or CRA project managers or the CRA QA
officers. The project laboratory may also undergo PE audit(s) by the USEP A, if
so requested.
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B.10.0 PREVENTIVE MAINTENANCE
All analytical instruments to be used in this project will be
serviced by ENSECO personnel at regularly scheduled intervals in accordance
with the manufacturer's recommendations. Instruments may also be
serviced at other times due to failure. Requisite servicing beyond the abilities
of ENSECO personnel will be performed by the equipment manufacturer or
their designated representative.
Daily checks of each instrument will be by the analyst
responsible for that instrument. These daily checks will include changing GC
inlet liners, GC/MS instrument checks, checking operation of data systems,
checking for leaks, etc. Manufacturer's recommended procedures will be
followed in every case.
The HNU, pH and conductivity meters will be calibrated
in the field as described in Section B.5.3. In addition, the following
preventive maintenance measures will be taken in the field:
HNU -The HNU meter is sent annually to the manufacturer for
recalibration and cleaning.
pH, Conductivity Keep probes clean and free of dirt by rinsing with
deionized water.
Keep deionized water around probes to prevent
dehydration.
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Water Level Tape Clean probe and lower three feet of tape with
pesticide grade isopropanol and deionized water to
prevent hard water and iron build up.
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SPECIFIC ROUTINE PROCEDURES USED TO ASSESS
DATA PRECISION. ACCURACY AND COMPLETENESS
B.11.1 OA MEASUREMENT QUALITY INDICATORS
B.11.1.1 Precision
Precision will be assessed by comparing the analytical
results between MS/MSD analyses and/or duplicate sample analyses.
B.11.1.2 Accuracy
Accuracy will be assessed by comparing a set of analytical
results to the accepted, or "true", values that would be expected. In general,
surrogate, MS/MSD analyses and check sample recoveries will be used to
assess accuracy.
B.11.1.3 Outliers
Procedures discussed previously will be followed for
documenting deviations from established control limits. In the event a result
deviates significantly from established control limits, this deviation will be
noted and its effect on the quality of the remaining data assessed and
documented.
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B.12.0 CORRECTIVE ACTION
The need for corrective action may be identified by system
or performance audits or by standard QC procedures. The essential steps in
the corrective action system will be:
-Checking the predetermined limits for data acceptability beyond which
corrective action is required;
-Identifying and defining problems;
-Assigning responsibility for investigating the problem;
-Investigating and determining the cause of the problem;
-Determining corrective action to eliminate the problem (this may include
reanalyses of resampling and analyses);
-Assigning and accepting responsibility for implementing the corrective
action;
-Implementing the corrective action and evaluating the effectiveness;
-Verifying that the corrective action has eliminated the problem; and
-Documenting the corrective action taken.
For each measurement system, the CRA QA Officer -
Analytical Activities will be responsible for initiating the corrective action
and the laboratory supervisor will be responsible for implementing the
corrective action. The corrective action taken will depend upon the QA/QC
criteria that did not meet the necessary criteria, and may range form
qualifying the data to resampling at the Site.
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QUALITY ASSURANCE REPORT TO MANAGEMENT
Management will receive reports on the performance of
the measurement system and the data quality, following each sampling
round and at the conclusion of the report.
Minimally, these reports will include:
-Assessment of measurement and quality indicators(i.e. data accuracy,
precision and completeness);
-Results of system audits; and
-QA problems and recommended solutions.
The CRA QA Officer -Analytical Activities will be
responsible within the organizational structure for preparing these periodic
reports. The final report for the project will also include a separate QA
section which will summarize data quality information contained in the
periodic QA/QC reports to management, and details and overall data
assessment and validation in accordance with the data quality objectives
outlined in this QAPP.
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ATTACHMENT B-1
LA BORA TORY CUSTODY PROCEDURES
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Enseco QA Program Plan
7. SAMPLE CUSTODY
Section No.
Revision No.
Date
Page
7
3.4
4/91
19 of 62
Upon receipt by Enseco, samples proceed through an orderly processing
sequence specifically designed to ensure continuous integrity of both the
sample and its documentation.
All samples are received by Enseco's Sample Control Group and are
carefully checked for label identification, and completed, accurate
chain-of-custody records. Photographs document the condition of samples
and each sample is then assigned a unique laboratory identification
number through a computerized Laboratory Information Management System
(LIMS) that stores all identifications and essential information. The
LIMS system tracks the sample from storage through the laboratory system
until the analytical process is completed and the sample is returned to
the custody of the Sample Control Group for disposal. This process is ,
summarized in Figure 7-1. Access to all Enseco laboratories is
restricted to prevent any unauthorized contact with samples, extracts, or
documentation.
An example of the Enseco Chain-Of-Custody Record used to transmit samples
from the client to the laboratory is given in Figure 7-2. The Chain-Of-
Custody Record (lnterlaboratory Analysis Form) used to transmit samples
between laboratories within Enseco is given in Figure 7-3.
Sample bottles provided to the client by Enseco are transmitted under
custody.
Enseco QA Program Plan
Figure 7-1
Section No.
Revision No.
Date
Page
7
3.4
4/91
20 of 62
ENSECO SAMPLE PROCESSING FLOW CHART
Sample Control
Proper Storage
Laboratories
Sample Control
*
*
*
*
*
*
*
*
*
Check and document physical condition
of sample
Verify documentation and parameter
assignment
Log into LIMS
Send acknowledgement letter to client
Store sample according to preservation
guidelines
Transfer sample to lab with proper
documentation
Document analytical work
Return unused samples to Sample Control
Return sample to client or arrange for
sample disposal
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:...i.M?LiNG SITE
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DATE TIME SAMPLE ID/DESCRIPTION
-
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·-·
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----
CUSTODY TRANSFERS PRIOR TO SHIPPING
. ----
RHINQUISHED BY (SIGNED) RECEIVED BY (SIGNED)
... ---·--
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ANodo, CO 80002
303/421-66l 1 FAX: [phone]
I SAMPLE SAFE'" CONDITIONS
PACKED BY SCAL NUMBER
SEAL INTACT UPON RECEIPT DY SAMPLING COMPANY CONDITION OF CONTENTS
SEALED FOR SHIPPING BY INITIAL CONTENTS T(MP
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SEAL NUMBER rAMPUNG STATUS
0 Dono O Continuing Un1il
SEAL INT ACT UPON RECEIPT BV LAB. J CONTENTS TEMPERATURE 1.,;PON RECEIPT BY LAB.
0 Yo, □No •c
SAMPLE TYPE # C0HTAIHEIS ANALYSIS PARAMETERS REMARKS
SHIPPING DETAILS
O[LIVEREO TO SHIPPER BY
DATE TIME
METI-100 Of SHIPMENT AIRBILL l'IUMBER
RECOVEO FOR LAB ISIGNCO IOAJ[/T11-1E
ENSECO PROJECT NUMBER
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ATTENTION: ATTENTION:
EXPORT ID COMMENTS
SAMPLE
CONDITION
UPON
I RECEIPT
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WRITTEN RESULTS IVERBAUfAC RESULTS rO.No TEST PRICE AEOUIRED Bl' (OATEI REQUIRED B'f (OATEJ
SUBTOTAL Q.C. DsrmoARoeNseco 0 ClP PROTOCOL O PROJECT SPECIFIC
DISCOUNT / SURCHARGE SAMPLE DISPOSAL 0 ENSECO O RETURN TO CllENT O PHONE
TOTAL DETECTION LIMITS □ co,.o.cON PRODUCTS 0 OTHER•
• SPECIAL INSTRUCTIONS HOLDING TIMES 0 ENSECO O EPA·Ct.P 0 TIER O OTHER•
RAW DATA COPIES NEEDED Oves □NO
CUSTODY SEALS INTACT Ov,s D NO I D WET WflGttf 0 OA'I' WEIGHT
AEUNOUISHED DATE I TIME
RECEIVED DATE I TIME
- ----- -- --· --· - -
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ATTACHMENT B-2
LABORATORY STANDARD OPERATING
PROCEDURES
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STANDARD
OPERATING
PROCEDURE
Page _l_ of .12_
GC/MS ANALYSIS OF VOLATILE ORGANICS
SOP No.: LM-RMA-3001 VOA by GC/MS
Supersedes: 2.0
1. SCOPE AND APPLICATION
Revision No. :
3.0
Effective Date:
4/24/90
1.1 Analytes: Quantitative analysis is performed for the compounds
listed in Appendix A. Qualitative analysis by mass spectral
identification can be performed on other purgeable, chromatographable
compounds.
1.2 Reporting Limits: Test Specific
1.3 Applicable matrices: Water, soil, solids, sludge and waste.
1.4 Dynamic range: Analytes can typically be quantitated between 5 ppb
and 200 ppb for water samples and soils analyzed by the low level
direct purge method. Analytes in soils analyzed by the methanol
extraction method can be quantitated between 500 and 20000 ppb.
1.5 Analysis time: Approximate analytical time is 40 minutes per GC/MS
run. The time required for data reduction will be dependent upon the
complexity of the sample.
Prepare y:
Date: LJ/zl( /<Jo
Management Approv ~~e
QA Officer
Appro,a~ rt
0
Date:
1/-.;} Y-'to
SOP No.:
1.6
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3OO1 VOA by GC/MS Revision No.:
3.0
STANDARD
OPERATING
PROCEDURE
Page 2 o 39 ---
Effective Date:
4/24/90
The applicability of this Standard Operating Procedure to particular
matrices and/or analytical requests not specifically stated herein is
detennined by the GC/MS department manager and communicated to the
client manager. The GC/MS department manager has the authority to
make modifications to the SOP for certain matrices and/or analyses if
his technical judgement deems it necessary and appropriate.
2. METHOD SUMMARY
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2.1 Aqueous samples are analyzed by quantitative and/or qualitative purge I
and trap-GC/MS using an i nterna·l standard method.
2.2 Solid samples are extracted with methanol and the extract is analyzed
by purge and trap-GC/MS for quantitative and/or qualitative
identification using the same internal standard method.
2.3 Alternatively, lower detection limits can be achieved for analytes in
soil samples by using the direct purge method.
3. COMMENTS
3.1 All deviations made from this SOP MUST be approved by the supervisor
and well documented.
3.2 All reusable glassware should be washed with hot, soapy water and
rinsed thoroughly. This is followed by a rinse with HPLC grade (or
better) Methanol. Finally, the glassware is baked in a 1050 oven.
3.3 Care should be taken not to introduce contamination into the samples.
Particular attention should be paid to common laboratory solvents,
such as acetone and methylene chloride.
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SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
STANDARD
OPERATING
PROCEDURE
Page_]_ of _l1__
Effective Date:
4/24/90
3.4 Care should be taken when handling samples for volatiles analysis to
avoid loss of analytes.
3.5 Do not overstock traps. Tenax has a lifetime of only a few months.
Traps will also degrade with use due to the breakdown of tenax from
rapid temperature changes.
4. SAFETY ISSUES
4.1 The toxicity or carcinogenicity of each chemical used in this
procedure has not been precisely defined, however, each chemical
compound should be treated as a potential health hazard. From this
viewpoint, exposure to these chemicals should be reduced to the
lowest possible.
4.2 A Material Safety Data Sheet (MSDS) is available for all laboratory
standard and reagent chemicals. The appropriate MSDS must be read
before handling the chemical(s).
4.3 All laboratory personnel should be thoroughly familiar with the
laboratory Safety Manual and Hazard Communication Standard before
undertaking any laboratory work.
4.4 Samples should be considered as hazardous. Appropriate protective
clothing, such as gloves, lab coat and safety glasses should be worn
when handling samples.
5. SAMPLE COLLECTION, PRESERVATION, CONTAINERS AND HOLDING TIMES
5.1 Standard 40 ml glass screw-cap VOA vials with Teflon-faced silicone
septa may be used for both liquid and solid matrices. Solid samples
may also be collected in wide-mouth glass jars with Teflon-lined
caps. Samples should be introduced into the containers with minimum
agitation to avoid loss of volatile components. For liquid samples,
each VOA vial should be filled without introduction of bubbles. Fill
until there is a meniscus over the lip of the vial. The lid with
septum (Teflon side toward the sample) should be tightened onto the
vial. After tightening the lid, the vial should be inverted and
SOP No.:
5.2
5.3
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
STANDARD
OPERATING
PROCEDURE
Page 4 of 39 ---
Effective Date:
4/24/90
tapped to check for air bubbles. If there are any air bubbles
present the sample must be retaken. Sample containers for solid
samples should be filled as completely as possible with minimum air
space.
Water samples may be preserved with HCl to extend the holding time of
samples to be analyzed for aromatic compounds. Aromatic compounds
are particularly susceptible to biodegradation at normal pH. The pH
of the sample should be adjusted to less than 2 with HCl in the field
at the time of sampling.
All samples must be iced or refrigerated at 40c from the time of
collection until analysis.
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5.4 All aqueous samples must be analyzed within 7 days of collection. If I
aqueous samples are preserved with HCl, the holding time is extended
to fourteen days from date of collection. Medium level soil/waste
samples must be extracted and analyzed within 14 days of collection. I
Soil samples which are analyzed by the low level method must be
analyzed within 14 days from the sampling date.
6. APPARATUS I
6.1 Gas-tight syringes: 10 ul, 25 ul, 50 ul, 100 ul, 250 ul, 500 ul, and
1 ml.
6.2 Syringe valve: two-way with Luer ends.
6.3 5 ml gas tight syringe, luer-lock type.
6.4 1 ml disposable pipet.
6.5 Top-loading balance capable of weighing 0.1 g.
6.6 Glass culture tubes with screw cap and teflon liner.
6.7 Volumetric flasks: 10 ml -100 ml.
6.8 Screw top vials with teflon-lined septa for storage of methanol
extracts and extract dilutions.
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GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page _5_ of 22._
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
6.9 Disposable pasteur pipets.
6.10 Stainless steel spatula.
6.11 Gas Chromatograph for screening with all required accessories such as
syringes, analytical columns, gases, flame ionization detector,
recording device and optional autosampler or optional headspace
analyzer. A data system is recommended for data acquisition,
integration and output.
6.12 Heated bath or heater capable of maintaining the purging chamber to
within+/-1°c over the temperature range of ambient to 100°c.
6.13 Purge-and-trap device including the sample purger, the trap and the
desorber. (Tekmar LSC-2 or equivalent) Device may include automatic
sampler (Tekmar ALS or equivalent.)
6.14 Purging Chamber
6.14.1
6.15 Traps
6.15.1
Two piece glass purge cell with ground glass joint and
airtight a-ring connection, single piece glass purge tube,
and/or glass-fritted sparger or equivalent.
Four phase: Supelco Volatile Purge trap, or equivalent.
1. 1 cm 3% SP-2100 on 60/80 Chromosorb WAW
2. 15 cm Tenax TA
3. 8 cm 35/60 Silica Gel Gd-15
4. 1.5 cm Carbosieve added to base
6.16 Chromatographic Columns
6.16.1
6.16.2
Screening column: JW P/N 125-1334 DB624. Mega-Bore
30m X .53mm I.D., or equivalent
Analytical Column:
A. JW P/N 125-1334. DB624 Mega-Bore 30m X .53mm I.D., or
equivalent.
GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page_£... of .l.2__
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
7.
6.17 Gas Chromatograph/Mass Spectrometer
6.17.1
6.17.2
6.17.3
6.17.4
Gas chromatograph: An analytical system that includes a
temperature-programmable gas chromatograph including all
required accessories such as syringes, columns, and gases.
Mass spectrometer: Capable of scanning from 35 to 300 amu
every 1 second or less, using 70 volts (nominal) electron
energy in the electron impact ionization mode.
GC/MS interface: An interface that gives acceptable
calibration points at 50 ng or less per injection for each
of the analytes and achieves all acceptable performance
criteria. An all glass interface is recommended.
Data system: A computer system must be interfaced to the
mass spectrometer which will allow the continuous
acquisition and storage on machine-readable media of .all
mass spectra obtained throughout the analytical run. The
software should be capable of producing extracted ion
profiles and integrating these abundances. The EPA/NIH
Mass Spectral Library should also be available on the
system.
REAGENTS AND STANDARDS
7.1
7.2
7.3
Reagent water -Carbon filtered house distilled water, continuously
sparged with an inert gas prior to use for volatiles analyses.
Interferents should not be observed at or above the reporting limit
of the parameters of interest.
GC/MS Calibration solution: 50 ng/ul bromofluorobenzene in methanol.
Internal standard and surrogate spiking solutions.
MS-VOA-IS (See SOP No. LS-RMA-010)
MS-VOA-SCS (See SOP No. LS-RMA-011)
7.4 Laboratory Control Sample standard spiking solution.
MS-VOA-LCS (see SOP No. LS-RMA-012)
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GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page 7 of 39 ---
SOP No.: LM-RHA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
7 .5 GC screening standard. (See RMAL SOP "Volatiles Screening Analysis
by GC/FID -SOP No. LM-RMA-3022.)
7.6 Calibration standard solutions:
A.
B. c.
D.
E.
MS-VOA-CS!
MS-VOA-CS2
MS-VOA-AP9-CSA
MS-VOA-AP I-CSA
MS-VOA-B&V-CSA
(See SOP No.
(See SOP No.
(See SOP No.
(See SOP No.
(See SOP No.
LS-RMA-001)
LS-RMA-009)
LS-RMA-015)
LS-RMA-013)
LS-RMA-039}
7.7 Standards containing other purgeable compounds can be prepared on
special request by clients.
7.8 Methanol: purge-and-trap grade or equivalent. Store apart from other
solvents.
8. PROCEDURE
8.1 Scheduling Samples for Analysis
8.1.1. Samples will be scheduled for analysis by experienced
analysts and/or supervisors according to the following
priorities:
a) Meet holding times
b} Meet promised due date
8.2 Methanol extraction of soil samples for analysis by the medium-level
method. (minimum reporting limit: 500 ug/kg)
8. 2 .1
8.2.2
8.2.3
Carefully mix the contents of the sample container. Do not
discard any supernatant liquids. Weigh 5 g of sample to
the nearest 0.1 g. Note and record the actual weight.
Determine the percent moisture as in section 8.4 (if
required).
Add 10 ml purge & trap methanol, (25 ug/mL). Cap and shake
for 2 minutes.
GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page_§_ of _l1___
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
8.2.4
8.2.5
8.2.6
Allow the soil to settle or centrifuge and transfer a
portion of the extract to a labelled autosampler vial,
leaving a minimum of headspace. Store these extracts at
40c prior to analysis.
Prepare methanol blank for each day of extraction using
same procedure as medium level.
Screen the methanol extracts as described in section 8.3
8.3 SCREENING. For complete information on the screening procedures for
GC/MS Volatile compounds, refer to RMAL SOP No. LM-RMA-3022,
Volatiles Screening Analysis by GC/FID.
8.4 Percent Moisture Determination (optional)
8.4.1 Weigh 5-10 g of sample into a tared weighing dish. Record
the samples wet sight. Allow to dry overnight at 1osoc.
Re-weigh the sample. Record the samples dry weight.
(Correct for weight of weighing dish) Calculate percent
moisture using equation 10.2.7.
8.5 Instrument Set-Up for the GC/MS
8.5.1 Chromatographic Conditions
8.5.1.2 Mega-bore Capillary Column (See Section 6.17.3)
8.5.1.3 Temperature Program for Capillary Column:
Initial Temperature: -1ooc
Temperature Ramp:
Program 1: 20°/min 1.5 minutes to 200
Program 2: s0/min 16 minutes to 100°
Program 3: 20°/min 3 minutes to 160°
Final Time: 7 minutes
These parameters are subject to change and are given
as guidelines.
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GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page 9 o 39 ---
SOP No.: LM-RMA-3001 VOA by GC/MS Rev i s ion No. :
3.0
Effective Date:
4/24/90
8.5.2 Mass Spectrometer parameters:
8.5.2.1 Mass range: 35-300 AMU
8.5.2.2 Scanning rate: 1 second/scan
8.5.3 Purge and Trap Parameters
8.5.3.1 Trap: As described in Section 6.16
8.5.3.2 Purge Flow: 30-50 ml/min (measured at vent in
purge mode).
8.5.3.3
8.5.3.4
Purge pressure:
gauge)
Purge Time:
Des orb Ti me:
Bake Time:
20 lb/in2 (measured on the
12 minutes
2-3 minutes
8-10 minutes
8.6 Installation and conditioning of trap in the purge-and-trap device.
8.6.1
8.6.2
All traps should be installed with accompanying brass nut
down and inlet marker to the top. A brass nut and ferrule
should be used at the bottom connections. A teflon ferrule
should be used at the top. The top nut should only be
finger tightened.
Purge flow is adjusted by measuring the flow at the vent in
purge mode.
The faster the purge flow the more efficient the purging
process. The limit to increasing the flow is governed by
the ability of the trap to adsorb and contain the purged
analytes.
SOP No.:
8.7
GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page 10 of 39 ----
LM-RMA-3001 VOA by GC/MS Revision No. :
3.0
Effective Date:
4/24/90
8.6.3
If the total purge volume is too large (flow rate too high)
then the lightest compounds such as the gases will break
through the end of the trap and their respective RFs will
drop correspondingly. If the purge flow is slow the
heavier and the more polar compounds will not purge
efficiently. Thus, to improve the response of the CS2
compounds, the purge flow should be decreased and to
improve bromoform response the purge flow should be
increased.
In general, the purge flow should be between 30 and 50
ml/min.
If optimization of overall RFs by changing the purge flow
cannot be attained, a new trap may need to be installed.
The trap is conditioned by placing an empty sparge cell on
the purge & trap device and placing the unit into purge
mode. After a few minutes, step into "bake" mode for 10-15
minutes.
Instrument Calibration
8.7.1 BFB
8.7.1.1 Each GC/MS MUST be hardware tuned to meet SW-846
3rd. Edition ion abundance criteria for BFB. The
instrument tune MUST be verified at the start of
every operation. When the tuning criteria are
met, standards and samples may be run for a
period of 12 hours depending on contract or
method requirements. Ion abundance criteria are
listed in SW-846 3rd Edition.
8.7.1.2 50 ng of BFB is directly injected on to GC column
and peak data are acquired.
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SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page 11 o 39 ----
LH-RMA-3001 VOA by GC/MS Revision No. :
3.0
Effective Date:
4/24/90
8.7.2
The spectrum of BFB is evaluated. Ion abundance
criteria given in Table C-1 must be met.
Choosing a scan that is one scan to the left or
right of the peak apex and reasonable background
subtraction or enhancement is acceptable.
Manipulations which will distort the spectrum,
such as excessive background subtraction or
multiple scan additions, are not acceptable.
8.7.1.3 If the ion abundance criteria are not met, the
instrument is retuned and BFB reinjected.
8.7.1.4 If the ion abundance criteria are met, a hardcopy
of the spectrum, mass abundance table, and ion
abundance summary is generated and stored on
file.
Initial calibration. An initial calibration must be
performed before analysis of samples can begin. This
consists of a five point calibration curve for the analytes
of interest. Low-level soil analysis requires an initial
calibration in which the standards in water are heated to
4D° C during the purge step. Standard solutions are
prepared in reagent water at concentrations of 20 ug/L, SD
ug/L, 100 ug/L, 150 ug/L and 200 ug/L, and purged, desorbed
and analyzed on the GC/MS/DS. All 5-points must be
injected within 12 hours of BFB injection which has met
abundance criteria.
Certain compounds have been selected to monitor instrument
performance. These compounds are identified as System
Performance Check Compounds (SPCC) and Calibration Check
Compounds (CCC).
The average response factor for each System Performance
Check Compounds (SPCC) MUST be greater than or equal to
0.300, except for bromoform, which must be greater than or
equal to 0.250.
SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS Rev i s ion No. :
3.0
STANDARD
OPERATING
PROCEDURE
Page __!L of _l1___
Effective Date:
4/24/90
The percent relative standard deviation (%RSD) for each
Calibration Check Compound (CCC) MUST be less than 30%. The
%RSD for all compounds should also be reviewed. Any values
greater than 40% should be evaluated before analyses are
continued.
If samples are NOT being analyzed for these specific
compounds, the criteria for these compounds need not be
met. The fact that these compounds are not in the analyte
set should be documented.
See current CLP-SOW for a summary of'CCC and SPCC criteria.
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8.7.2.1 The five standard solutions are typically analyzed in I
the following order: 50 ppb, 20 ppb, 100 ppb, 150
ppb and 200 ppb.
Standards are prepared using a 5 ml calibrated gas-
tight syringe which is rinsed with purged reagent
water and then filled to a volume of 5 ml.
Internal standards, surrogates and analytes are then
added.
8.7.2.2 Standards are analyzed using the ALS. Standards are
introduced into a purge chamber on the ALS followed by
purging & desorption into the GC/MS/DS as previously
described.
8.7.2.3 The area counts of the internal standards in the 50
ppb standard are evaluated before calibration is
continued. The first internal standard EICP
(Bromochloromethane) should be between 15,000-50,000
counts depending on the instrument. This will
minimize saturation in the higher level standards. If
the peak area is outside these limits, the analyst
should adjust the electron multiplier and re-inject
the 50 ppb standard.
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SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS Revision No. :
3.0
STANDARD
OPERATING
PROCEDURE
Page _li_ o .J1.._
Effective Date:
4/24/90
8.7.2.4 The SPCC and CCC limits MUST be verified and met. If
any criteria is not met, the analyst and supervisor
will choose appropriate corrective action. Sample
analysis cannot take place until CCC and SPCC criteria
are met for the initial calibration.
8.7.2.5 The quantitation list is reviewed to ensure that the
internal standards are correctly identified and that
the analytes are properly quantitated. Special
attention is payed to the following compounds to
ensure correct peak assignment:
dichlorodifluoromethane
chloroethane
vinyl chloride
acetone
cis-1,3-dichloropropene
trans-1,3-dichloropropene
2-butanone
2-hexanone
4-methyl-2-pentanone
xylene isomers
cis-1,2-Dichloroethene
trans-1,2-Dichloroethane
dichlorobenzene isomers
cis-1,2-Dichloroethene
trans-1,2-Dichloroethene
8.7.2.6 If the standard evaluation criteria have been met,
update with the response factors and retention times
of the 50 ppb standard just analyzed. Standards and
samples are processed.
8.7.2.7 The 20 ppb, 100 ppb, 150 ppb and 200 ppb standard are
then analyzed and evaluated in the same manner as the
50 ppb standard, using programs on the data system
designed for multipoint calibration data.
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8.7.3
8.7.2.8 A table which lists each standards Response factors,
the average Response factors and% RSD for each
compound is generated. The% RSD for CCC and Response
factors or SPCC are then evaluated. Compounds having
% RSD greater than 30% are checked to verify accuracy
of quantitation of each standard. Response factors
which differ greatly from the compound average are
also investigated.
8.7.2.9 If all CCC and SPCC criteria are met, the data are
stored in an Initial Calibration file. This file is
then referred to during continuing calibration.
Continuing calibration
The 50 ppb standard is used as the continuing calibration
standard. It MUST be analyzed for each twelve hour period,
immediately following a successful BFB analysis. The BFB
injection time starts the twelve hour clock.
The response factor of each CCC compound should be compared
to the initial calibration using multipoint calibration
software. The percent difference for each CCC compound
should be less than or equal to 25%. Analyses may continue
if any one CCC or any one SPCC is not within limits but
only if contractually allowable or approved by a
supervisor. Response factors for all analytes should be
reviewed. Any significant deviations from the initial
calibration should be evaluated and quantities checked
before analyses are continued. (e.g. deviations of greater
than 30%)
8.7.3.1 The continuing calibration standard is run as
described in section 8.7.2.1. The concentration of
each of the surrogate compounds and the internal
standard compounds is 50 ppb.
8.7.3.2 Process the data file as described in Section 8.7.2.2.
(See Section 8.10.1).
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8.7.3.3 The quantitation list is reviewed to ensure that the
internal standards are correctly identified and that
the analytes are properly quantitated. Check the
compounds listed in 8.7.2.5 for proper integration and
peak assignment.
8.7.3.4 A program on the data system is used to compare the
continuing calibration standard to the initial
calibration. The CCC and SPCC compounds are evaluated
as outlined in Section 8.7.3. The RF and percent
deviations from the initial calibration of all the
other compounds are reviewed. (e.g. compounds with
deviations> 30% are checked for proper peak
assignment and integration.)
8.7.3.5 If the standard evaluation criteria are NOT met,
corrective action must be taken. Corrective action
may include replacement of the trap or the analytical
column or replacement of calibration standards which
may have degraded. Document corrective action taken.
Repurge the continuing calibration standard and/or
perform a new initial calibration. (See Section
8.7.2.)
8.7.3.6 If these criteria are not met and the decision is made
to continue analysis, the rationale must be
documented, approved by a supervisor, and kept on file
with the continuing calibration record.
8.7.3.7 If the standard evaluation criteria have been met or
the decision has been made to continue, update the
data system with the Response factors and retention
times of the continuing calibration standard just
analyzed.
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8.8 File Naming Conventions
The file names of BFB, standards, QC, and samples acquisitions are
based on the instrument letter designation, and a continuing numeral
integer progression from 0001 to 9999. When file number 9999 is
reached, go to 0001. File names are recorded in the instrument log
book on a daily basis as acquisitions are conducted.
8.9 Sample Analysis
8.9.1 Scheduling
8.9.1.1 Analyses are scheduled by the supervisor or a senior
analyst generated from the Laboratory Information
Management System (LIMS). Backlogs are available in
the laboratory.
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8.9.1.2 The analyst will determine the type of analysis I
requested. Modifications to the normal analytical
protocol such as low detection limits, special
compounds or special criteria will be indicated on the I
backlog or found in the LIMS database.
8.9.1.3 Sample !D's are tracked based on RMA project and
sample numbers assigned by Sample Receiving. These
!D's should be used when entering the "Sample ID"
accounting parameter in data acquisition programs.
8.9.2 Analysis Sequence
8.9.2.1 A method blank (surrogate control sample) must always
be analyzed after a calibration standard. See section
9.3 for method blank acceptance criteria. Duplicate
control samples (DCS) are analyzed as required by SOP
No. M-EQA-002. SCS and DCS sample results must be
verified before samples can be analyzed. See Section
9.0 for QC criteria for SCS and DCS samples.
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8.9.2.2 If the QC criteria are met, the sample analysis can
begin. Consult the Enseco QAPP for specific
requirements. Matrix spike and matrix spike
duplicates and any other Project Specific QC when
requested by the client, are analyzed in conjunction
with the associated sample.
8.9.2.3 Samples must be injected within 12 hours of the BFB
injection, unless a method or contract specifies
otherwise.
8.9.3 Analysis of Water Samples
8.9.3.1 All samples must be allowed to warm to ambient
temperature before analysis.
8.9.3.2 All purging cells are washed with soap and hot
water, rinsed with water, then methanol and baked
dry.
8.9.3.3 Screen data is first reviewed to determine if any
samples require dilutions. When screens indicate
samples are clean, or have low levels of volatile
compounds, 5 ml will be used for analysis.
Sample volume will be measured using a 5 ml gas-
tight syringe. If screens indicate high levels
of volatile compounds are present, sample volume
will be adjusted so that the compound in highest
concentration will quantitate at approximately
100 ppb. The final volume of sample is adjusted
with reagent water so that 5 ml is always purged.
Dilutions of up to 1:1000 (5 ul of sample or
more) can be made directly in the 5 ml syringe.
If necessary, serial dilutions of 1:10 are made
so that 5 ul of sample will be the minimum volume
injected into the 5 ml syringe.
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8.9.3.4 The sample is carefully poured into the syringe
barrel nearly filling the barrel. Vent any
residual air while adjusting the samples volume
to 5.0 ml. A second syringe may be filled at
this.time (if capped off), if there is only one
vial for analysis. This will maintain the
integrity of the sample. A sample may be stored,
refrigerated, in a syringe for 24 hours.
8.9.3.5 Add 10 ul of the internal standard+ surrogate
(VOA IS/SCS) mix to the sample using 25 ul gas-
tight syringe.
8.9.3.6 The syringe valve assembly is attached to the
valve on the purging chamber. The valve on the
chamber is opened and the sample is injected into
the purging chamber.
8.9.3.7 The valve on the purging chamber is closed and
the syringe is removed. The sample is then
purged and analyzed using the same instrument
parameters as those used to analyze the
calibration standards.
8.9.3.8 Sample number and sample concentrations are
recorded in the instrument log book.
8.9.3.9 Surrogate control samples and duplicate control
samples are prepared using 5.0 ml of purged
reagent water. Add 10 ul of internal standard
and surrogate solution (VOA IS/SCS) to the water
in the syringe. For DCS samples, add 10 ul of
DCS spike solution in addition to the surrogates
and internal standards. Place each aliquot into
adjacent purge vessels. SCS must meet blank
criteria described in Section 9.3.
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8.9.4
8.9.3.10 Matrix spikes are prepared in the same manner.
The additional aliquot(s) of the sample to be
spiked is (are) placed in 5 ml gas-tight
syringes. If the sample requires dilution,
dilute the matrix spike aliquot as well. Add 10
ul of the internal standard+ surrogate (VOA
IS/SCS) mix and 10 ul of the matrix (VOA-DCS)
spike solution to each aliquot prepared. Analyze
the sample and matrix spike(s) consecutively, if
possible.
Analysis of Methanol Extracts for the Medium Soil Method
8.9.4.1 The samples are extracted and screened as
described in Section 8.2 and 8.3.3. A medium
level blank consisting of 5 ml reagent water, 10
ml IS/SCS mix and 100 ul of methanol is run with
each set of medium level samples.
8.9.4.2 A 5 ml gas-tight syringe is filled with purged
reagent water. Adjust the volume to 5 ml. If
screening data indicates sample requires between
5 ul and 100 ul of extract, then the appropriate
volume of the methanol extract is added to the
reagent water. If less than 5 ul of extract is
indicated, a 1:10 dilution in Methanol is
required. The extract is further diluted as
necessary so that at least 5 ul of diluted
extract is added to the reagent water purged.
The maximum amount of Methanol extract that
should be purged is 100 ml. It is acceptable to
add the extract directly to the syringe, or
directly to the reagent water after it has been
added to the purge cell. Use Hamilton microliter
syringes to deliver the 5 ul to 100 ul aliquot.
8.9.4.3 Add 10 ul of VOA IS/SCS mix to the syringe and
place the sample in the purging chamber as
described above.
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8.9.5
8.9.4.4 Matrix spike samples are prepared at the
instrument. The same volume of extract used in
the sample analysis is used in the matrix spike.
The matrix is prepared as described in sample
analysis using 5 ml reagent water, 10 ul VOA
IS/SCS mix, and 10 ul DCS mix.
Low Level Soil Analysis
8.9.5.1 QC SCS and DCS samples will be analyzed as
described in Section 8.9.3.9, with one exception,
soil DCS samples are to include 5 grams of Ottawa
sand.
8.9.5.2 The screen data is required to determine the
weight of samples to be purged (between 0.5g and
5.0g).
8.9.5.3 Mix the contents of the sample container. Do not
discard any supernatant liquids. The amount of
sample to be purged as determined by the screen
is weighed into a tared purge vial. Note and
record the actual weight to the nearest 0.1 g.
8.9.5.4 Prepare a 5.0 ml aliquot of reagent water
containing 10 ul of VOA IS/SCS solution in a 5 ml
syringe. Add the water to the vial, purge vial +
sample by injecting the water through the valve
on the purge and trap device as the purge cell is
lifted into position. This will mix the soil and
water and ensure the helium purge tube will not
be blocked. Low level soils (and their
corresponding calibrations) are purged at a
temperature of 400c.
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8.9.5.5 Repeat steps 8.9.5.3 and 8.9.5.4 for each sample.
8.9.5.6 Surrogate control samples and duplicate control
samples are prepared as stated in section 8.9.3.9
with one exception. Each DCS sample also
contains 5.0 grams of a solid, contaminant-free
matrix, such as Ottowa Sand. No solid matrix is
used. Add 10 uL of VOA IS/SCS solution to the
water in the syringe. For DCS samples, also add
10 ul of matrix spike (VOA DCS) solution. Place
each aliquot into a purge vial and affix to the
unit as described above.
8.9.5.7 Matrix spikes are prepared using the same
procedure as the samples. Weigh the same amount
of sample for each aliquot required. In addition
to the 10 ul of VOA IS/SCS added to the reagent
water, 10 ul of DCS solution is added. Matrix
spike samples should be analyzed along with the
corresponding sample .. Affix each aliquot to the
unit as described above.
8.9.6 Data Acquisition
8.9.6.1 Samples are analyzed using the same instrument
parameters as the calibration standards.
Recommended conditions are listed in section 8.5.
Blank, SCS and DCS data must be verified before
sample analysis.
8.9.6.2 Sample data is acquired either as a single run,
or as in an automated series of sample runs.
If a limited list of compounds is being used, the
run time (number of scans desired) may be
shortened, as appropriate to the compounds being
analyzed. The actual number or scans collected
may vary slightly from one instrument to another.
8.9.6.3 File names, the date, analyst initials, sample
identification and appropriate dilution are
recorded in the instrument log book.
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8.10 Data Processing and Reduction
8 .10 .1
8 .10. 2
Following sample data acquisition, each sample data
file is processed using the same software used to
search for, identify and quantitate target compounds
as was used for calibration data.
The data package generated contains many of the
following printouts:
8.10.2.1 Log Page: Included on this page are the I
header information, GC conditions, scan
parameters, and instrument tuning parameters
that were used at the time of data
acquisition. I
8.10.2.2 Chromatogram: Included on this page is the
header information and the reconstructed .ion I
chromatogram displaying the range of scans
used during data acquisition.
8.10.2.3 Diagnostic Report: Included in this page I
is a Table of Library entries and
chromatographic and library search
information used in the computerized target I
compound evaluation.
8.10.2.4 Quantitation Report: Included in this
section is the list of target compounds,
internal standards and surrogate standards
used for processing the data file, and
compound library entry numbers. This
section contains: 1) Chromatographic
information such as retention times (scan
numbers) and relative retention times and,
2) Quantitation information such as peak
areas, updated library response factors,
calculated response factors and quantitated
amounts for all library entries.
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STANDARD
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8.10.2.5 Quantitation Su11111ary: Included on this page
is a list of internal standards, surrogates
and those target compounds which were found
in the AutoQuan target compound search
routine. Listed along with each compound is
the mass, scan, indication of internal
reference standard, peak area, response
factor and quantitation amounts.
8.10.2.6 Spectra: A mass spectra of the peak or each
target compound is printed.
8.10.2.7 Su11111ary Cover Page: Sample summary which
lists surrogate recoveries+ all target
compounds. These target compounds which
were found to have quantitation amounts,
have dilution adjustments.
8.10.3 Internal Standard area counts must be monitored
on all sample and QC runs. Areas or Percents are
recorded in the log book. The areas should not
vary by more than a factor of two (-50% to
+100%). If the areas do vary by more than a
factor of two, the analyst should first check to
see if the peak has been correctly integrated.
If the area is still outside the limits, the
purge & trap/GC/MS system should be checked and
corrections made if necessary. The sample will
be reanalyzed if problems were detected and
corrected. If, upon verification that the
instrument is operating properly, the areas are
still outside of the limits, submit both analyses
with the data package and document the actions
taken. If no problems were detected with the
instrument, involve a supervisor to determine if
sample reanalysis is necessary.
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8.10.4
8 .10. 5
8.10.6
Surrogate recovery values are calculated and compared
to recovery limits in Table D-2. Samples with
surrogate recoveries outside QC limits should be
checked for proper quantitation. Secondary ions may
be used if there are interferences on primary
quantitation ions. CLP contracted samples having
surrogates outside the limits are reanalyzed. If
surrogates are outside limits for the second analysis,
both analyses are submitted with data package.
Non-CLP samples, with one or more surrogates outside
limits, are documented and evaluated on a case-by-case
basis. Need for reanalysis will be determined by the
analyst and supervisor.
Verify that the_ sample -was analyzed at the proper
dilution. If any sample contains target compounds
that are greater than the highest point in the initial
calibration plus 10% (over 220 ug/L on the QUAN
report), the sample should be diluted by the
appropriate factor and reanalyzed. Exceptions to this
include acetone and 2-butanone for non-CLP work which
have demonstrated linearity to 1200 ug/L and 500 ug/L
respectively. Any sample that has been diluted should
contain levels of compounds (either target or non-
target compounds) that are high enough to justify the
dilution. In the absence of target compounds, the
peak height of non-target compounds should be
approximately greater than or equal to the peak height
of the nearest internal standard. If not, the sample
should be reanalyzed at the correct dilution.
Spectra Verification
The data processing routines generate spectra for all
target compounds> 1 ug/L for analyst interpretation.
Each positive hit picked by the data system, must be
examined by the analyst to either confirm or negate
what the processing routine has chosen.
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Prior to quantitative identification of target
compounds in a sample "standard" mass spectra of known
identity should be obtained on the instrument(s) used
for sample analysis. Hardcopies of mass spectra from
a calibration standard (e.g. 50 ug/mL continuing
calibration standard) run on the instrument under
similar tuning conditions would serve this purpose.
8.10.6.1 Each mass spectrum generated for a sample data
file should be compared to the standard spectrum.
EPA criteria for quantitative identification by
comparison of mass spectra should be followed.
The EPA criteria for comparing spectra are:
1) All ions present in the standard spectrum at
a relative intensity greater than 10% of the base
peak MUST be present in the sample spectrum.
2) The relative intensities of the ions
specified in (1) must agree within plus or minus
20% between the standard and sample spectra.
(Example: For an ion with an abundance of 50% in
the standard specrtum, the corresponding sample
ion abundance must be between 30% and 70%.)
3) Ions greater than 10% in the sample spectrum,
but not present in the standard spectrum must be
considered and accounted for by the analyst
making the comparison. If the analyst can easily
identify a co-eluting compound (e.g. an alkane or
a surrogate spike compound) then the sample
spectrum should be labelled with the contaminant.
8.10.6.2 The analyst should circle the name of target
compound on the spectrum hard copy of spectra
that meet the criteria listed in Section
8.10.6.1. All spectra that do not meet the EPA
criteria should be labelled with the word "No"
and the corresponding entries on the quantitation
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summary should be crossed out (line out the
amounts calculated for those compounds which are
not "hits") by the analyst making the judgement.
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8.10.6.3 If a compound cannot be verified by all of the I
criteria listed in 8.10.6.1, but in the technical
8 .10. 7
judgement of the analyst the identification is I
correct, the compound should be reported.
Summary Sheets
A number of summary sheets are computer generated at
the instrument following data file processing and
pulling (hardcopying) target compound spectra. These
summaries include:
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8.10.7 .1 -~-~_._,,~---~ (Also referred to as 1 "Sum Sheets" : This one or two page summary
tabulates pertinent information about a sample
analysis including header information (e.g.
sample number, dilution used for analysis, sample I
matrix), data analyzed, analyst's initials, run
factor (refer to calculations in Section 10.1.1,
final reporting units, surrogate% recoveries, I
target compounds, amounts >1.0 ug/L, scan number,
amount listed on quantitation summary and
concentration in sample (expressed in final 1 reporting units, usually ug/L for waters and
ug/kg for soils) are tabulated.
8.10.7.2 DCS Summary (Refer to section 9.0 for discussion I
of DCS QC samples): This one page summary
tabulates pertinent information about the DCS
samples representing a specific QC lot including I
QC Lot number, matrix (soil or water), date
analyzed, analyst's initials, DCS data file
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8.10.7.3
numbers, list of samples belonging to the QC lot
and the QC limits. The program calculates the
amount and average percent recovery for each
spike compound and the RPD (Relative Percent
Difference) between the two DCS recoveries for
each spike component. Percent recoveries and
RPD's that fall outside the acceptable QC limits
are flagged with an asterisk (*) and require
further action by the analyst (see Section 9.0).
When generating this summary sheet the analyst
can input a complete list of samples belonging to
the QC lot for QC tracking purposes. This
information can be found in the QC summary
notebook kept at each instrument.
SCS Summary (See Section 9.0 for discussion of
QC samples : This one page summary tabulates
pertinent information about the surrogate control
sample representing a specific ongoing
calibration. Included are QC lot number, matrix
(soil or water), date analyzed, analyst's
initials, data file number, list of samples
belonging to the lot, names of surrogates and QC
limits for surrogate% recoveries, and calculated
amount and% recovery for each surrogate.
Percent recoveries that fall outside the
acceptable QC limits are flagged with an asterisk
(*) and require further action by the analyst see
Section 9.0). When generating this summary
sheet, the analyst inputs the complete list of
samples associated with the SCS sample for QC
tracking and data reporting {Blank Subtraction)
purposes. This information can be found in the
QC summary note book kept at each instrument.
8.10.8 Library Searches {Optional)
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Some data packages will include mass spectral library
searches on non-target compounds (excluding internal
standards, surrogates & spikes) as outlined in
contract requirements or requested by the client. If
library searches (also referred to as "TIC's", "TID's"
or Tentatively Identified Compounds) are necessary to
the data package, the 10 or 15 largest unidentified
peaks that are greater than 10% of the peak (RIC) area
of the nearest internal standard will be searched
against the NBS library for possible matches.
8.10.8.1. The generation of TIC data is partially automated
through the use of several RMA programs which
perform the following functions:
1) Select non-target, unidentified peaks from
the chromatogram for tentative identification,
2) Quantitate unknown peaks using RIC area of
closest uninterfered standard as reference peak
using a response factor of 1 and run factor
adjustment. (See Section 10.2.8 for run factor
calculations)
3) Perform and generate hardcopy mass spectral
library searches on the unknown peaks (searching
against the NBS library of mass spectra),
4) Select preliminary "Best Match" spectra from
the library searches and tabulate them with
quantitation information for all unknowns,
5) Allow editing of computer's final selections
for compound names,
6) Allow manual quantitation of unusually shaped
peaks,
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SOP No.:
GC/HS ANALYSIS OF VOLATILE ORGANICS
LH-RHA-3OO1 VOA by GC/HS Revision No.:
3.0
STANDARD
OPERATING
PROCEDURE
Page -1.2._ of __l2_
Effective Date:
4/24/90
7) Generate final summary with amounts
calculated to reflect concentration in sample
(i.e. run factor applied).
8.10.8.3 After reviewing each library search spectrum, the
analyst should indicate the compound name
selected by labelling the spectrum (or circling
the correct name if it appears on the library
search spectrum as one of the computer's
selections). If the compound is to be reported
as "Unknown" (See Section 8.11.6.5) the spectrum
should be labelled as such.
8.10.8.4 When all of the library comparisons have been
printed out, a summary sheet listing each peak
with the best library fit will print out or be
filled out by the analyst. The operator should
go through each comparison, determine the
probability that the match is correct, and assign
a confidence level based on that probability.
The confidence levels are:
3 = High, verfied by an authentic standard
2 = Moderate
1 = Low
In addition, two qualifiers,
I= Isomer
C = Chemical Class
can be assigned to the identification.
8.10.8.5 The EPA criteria to be used for making these
decisions for tentative identifications are as
follows:
1) Relative intensities of major ions present
in the library spectrum at a relative
intensity greater than 10% of the base peak
should be present in the sample spectrum.
SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page _]Q_ of _l2_
LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
2) The relative intensities of the ions
specified in (1) must agree within+/-20%
between the library and sample spectra.
(Example: For an ion with an abundance of
50% in the standard spectrum, the
corresponding sample ion abundance must be
between 30% and 70%.)
3) Molecular ions present in the library
spectrum should be present in the sample
spectrum.
4) Ions present in the sample spectrum, but not
present in the standard spectrum should be
considered and accounted for by the analyst
making the comparison. If the analyst can
easily identify a co-eluting compound (e.g.
an alkane or a surrogate spike compound)
then the sample spectrum should be labelled
with the contaminant.
5) Ions present in the library spectrum but not
in the sample spectrum should be reviewed
for possible subtraction from the sample
spectrum because of background contamination
or co-eluting compounds.
8.10.8.6 If in the technical judgement of the analyst, no
valid tentative identification can be made, the
compound should be reported as unknown. The
analyst should consult with a more experienced
analyst or a supervisor if there are questions
concerning compound identification.
8.10.9 Label the RIC to identify the internal standards
surrogate compounds, target compounds, and TIC if
requested. If the sample is particularly dirty and
the peaks are buried in other peaks, estimate the
location of the peak.
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GC/MS ANALYSIS 'OF VOLATILE ORGANICS
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
STANDARD
OPERATING
PROCEDURE
Page 31 of 39 ----
Effective Date:
4/24/90
For industrial, non-CLP work the abbreviations IS-
internal standard, SS-surrogate standard, SP or SC-
spike compound, TC-target compound and TIC-tentatively
identified compound are sufficient. In CLP work the
internal standards and surrogates are usually stamped
with the compound names; the abbreviations SC, TC and
TIC are normally sufficient for contract work for
spike compounds, target compounds and tentatively
identified compounds provided a legend is clearly
indicated on each chromatogram page.
8.10.9.1 Each data package submitted by the analyst for
secondary review must include an anomaly sheet
summarizing any problems or unusual circumstances
incurred ·during sample analysis. If no problems
were encountered during analysis, the analyst
must still submit an anomaly sheet to that
effect. ·The supervisor must sign the anomally
sheet before the package progresses to the data
review g~oup.
' 8.10.9.2 QC Summary Sheets (SCS & DCS)
Each data package submitted for secondary review
must incl,ude copies of DCS and SCS summary sheets
for all QC related to the sample set in the data
package.
8.10.10.3 Instrument and sample data are organized by the
analyst at each instrument. Instrument tuning
records and BFB data are filed at the instrument.
STD, SCS, '.,and DCS Raw data are filed separately
by date at the instrument. If the above data is
required as part of the client deliverable
package, copies are made and added to the data
package assembly. The data package assembly will
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page _R_ of _l2_
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
include hardcopies of printouts described in
Section 8.10.11 for each sample. TIC library
comparison spectra and summaries are included
when required.
8.10.11 Summary of Data Package Requirements
When initial data review has been completed by the
analyst the data package should be assembled to
include the following:
Anomaly Sheet
DCS Summary Sheet
SCS Summary Sheet
Blank Target Compound Summary Sheet
Calibration Data
Out of Control Forms (if necessary) see Section
9.0
Sample Raw Data
Sample Target Compound Summaries
(attached to sample raw data)
TIC data and summary (when requested) in some cases
contract requirements or client requests will
necessitate including tuning and calibration
information (i.e. BFB), daily standard raw data and
initial and continuing calibration response factor
tables.
8.10.12 Upon completion of the data package assembly and
review, the data package is passed on to the data
review specialist for Level 2 review.
9. QA/QC Requirements (See SOP no.: M-EQA-002)
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GC/MS ANALYSIS 'OF VOLATILE ORGANICS
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
STANDARD
OPERATING
PROCEDURE
Page _ll___ of _l1___
Effective Date:
4/24/90
9.1 DCS. Duplicate laboratory control samples are analyzed for every 20
samples. DCS components are spiked into organic-free water. A
solid matrix (Ottawa sand) is incorporated as a representative solid
matrix. Aqueous and Solid DCS Q.C. lots are maintained separately.
9.2 SCS. A single control sample is analyzed with every analytical lot.
This sample serves as the method blank. An analytical lot for
volatile organics is defined. as samples analyzed within a twelve hour
period.
9.3 Blank. A Method Blank is run with each daily calibration. For
samples run under Enseco QC guidelines the SCS will serve as the
Method Blank. Medium level soils will also require a medium level
blank. All target compounds,,should be below reporting limits.
Consult with a supervisor if, any target compound is present at or
above rep. limit. Surrogate!1recoveries must fall between limits set
for SCS acceptance. Reanalyze blank or SCS if surrogate recoveries
are outside of limits. If recoveries still out, troubleshoot system
and recalibrate if necessary.
9.4 Surrogates Spiked into Sampl~s. Surrogate compounds are required to
be spiked into all samples and QC samples for this method.
9.5 Matrix specific QC. Matrix spike and matrix spike duplicates are
performed at the request of the client. Matrix spike compounds will
be the same as those used fo~ the DCS. These compounds will be
spiked into aliquots of the sample specified by the client at the
same concentration level as the DCS.
9.6 Data acceptability is based upon the results of the Duplicate Control
Samples unless otherwise negotiated with the client. QC data must
fall within established control limits in order for the laboratory to
be considered "in control" when samples from that QC lot were
analyzed. An out-of-control form must be filled out if any of the
DCS or SCS criteria is not met.
SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page 34 of 39 ----
LM-RMA-3D01 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
9.6.1
9.6.2
At least 80% of the DCS average recovery data, and at least
80% of the DCS precision data and at least 80% of the SCS
recovery data must be within established control limits in
order for the laboratory to be considered "in control".
Blank values must be acceptable. For this method the
maximum number of values permitted outside control limits
are:
average
recovery precision
DCS: 1 1
SCS: 0
Control Limits: Control limits can be found in the current
CLP-SOW. Data will be accumulated and limits statistically
adjusted over time.
9.6.3 Holding blanks will be run at a frequency.determined by the
Enseco QC Department. A holding blank consists of a VOA
vial properly filled with purged reagent water. These will
be analyzed at a frequency that reflects the maximum
allowable holding time of a sample.
9.6.4 When trip blanks are generated by the laboratory to be
shipped to a sampling site, a separate blank will be
prepared on a weekly basis. This blank is analyzed for
volatile organics and the data evaluated for contaminants,
to ensure that contaminant-free trip blanks are sent into
the field.
10. Calculations
10.1 Calculations required to reduce data
10 .1.1 Concentration factor for sample (CF):
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SOP No.:
STANDARD
OPERATING
PROCEDURE
Page 35 of 39 ----
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS I Revision No.: Effective Date:
4/24/90
10. 1.2
3.0
' CF= NOMINAL SAMPLE SIZE/ACTUAL SAMPLE AMOUNT USED
The nominal sampl~ size is 5 ml for water and 5 g for soil.
VOA SURROGATE CONCENTRATION FACTOR (SCF):
SCF = (Vol purged X 100) / amt spiked (total ng)
10.2 Calculations required to verify automated data reduction
10.2.1 Response factors
10.2.2
10.2.3
RF= Ax X Cis Wis Cx
Where:
Ax = Area of the characteristic ion for the
co~pound to be measured.
Ais = Area of the characteristic ion for the
specific internal standard.
Concentration of the internal standard
(ng/uL).
I
Concentration of the compound to be
measured (ng/uL).
Average response factor
RFave=[(RF20)(2.5)+RF5o+(RF100/2)+(RF150/3)+(RF200/4)]/
5
Where RFx = Response factor of a compound in each of
the calibration solutions.
Percent Relative Standard Deviation
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page 36 o 39 -- --
GC/MS ANALYSIS OF VOLATILE ORGANICS
LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
%RSD = SD X 100
RFave
Where:
RSD = Relative Standard Deviation
Effective Date:
4/24/90
SD = Standard Deviation of initial response
factors (per compound)
N
Where: SD = i=l Qi x)2
N-1
RFave = mean of initial response factors (per
compound)
10.2.4 Percent Deviation from average response factor
RF1 _ RFc
% Difference =
RF1
Where:
X 100
RF1 = average response factor from initial
calibration.·
RFc = response factor from current calibration
check standard.
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SOP No.:
GC/MS ANALYSIS OF VOLATILE ORGANICS
I
STANDARD
OPERATING
PROCEDURE
Page_]]_ o .l.2.._
LM-RMA-3OO1 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
10.2.5 Percent Recovery
10.2.6
10.2.7
SSR -SR
Matrix Spike Percent Recovery=---------x 100
SA
Where:
SSR =
SR =
SA =
Relative
RPO =
Where:
RPO =
D1 =
Spike Sample Results
Sample Result
Spike Added from spiking mix
percent difference
D1 -D2
-------------X lQQ
(D1 + D2)/2
Relative Percent Difference
First Sample Value
D2 = Second Sample Value {duplicate)
Percent moisture
wet sam le+dish -le+dish
wet samp e+ X 100 = % moisture
10.2.8 Run factors: CF are multiplied by the actual T.C.
concentration found in the quan list to get the concentration
found in sample.
STANDARD
OPERATING
PROCEDURE
Page ..l§_ of .J1..
GC/MS ANALYSIS OF VOLATILE ORGANICS
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No. :
3.0
Effective Date:
4/24/90
10.2.8.1 Aqueous:
CF = .005 l where X = Volume of sample used.
XL
10.2.8.2 Soil (Low Level):
10.2.8.3
11. Reporting requirements
CF= .005 kg
Xkg
X = Weight of sample used.
Projects which require% moisture corrections
CF= 0.005 kg
Xkg
(1-% moisture)
100
Medium Level:
CF = .005 l f 10 ml)
(Xkg) Yml)
act used
X=amount of sample used
in extraction
Y=volume of MEOH from extr
Projects which require% moisture
CF= 10 ml
l-%mo1sture)
100
11.1 Units: Aqueous samples will be reported in ug/L
Solid and sludge samples will be reported in ug/Kg or mg/kg on
a wet weight basis, unless requested otherwise by the client.
11.2 Reporting limits: Test Specific
Reporting limits will be adjusted according to sample dilution.
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GC/MS ANALYSIS OF VOLATILE ORGANICS
STANDARD
OPERATING
PROCEDURE
Page __l1___ of __l1_
SOP No.: LM-RMA-3001 VOA by GC/MS Revision No.:
3.0
Effective Date:
4/24/90
11.3 Significant figures:
significant figure.
significant figures.
All data <10 ug/L will be reported with one
All other data will be reported with two
11.4 LDMS data entry
12. References
12.1 Method Source: Method 8240, SW-846 Third Edition, USEPA, Office of
Solid Waste and Emergency Response, Washington, DC 20460, September
1986.
12.2 Deviations from Source Methods
12.2.1 Deviations from the·specified criteria for continuing
calibration are all9wed, provided the rationale is documented.
Additionally, non-routine compounds may be analyzed for using
a single, midpoint calibration.
12.2.2 An internal QA/QC program has been adopted by Enseco, Inc.
This is described in Enseco's "Quality Assurance Program Plan
for Environmental Chemical Monitoring." Specific elements of
the QC program are described in SOP NO. M-EQA-002: "Internal
QC Checks--Laboratory Performance QC." The laboratory control
samples generated in this program are used to monitor method
performance. Matrix spikes are performed at the request of
the client.
12.2.3 The medium level method for soil referred to in this SOP is
equivalent to the High-level method described in method 8240.
The only exception is that this SOP uses a 5 g sample compared
to the 4 g sample recommended in Method 8240.
l:lt(UMU\,;Hl.Ut(UMI:. I HANI:.
1,4-DIFLUOROBENZENE
CHLOROBENZENE-D5
1,2-DICHLOROETHANE-D4
TOLUENE-OS
BROMOFLUOROBENZENE
CHLQROMETHANE
BROMOMETHANE
DICHLORODIFLUOROMETHANE
VINYL CHLORIDE-
CHLORCETHANE
METHYLENE CHLORIDE
ACETONE
CARBON DISULFIDE
TRICHLOP.OFLUOROMETHANE
L 1-DICHLOROETHENE
1, 1-DICHLOROETHANE
TRANS-1,2-DICHLOROETHENE
CHLOROFORM
TRICHLORO-TRIFLUORO-ETHANE
1,2-DICHLOROETHANE
1,4-DIOXANE
2-BUTANONE
1, 1, 1-TRICHLORCETHANE
CARBON TETRACHLORIDE
VINYL ACETATE
BRCMCDICHLOROMETHANE
1,2-DICHLOROPROPANE
CIS-1_, 3-DICHLOROPROPENE
TRICHLOROETHENE
DIBROMOCHLOROMETHANE
1, 1, 2-TR I CHLOROETHANE
BENZENE
TRANS-1,3-DICHLOROPROPENE
1,2-0IBROMOETHANE
2-CHLOROETHYL VINYL ETHER
BROMOFORM
4-METHYL-2-PENTANONE
2-HEXANONE
TETRACHLOROETHENE
1, 1,2,2-TETRACHLOROETHANE
TOLUENE
CHLQROBENZENE
ETHYLBENZENE
STYRENE
M-XYLENE
O+P XYLENES
M-DICHLOROBENZENE
0-DICHLOROBENZENE
P-DICHLOROBENZENE
·~
PAbE 1c..oFl
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-:D-1.~L-{BROMOCHLOROMETHANE
~S 1. 4-0IFLUOROBENZENE
CHLOROBENZENE-D5
OICHLORODIFLUOROMETHANE
ACETONITRILE
IODOMETHANE
ACROLEIN
ACRYLONITRILE
TRICHLOP.OFLUOROMETHANE
ETHYLCYANIDE
3-CHLOROPROPENE
DIBROMOMETHANE
METHACRYLONITRILE
ISOBUTYL ALCOHOL
1,4-DIOXANE
2-CHLOR0-1,3-BUTADIENE
1,2-DIBROMOETHANE
1, 1,1,2-TETRACHLOROETHANE
1,2,3-TRICHLOROPROPANE
T-1,4~DICHLOR0-2-BUTENE
1,2-DIBROM0-3-CHLOROPROPANE. ' i
!
Apri 1 23, 1990
GCMS Staff
LM-RMA-3013:
Th following corrections will be done by the admin. staff:
1. Complete SOP# in section 1. Scope and Application
2. Correct degrees notation in document.
3. Correct references to Enseco QAPP from Rev. 3.2 to Rev. 3.3.
4. Correct spelling section 8.6.3 form to from.
5. Correct ref. to CLPSOW dates (update to 1988} Section 12.2.4.1.
,d $ The following corrections will be done by the GCMS staff.
-~ ~~ -~ 1. Need more detail on sonicator use, or reference a seperate SOP on ~-f sonicator use. Section 8.3.3.4. de)cft, JU,,J:i«..;l-S".J,3, 15
{. · 2; GPC cleanup is referencecYto section 8.5. Section 8.5 is "Screening
\ Extracts". Need to include somewhere or as seperate SOP.
~ 3. Section 8.10.10 Data package should also include prep sheets and level
1 review sheets.
LM RMA-3001.
1-Need appeRdices.
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subject or Title:
STANDARD .
OPERATING·
PROCEDURE
Page 1 of 64 -- --
GC/MS Analysis of Semivolatile Organics
SOP No.: LM-RMA-3013 BNA 625
Supersedes: r1 . . 11
V/'vl.rM' o.-,,...d
1. Scope and Application
Revision No.:
1.0
LM-12 MA-300.;;i_
Effective Date:
12/01/89
Capillary GC/MS is used to analyze a wide range of extractable organic
.compounds in a variety of matrices. Although the method for preparation of
samples is dependent on the matrix, most aspects of the instrumental
analysis are not dependent on the matrix or compounds to be determined,
consequently the scope of the method may be extended to include quantitative
analysis of extractable, chromatographable compounds not explicitly listed
in Appendix A provided they are amenable to analysis as semivolatiles and a
standard is analyzed and evaluated for those compounds.
Several Analytical Test References are contained in Appendix F. The
Analytical Test References document analyses currently performed at RMAL
which deviate in target compound; list, analytical protocol and/or data
package requirements from those specified in Appendix A and Sections 8.7
through 12.3.
' The applicability of this Standard Operating Procedure LM-RMA-3013 to
particular matrices and/or analytical requests not specifically stated in
this S.O.P. is determined by the::Gc/MS department manager and communicated
to the client manager. The GC/MS department manager has the authority to
make modifications to the S.O.P. for certain matrices and/or analyses if his
technical judgment deems it necessary and appropriate.
1.1 Analytes: Quantitative analysis is performed for the compounds listed
in Appendix A. Qualitative analysis by mass spectral identification
can be performed on other extractable, chromatographable compounds.
Date:
Date:
Date:
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page __1__ of~
LM-RMA-3013 BNA 625
Revision No.:
1.0
Effective Date:
12/01/89
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1.2 Reporting Limits: For most compounds, the instrument reporting limit I
is 10 ug/mL. The extraction recovery of some compounds and
consequently their detection limits depend on the sample matrix (e.g.
soil, water, waste). The detection limit also depends on the I
characteristics of individual samples. All aspects of this S.O.P.
assume target compounds will be found and quantitated at levels within
the specified range of calibration for each analysis. Therefore, if a
sample contains a high concentration of target compounds or a large I
amount of interfering material, it will be diluted prior to analysis. .
This increases the reporting limit proportionally to the dilution. If
the sample extract is diluted to 10% (i.e. 1:10 dilution) or less, the I
surrogates and spiked compounds will be diluted to levels below
reporting limits and will not be reported. Refer to Appendix A for HSL
(Hazardous Substance List) and PP (Priority Pollutant) semivolatiles I
and their nominal reporting limits for each matrix. Refer to Appendix
F for summaries of other common analyses performed at RMAL. Included
in each Analytical Test Summary is the typical range of calibration for 1 analytes.
1.3 Applicable matrices: Water, soil, solids, sludge, waste and TCLP
leachates (Toxicity characterization leaching procedure.) I 1.4 Dynamic range: Analytes can typically be quantitated between 5ug/mL
and 160 ug/mL. Samples which exceed this concentration range for any I
analyte in Table A-1 should be diluted to be within the dynamic range
of the method. Sample extracts should also be diluted when any other
semivolatile component of the sample exceeds this range. Reporting
limits will be adjusted to reflect the dilution performed. ,1
1.5 Analysis time: Approximate analytical time is 50 minutes per GC/MS
run. The time required for data reduction will be dependent upon the
complexity of the sample.
2. Method Summary
2.1 Aqueous samples are extracted with dichloromethane (methylene chloride)
into base/neutral and acid fractions. The base/neutral and acid
fractions are concentrated and combined for quantitative and/or
qualitative capillary GC/MS analysis.
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SOP No.:
LM-RMA-3013 BNA 625 Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page 3 of 64 ---
Effective Date:
12/01/89
2.2 Solid samples are extracted:with an appropriate solvent. The extract is
concentrated and then analyzed by capillary GC/MS for quantitative
and/or qualitative identification.
3. Comments
3.1 All deviations made from this SOP should be approved by the supervisor and be well documented.
3.2 All reusable glassware should be solvent rinsed prior to use.
3.3 Care should be taken not to 'introduce contamination into the samples.
Particular attention should .be paid to selecting a protective glove
that does not contribute contamination during sample preparation.
3.4 pH adjustments required for the preparation of aqueous samples are
critical. Analyte recoveries can be adversely affected if the pH of
the sample is not sufficiently basic or acidic.
4. Safety Issues
I 4.1 The toxicity or carcinogenicity of each chemical used in this procedure
has not been precisely defined, however, each chemical compound should
·be treated as a potential health hazard. From this viewpoint, exposure
to these chemicals should be reduced to the lowest possible.
4.2 A Material Safety Data Sheet (MSDS) is available for all laboratory
standard and reagent chemic~ls. The appropriate MSDS must be read
before handling the chemical(s).
4.3 All laboratory personnel should be thoroughly familiar with the
laboratory Safety Manual and:Hazard Communication Standard before
undertaking any laboratory work.
5. Sample Collection, Preservation, ·containers and Holding Times
5.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not
SOP No.:
lM-RMA-3013 BNA 625
Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page 4 of 64 ---
Effective Date:
12/01/89
be pre-rinsed with sample before collection. Automatic sampling equipment must be as free as possible of Tygon tubing and other potential sources of contamination. Solid samples should be collected in wide mouth glass jars.
5.2 All samples must be iced or refrigerated at 4°C from the time of collection until extraction.
5.3 All aqueous samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction. Soil/waste samples must be extracted within 10 days of collection and completely analyzed within 40 days of extraction.
5.4 Refer to Enseco, Inc. QA Program Plan for Environmental Chemical Monitoring Rev. 3.3, Sections 4-5 and Appendix I for more information.
6. Apparatus
6.1 Separatory funnel -2 l, with Teflon stopcock.
6.2 Filtering Funnel -75 mm top diameter.
6.3 Pyrex glass wool
6.4 Disposable 1 ml pipet
6.5 Concentrator tube, Kuderna-Danish -10 ml graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test.
6.6 Evaporative flask, Kuderna-Danish -500 ml (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
6.7 Snyder column, Kuderna/Danish -Three ball macro (Kontes K-503000-0121 or equivalent).
6.8 Vials -2 ml capacity with Teflon-lined screw cap suitable for GC autosampler.
6.9 Boiling chips -Approximately 10/40 mesh.
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6.10 Water bath -Heated, wit~ c~ncentric ring over cover, capable of
temperature control (! 2 C). The bath should be used in a hood.
6.11 Top loading balance capable of accurately weighing 0.01 g.
6.12 Analytical balance capable of accurately weighing 0.0001 g.
6.13 Spatula -stainless steel or teflon
6.14 Soni ca tor - A horn-type sonicator equipped with a titanium tip should
be used.
6.15 Sonabox -Recommended with above disrupters for decreasing cavitation
sound.
6.16 Gas Chromatograph for screening - A capillary chromatography system
suitable for splitless injection and all required accessories such as
syringes, analytical columns, gases, flame ionization detector, and
recording device. A data system is recommended for data acquisition,
integration and output. ·
6.17 Nitrogen evaporation device equipped with a water bath that can be
maintained at 35-40°C.
6.18 Continuous liquid-liquid extractors-equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication.
' 6.19 Capillary column. One of the following or an approved substitute
should be used.
6.19.1 J&W 30 m DB-5, 0.25 mm id, 0.25 um film thickness
6.19.2 Quadrex 25 m Methy Phenyl (5%) Silicone, 0.25 mm id, 0.5
um film thickness.
6.19.3 Restec 30 m RTX-5, 0.32 mm id, 1.0 um film thickness.
6.20 Syringes and/or micro pipets -10 uL, 25 ul, 50 ul, 100 uL, 500 uL and
1 ml, as appropriate for making injections, adding internal standard
and preparing sample diluti~ns.
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6.21 Gas Chromatograph/Mass Spectrometer
6.21.1 Gas chromatograph: An analytical system that includes a
temperature-programmable gas chromatograph suitable for
splitless injection including all required accessories such as
syringes, columns, and gases.
6.21.2 Mass spectrometer: Capable of scanning from 35 to 500 amu
every 1 sec or less, using 70 volts (nominal) electron energy
in the electron impact ionization mode.
6.21.3 GC/MS interface: An interface that allows direct coupling of
the capillary column and adequate analyte response.
6.21.4 Data system: A computer system must be interfaced to the mass
spectrometer which will allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained
throughout the analytical run. The software should be capable
of producing extracted ion profiles and integrating these
abundances. The EPA/NIH (NBS) Mass Spectral Library should
also be available on the system.
7. Reagents and Standards
7.1 Reagent water -Carbon filtered house distilled water. Interferents
not observed at or above the reporting limit of the parameters of
interest.
7.2 Sodium hydroxide solution (10 N)-Dissolve 40 g NaOH in reagent water
and dilute to 100 ml.
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7.3 Sulfuric Acid (1+1)-Slowly add 50 ml of H2S04 (ACS sp. gr. 1.84) to 50 I
ml of reagent water.
7.4 Acetone, methanol, methylene chloride -Pesticide quality or I
equivalent.
7.5 Sodium sulfate-(ACS), anhydrous. Granulated for drying extracts, I
powdered for extracting soil samples.
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7.6 Surrogate standard spiking solution. (See Appendix B)
7.7 Laboratory Control Sample standard spiking solution. (See Appendix B).
7.8 GC calibration standard. (See Appendix B)
7.9 Internal standard solution. (See Appendix B)
7.10 Calibration standard solutions. (See Appendix B) I 8. Procedure
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8.1 Scheduling Samples for Extraction
8.1.1 Samples will be scheduled for extraction by the section
supervisor. Samples should be scheduled for preparation
according to the following priorities:
a) Meet holding times
b) Meet promised due date
8.2 Preparation of Water Samples
NOTE: ALL GLASSWARE MUST BE SOLVENT RINSED BEFORE USE.
RINSE WITH ACETONE AND METHYLENE CHLORIDE.
8.2.1 Emulsion test. This test is performed if a sample contains
particulate matter. ' It is used to determine 1f the sample w1l l
be extracted using a separatory funnel or a continuous liquid-
liquid extractor. ·
8.2.1.1 3-4 ml of sample is transferred to a 12 ml screw top
glass vial with a Teflon liner.
8.2.1.2 Approximately 1 ml of CH2Cl2 is added. The vial
should be shaken vigorously for about 30 seconds and
the layers allowed to separate.
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8.2.1.3 If no emulsion forms, the prep should proceed with the I
shakeout technique in Section 8.2.2.
8.2.1.4 If an emulsion forms, the prep should proceed with the I
continuous extractor technique in Section 8.2.3.
8.2.2 Separatory Funnel Extraction (Shakeout Technique)
8.2.2.1 Samples that are clearly described as ground waters in
the project folder are decanted from any sediment in
the bottle, all others are mixed by shaking the
bottle.
8.2.2.2 If the sample is in a larger bottle or requires
decanting, a 1 L graduated cylinder is used to measure
the sample volume. The sample is poured into a 2 L
separatory funnel.
8.2.2.3 If the sample does not require decanting and is in a 1
Lor smaller bottle, the water meniscus is marked on
the side of the sample bottle and used to measure the
sample volume. The sample is then poured into a 2 L
separatory funnel. After the sample bottle is rinsed
with methylene chloride (Section 8.2.2.11), the
sample volume used is measured by adding tap water to
the bottle to the marked level. The volume added is
measured with a graduated cylinder.
8.2.2.4 The volume of each sample is recorded on the
benchsheet.
8.2.2.5 For blanks and quality control samples, 1 L of carbon
filtered water is poured into the separatory funnel.
8.2.2.6 For matrix specific QC, 1 L of the appropriate sample
required for each QC sample is poured into a
separatory funnel. If insufficient sample is
available to use at least 500 ml per aliquot, the
supervisor is consulted. The volume of sample used
for each portion is recorded on the benchsheet.
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8.2.2.7
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1 ml of the surrogate standard spiking solution is
added to each sample and QC sample using a 1 ml
disposable pipet, making sure the pipet tip is below
the surface of the sample while the standard is being
added. The sample is mixed immediately by stoppering
and shaking the separatory funnel. The addition of
the surrogate spiking solution is noted on the bench
sheet, including who added it and the date and by whom
the standard was made.
8.2.2.8 0.5 ml of the DCS or matrix standard spiking solution
is added if appropriate, using the procedure described
in 8.2.2.7.
8.2.2.9 The pH is checked by removing a small aliquot of the
sample with a pasteur pipet, placing enough of the
sample on a pH paper to thoroughly soak the paper.
The pH paper is compared with the chart on the
container and the initial pH is recorded on the prep
sheet.
8.2.2.10 The pH is adjusted to )12 with 10 N NaOH and the
adjusted pH is noted on the prep sheet.
8.2.2.11 For samples that were mixed before pouring, 60 ml
methylene chloride (CH2Cl2) is added to the sample
container to rinse the inner walls. The solvent is
then transferred to the separatory funnel. For
samples that were decanted, the first aliquot of
CH2Cl2 is added directly to the separatory funnel.
8.2.2.12 The sample is extracted by shaking it for two minutes
with frequent ventilation. The layers are allowed to
separate. If there is an emulsion it is broken up
using one of several techniques. The optimum
technique will depend upon the sample, and may
include: stirring, centrifugation, filtration through
glass wool or other physical methods. If the emulsion
cannot be broken, the sample must be transferred to a
continuous extractor. See section 8.2.3.
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8.2.2.13 After separation, the bottom layer (CH2Cl2) is drained
into a 400 ml beaker.
8.2.2.14 The extraction is repeated twice more using a 60 ml
aliquot of CH2Cl2 each time. The solvent is collected
in the same beaker described in 8.2.2.13.
8.2.2.15 The pH is then adjusted to < 2.
NOTE: THIS pH ADJUSTMENT IS CRITICAL. PHENOL
RECOVERIES MAY BE LOW IF THE pH IS NOT LESS THAN 2.
8.2.2.16 The extraction is repeated another three times at the
acidic pH using a 60 ml aliquot of CH2CL2 each time.
The solvent is collected in the same beaker described in 8.2.2.13.
8.2.2.17 A plug of glass wool is placed in a funnel and the
funnel is filled about 2/3 full with granular Na2S04.
The funnel and Na2S04 are rinsed with 30-40 ml of
CH2Cl2 which is discarded after being used for
rinsing.
8.2.2.18 The sample extract is poured through the Na2S04 into a
500 ml Kuderna-Danish (K-D) evaporative concentrator.
The beaker which contained the extract and the Na2S04
in the funnel are rinsed with small amounts of CH2Cl2.
These rinses are added to the K-D.
8.2.2.19 A boiling chip is added to the K-D and a 3-ball
Snyder column is attached to the top. The column is
prewet by adding about 1 ml of CH2Cl2 to the top of
the Snyder column.
NOTE: THE CONCENTRATION STEP IS CRITICAL; LOSSES OF
TARGET COMPOUNDS CAN OCCUR IF CARE IS NOT TAKEN.
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8.2.3
8.2.2.20 The K-D is placed in a 95°C hot water bath so that the
receiver tube is immersed in hot water below the joint
and the entire lower rounded surface is bathed in
steam. At a proper rate of distillation, the balls of
the column will actively chatter, but the chambers
will not flood. When the apparent volume reaches 5-10
ml, the K-D is removed from the bath and allowed to
cool completely.
8.2.2.21 When the K-D has cooled, the column and flask are
rinsed with a small amount of CH2Cl2. The extract is
transferred to a calibrated 15 ml centrifuge tube,
rinsing with a small amount of CH2Cl2. It is
important to rinse all of the ground glass joints of
the K-D well, as compounds collect on the ground
glass.
8.2.2.22 The extract is carefully concentrated to 1.0 ml under a gentle stream of nitrogen using the N-evap
apparatus. The temperature of the water bath should
be 35-40°C. If the extract is highly colored, forms a
precipitate, or stops evaporating, the supervisor is
consulted before the procedure is continued.
8.2.2.23 The extract is transferred to a labelled autosampler
vial with Teflon lined cap. The meniscus is marked and
the extract is placed on a tray in the BNA extract
refrigerator with any other samples having the same QC
Lot number. The tray number is recorded on the
outside of the prep folder containing the bench
sheets.
8.2.2.24 As the final step, the prep sheet fs completed for the
extraction and concentration steps.
Continuous Extractor
8.2.3.1 The continuous extractor is set up in a hood or well-
ventilated area.
SOP No.:
lM-RMA-3013 BNA 625
8.2.3.2
8.2.3.3
8.2.3.4
8.2.3.5
8.2.3.6
8.2.3.7
Revision No.:
1.0
250 ml of CH2Cl2 is placed in a
a few boiling chips are added.
added to the extractor flask.
STANDARD
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round bottom flask and
300 ml of CH2Cl2 is
500 ml of carbon filtered water is carefully poured
into the extractor, minimizing the disturbance of the
solvent layer and preventing water from entering into
either sidearm by pouring the water down the back of
the extractor.
The pH of the sample is checked by removing a small
aliquot with a pasteur pipet, placing enough of the
sample on a pH paper to thoroughly soak the paper.
The pH paper is compared with the chart on the
container and the initial pH is recorded on the prep
sheet.
Samples that are clearly described as ground waters in
the project folder are decanted from any s.ediment in
the bottle, all others are mixed by shaking the
bottle.
If the sample is in a larger bottle or requires
decanting, a 1 l graduated cylinder is used to measure
the sample volume. The sample is then carefully
poured into the extractor flask.
If the sample does not require decanting and is in a 1
l or smaller bottle, the water meniscus is marked on
the side of the sample bottle and later used to
measure the sample volume. The sample is carefully
poured into the extractor flask. After the sample
bottle is rinsed with methylene chloride (section
8.2.2.11), the sample volume used is measured by
adding tap water to the bottle to the marked level.
The volume added is measured with a graduated
cylinder.
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Revision No.:
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8.2.3.8 The volume of each sample is recorded on the
benchsheet.
8.2.3.9 For blanks and quality control samples, 1 l of carbon
filtered water is poured into the extractor flask.
8.2.3.10 For matrix specific QC, 1 l of the appropriate sample
required for each QC sample is measured into the
extractor flask. If insufficient sample is available
to use at least 500 ml per aliquot, the supervisor is
consulted. The volume of sample used for each portion
is recorded on the bench sheet.
8.2.3.11 Sufficient carbon filtered water is added to the
extractor to allow the solvent in the removable
sidearm to begin to drip into the round bottom flask.
It is important that the extractor stays in a strictly
vertical position.
8.2.3.12 1 ml of the surrogate spiking solution is added to
each sample and QC sample using a 1 ml disposable
pipet, making sure that the tip of the pipet is below
the surface of the liquid in the extractor as the
standard is being added. The sample is mixed
immediately using a glass stirring rod. The addition
of the surrogate spiking solution is noted on the
bench sheet, including who added it and the date and
by whom the standard was made.
8.2.3.13 0.5 ml of DCS or matrix spike mix is added if
appropriate, using the procedure described in 8.2.3.12
8.2.3.14 The pH is adjusted to )12 with 10 N NaOH, stirring the
sample carefully with a glass rod. If an excessive
amount of NaOH is used (more than about 15 ml), this
is recorded along with the adjusted pH on the prep
sheet.
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Revision No.:
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8.2.3.15 The condenser is wiped clean with solvent at the lower
joint and lip and then placed on the top of the
extractor. The water chiller (set at 10°C) is turned
on and flow indicators checked.
8.2.3.16 The heating mantle beneath the round bottom (rb) flask
is turned on and the extraction starting time is
recorded on the bench sheet. The extractor is checked
after 15 minutes to ensure it is operating correctly
and that there are no leaks.
8.2.3.17 The extraction is allowed to proceed for a minimum of
eighteen hours.
8.2.3.18 The heating mantle is turned off and the apparatus is
allowed to cool (30-60 minutes) with water flowing
through the condenser.
8.2.3.19 The solvent contained in the round bottom flask is the
base/neutral extract. The flask is removed, capped,
refrigerated and replaced with a clean round bottom
flask containing 250 ml CH2Cl2 and a few bolling
chips.
8.2.3.20 The condenser is removed and the pH is adjusted to < 2.
NOTE: THIS pH ADJUSTMENT IS CRITICAL. PHENOL
RECOVERIES MAY BE LOW IF THE pH IS NOT LESS THAN 2.
8.2.3.21 Steps 8.2.3.16-8.2.3.19 are then repeated for the acid
extraction.
8.2.3.22 The solvent contained in the round bottom flask is the 1 acid fraction. The round bottom flask is removed,
_capped and refrigerated.
8.2.3.23 The contents of the extractor are poured into a
separatory funnel to separate the water from the
methylene chloride. The water layer from the
extractor flask is discarded into the sink with plenty
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of cold tap water.
extractor flask is
bottle.
The solvent layer from the
discarded into a contaminated waste
8.2.3.24 The drying and concentration steps are similar to
those described in section 8.2.2.17 to 8.2.2.18. Due
to the larger volume of solvent the base/neutral
fraction must be concentrated first to an apparent
volume of 10-15 ml. Then a new boiling chip is added
and the acid fraction is poured through Na2S04 into
the same K-D. The concentration is then completed as
described in sections 8.2.2.19 to 8.2.2.23.
8.2.3.25 As the final step, the prep sheet is completed for the
extraction and concentration steps.
8.3 Preparation of Soil Samples
8.3.1 Percent Moisture Determination (optional)
5-10 g of the sample is added to a tared weighing dish. The wet
weight of the sample is recorded. The weighed sample is allowed
to dry overnight at 105°C and then reweighed. The dry weight
of the sample is recorded, correcting for weight of the
weighing dish. The percent moisture of the sample is then
calculated using equation 10.2.7.
8.3.2 pH Determination (optional)
50 g of sample is transferred to a 100 ml disposable beaker.
50 ml of water and a teflon-coated magnetic stirring bar are
added and the beaker is stirred for one hour on a magnetic stir
plate. The pH of the sample is determined with glass electrode
and pH meter while stirring. The pH value is reported on
appropriate data sheets.
8.3.3 Extraction by Sonication Technique
NOTE: ALL GLASSWARE MUST BE SOLVENT RINSED BEFORE USE.
RINSE WITH ACETONE AND METHYLENE CHLORIDE.
STANDARD
OPERATING
PROCEDURE
Page 16 of 64
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8.3.3.1 Any water layer on a sediment sample is discarded.
Samples are mixed thoroughly, discarding any foreign
objects such as sticks, leaves and rocks.
8.3.3.2 Approximately 30 g (to the nearest 0.1 g) of sample is
weighed into a 250 ml bottle. 60 g of anhydrous
powdered sodium sulfate is added and mixed well. 100
ml of 1:1 methylene chloride-acetone is added to the
sample, followed by 0.5 ml of surrogate spiking
solution. The addition of the surrogate spiking
solution is noted on the bench sheet, including who
added it and the date and by whom the standard was
made.
8.3.3.3 1.0 ml of the DCS or matrix spike mix is added, if
appropriate, using the procedure described in Section
8.3.3.2.
8.3.3.4 The bottom surface of the tip of the sonicator horn is
placed about 1/2 inch below the surface of the solvent
but above the sediment layer.
8.3.3.5. The sample is sonicated for 1 1/2 minutes.
8.3.3.6 The solvent layer is decanted into a rinsed 400 ml
beaker.
8.3.3.7 The extraction is repeated twice more using 100 ml
aliquots of 1:1 CH2Cl2-acetone for each extraction
making certain that the sodium sulfate is free flowing
and not a consolidated mass. As required, large lumps
are broken up with a clean spatula. These extracts
are collected in the the same beaker described in
8.3.3.6.
8.3.3.8 A funnel is plugged with glasswool and filled 2/3 full
with Na2S04.
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8.3.3.9 A boiling chip is added to the K-D and a 3-ball
Snyder column attached to the top. The column is pre-
wet by adding about 1 ml of CH2Cl2 to the top of the
Snyder column.
NOTE: THE CONCENTRATION STEP IS CRITICAL; LOSSES OF
TARGET COMPOUNDS CAN OCCUR IF CARE IS NOT TAKEN.
8.3.3.10 The K-D is placed in a heated water bath set at 95°c
so that the receiver tube is immersed in hot water
below the joint and the entire lower rounded surface
is bathed in steam. At the proper rate of
distillation, the balls of the column will actively
chatter, but the chambers will not flood. When the
apparent volume reaches 5-10 ml, the K-D is removed
from the bath and allowed to completely cool.
8.3.3.11 After the K-D has cooled, the Snyder column and flask
are rinsed with a small amount of methylene chloride.
The extract is transferred to a calibrated 15 ml
centrifuge tube, rinsing the K-D flask with a small
amount of methylene chloride. It is important to
rinse all of the ground glass joints of the K-D well,
as compounds collect on the ground glass.
8.3.3.12 The extract is carefully concentrated to 1.0 ml under
a gentle stream of nitrogen using the N-evap
apparatus. The temperature of the water bath should
be 35-4ooc. If the extract is highly colored, forms a
precipitate, or stops evaporating, a supervisor is
consulted before the procedure is continued.
8.3.3.13 The extract is transferred to a labelled autosampler
vial with Teflon lined cap. The meniscus is marked and
the extract is placed on a tray in the BNA extract
refrigerator with any other samples having the same QC
Lot number. The tray number is recorded on the
outside of the prep folder containing the bench
sheets.
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Revision No.:
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Effective Date:
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8.3.3.14 The prep sheet is completed for the extraction and concentration steps.
8.3.3.15 If GPC cleanup is required, see section 8.5.
8.3.4 Other Extraction Techniques
8.4 Preparation of Sludge Samples
8.4.1 Approximately 10 g of sample is weighed into a pre-weighed aluminum weigh boat and allowed to air-dry overnight. The percent moisture is determined using equation 10.2.7.
8.4.2 A continuous extractor is set-up as described in Sections 8.2.3.1 to 8.2.3.4.
8.4.3 Weigh the bottle containing the sample and carefully transfer {insert approximate amount of sample used} g of the sample to the extractor flask. Re-weigh the bottle, calculate the difference, and record it as the amount extracted on the prep sheet.
8.4.4 The continuous extractor method is followed as described in Sections 8.2.3.9 to 8.2.3.26.
8.5 Screening Extracts
8.5.1 Chromatographic conditions.
8.5.1.1 Column: 15 m DB-5, 0.25 mm id, 0.25 um: or equivalent
8.5.1.2 Temperature Program: 50°(1)-20°/min-280°C
8.5.2 Inject 1 ul of the GC Calibration Standard on the screening GC. I This solution contains 50 ug/ml of phenol, phenanthrene, and di-n-octyl phthalate. The response of phenanthrene should be approximately 50% full scale deflection (FSD). The response of 1 di-n-octyl phthalate should be) 25% FSD. . ... ·
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8.5.3 For water samples screen only if the extract is colored. If
the extracts were not combined during the concentration step,
screen both fractions. If there are no non-surrogate peaks
greater than 400% of the peak height of the phenanthrene peak
in either fraction, submit as is. If either fraction has peaks
greater than 400% of the peak height of the phenanthrene peak,
dilute both fractions so that the largest peak is approximately
four times the peak height of phenanthrene, i.e., both
fractions will always have the same dilution factor. Note the
dilution factor on the benchsheet.
8.5.4 If acid and base/neutral fractions were not combined in the
concentration step, combine 0.5 ml aliquots of each fraction in
one autosampler vial. Clearly label as BNA with the sample
number.
8.5.5 For solid samples screen the extract at an appropriate volume
(i.e. a clear extract may be screened at 1 ml; a dark extract
at 10 ml.) Adjust final volume such that the largest non-
surrogate peak is between 200% and 400% of the phenanthrene
peak. Note the dilution factor on the benchsheet.
8.5.6 Put aliquot of any dilutions performed in a labeled autosampler
vial. If any of the undiluted extract remains, label and store
this autosampler vial with the dilution.
8.6 Instrument Set-Up for the GC/MS
8.6.1 Chromatographic Conditions
8.6.1.1
8.6.1.2
Column: See section 6.19.
Temperature Program:
Initial Temperature:
Initial hold time:
Temperature ramp:
Final temperature:
*Final hold time:
30°c
1 minute
10°c/min
325°C
10 minutes
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*The final hold time should be adjusted according to the retention time of the final compound in the standard.
8.6.1.3 These parameters are verified and/or changed using the· DESC procedure for the Finnigan 4500's or GC method for the Finnigan Incos 50 instruments.
8.6.2 Mass Spectrometer Parameters:
8.6.2.1 Mass range: 35-500 amu
8.6.2.2 Scanning rate: 0.75 second/scan
8.6.2.3 Zone temperatures:
Injection port:
Transfer line:
Manifold temperature:
Source temperature:
(if applicable)
250°c
215°c
100°c
150°c
8.6.3 Acquisition Parameters (Program ACQU)
Consult your supervisor if your acquisition parameters differ from the following:
minimum peak width = 3 minimum area = 30 threshold = 1
8.7 File Naming Conventions
For each semivolatiles instrument, the filenames for DFTPP, calibration standards, QC samples and client samples acquisitions are based on the use of common prefix abbreviations followed by instrument letter designation and a consecutive integer progression from 001 to 999. This numeric portion of the filename is commonly referred to as the "run number". When the run number on a particular instrument reaches 999, the progression begins again with 001.
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Filenames are recorded in the instrument log book at the time of data
acquisition along with other pertinent sample information (e.g. project
& sample number, extract dilution, and analyst's initials and date of
acquisition).
8.7.1 The filename for DFTPP uses the prefix DF followed by
instrument letter designation and run number (next consecutive
integer -up to 999 -in instrument log book).
For Example:
DFU006 is the filename for DFTPP analyzed on instrument U at
run number 006 in the consecutive integer count maintained in
the log book for instrument U.
8.7.2 The filenames for standards use the prefix STD followed by
instrument letter designation and run number (next consecutive
integer -up to 999 -in instrument log book).
For Example:
STDU007 is the filename for a standard analyzed on instrument U
at run number 007 in the consecutive integer count maintained
in the log book for instrument U.
8.7.3 The filenames for QC samples (Refer to Section 9. for a
discussion of DCS and Blank. QC Samples) use either the prefix
DCS or Blank, depending on the type of QC sample, followed by
instrument letter designation and run number (next consecutive
integer -up to 999 -in the instrument log book).
For Example:
DCSU008 is the filename for a Duplicate Control Sample (DCS)
analyzed on instrument U at run number 008 in the consecutive
integer count maintained in the log book for instrument U.
8.7.4 The filenames for client samples use the prefix S followed by
the RMA project number, instrument letter designation and run
number (next consecutive integer -up to 999 -in the
instrument log book).
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For Example:
S6450U009 is the filename for a sample belonging to RMA project number 6450, run on instrument U at run number 009 in the consecutive integer count maintained in the log book for instrument u.
8.8 Instrument Calibration
8.8.1 DFTPP
8.8.1.1 Each GC/MS MUST be hardware tuned to meet the EPA ion abundance criteria for DFTPP. The instrument tune MUST be verified at the start of every 12 hours of operation or as specified by client contract. Ion abundance criteria are listed in Appendix C, Table C-l.
8.8.1.2 50 ng of DFTPP is directly injected into the GC using the following chromatographic conditions:
Initial temperature:
Initial hold:
Rate:
Final temperature:
175°c
1 min
35°C/min
250°c
DFTPP will generally elute between scans 250-450.
8.8.1.3 The spectrum of DFTPP is evaluated for overall intensity and ion abundances. Ion abundance criteria given in Table C-1 must be met. Averaging scans across the peak and reasonable background subtraction is ac€eptable. Manipulations which will distort the spectrum, such as excessive background subtraction, are not acceptable.
8.8.1.4 If the ion abundance criteria are not met, the instrument must be retuned and DFTPP reinjected.
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8.8.1.5 If the ion abundance criteria are met, daily
instrument calibration may proceed. Hardcopies of the
DFTPP spectrum, mass list and ion abundance summary
are kept on file for QC purposes.
8.8.2 Initial Calibration
An initial calibration must be performed before analysis of
sample extracts can begin. This consists of a five point
calibration curve for all of the analytes listed in Appendix A.
Standard solutions are prepared at concentrations of 20 ug/mL,
50 ug/ml, 80 ug/ml, 120 ug/ml and 160 ug/ml.
Certain compounds have been selected to monitor instrument
performance. These compounds are identified as System
Performance Check Compounds (SPCC) and Calibration Check
Compounds (CCC).
The average response factor for each System Performance Check
Compound (SPCC) MUST be greater than 0.05.
The percent relative standard deviation (%RSD) for or equal to
each Calibration Check Compound (CCC) MUST be less than or
equal to 30%. The %RSD for all compounds should also be
reviewed. Any values greater than 50% should be evaluated
before analyses are continued.
If samples are NOT being analyzed for these specific compounds,
the criteria for these compounds need not be met. The fact
that these compounds are not in the analyte set should be
documented.
See Table C-2 for a summary of CCC and SPCC criteria.
8.8.2.1 The following five standard solutions are analyzed:
50 ug/ml, 20 ug/ml, 80 ug/ml, 120 ug/ml and 160 ug/ml.
For each standard to be analyzed, a 1-2 uL injection
is made under the conditions specified in 8.7.
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8.8.2.2 Immediately following the analysis of the 50 ug/ml standard, the data acquired should be processed and evaluated to ensure that certain criteria are met before proceeding with initial calibration.
8.8.2.2.1
, 8.8.2.2.2
To minimize saturation in the higher level standards, the peak area of the quantitation ion for the 1st internal
standard, d4-1,2-dichlorobenzene, should be between 10,000 and 30,000 counts, depending on the instrument. If the peak area is outside these limits, the analyst should adjust the electron multiplier
and re-inject the 50 ug/ml standard. (DFTPP criteria must first be met under the new instrument operating conditions. See Section 8.9.1).
The SPCC limits MUST be verified. If the response factor of an SPCC compound is (0.05, a supervisor should be consulted to determine if corrective action will be taken.
8.8.2.3 The following target compounds are at 100 ug/ml in the 50 ug/ml standard:
Benzi dine
3,3'-Dichlorobenzidine
8.8.2.4 The concentration of acid surrogate compounds is 100 ug/ml. The concentration of base/neutral surrogate compounds is 50 ug/ml. The concentration of internal standard compounds is 40 ug/mL.
8.8.2.5 The quantitation list is reviewed to ensure that the internal standards are correctly identified and that the analytes are properly quantitated. The following compounds should be checked for proper integration:
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Benzy l Alcohol
Benzoic Acid
4-Nitrophenol
4-Nitroaniline
Benzo(b &/or k)fluoranthene
Indeno(l,2,3-cd}pyrene
Dibenzo(a,h}anthracene
Benzo(g,h,i}perylene
These compounds do not chromatograph well,
particularly as a column is used.
8.8.2.6 Structural isomer pairs are checked for correct peak
assignment. Identification is based on elution order,
as they appear in the library. These pairs are:
2,4,6-/2,4,5-Trichlorophenol
Anthracene/Phenanthrene
Chrysene/Benzo(a)anthracene
Benzo(b)/Benzo(k)fluoranthene
8.8.2.7 If the standard evaluation criteria have been met, the
component libraries are updated with the response
factors and retention times of the 50 ug/ml standard
just analyzed •
8.8.2.8 Each of the other standards analyzed should be
evaluated in the same manner as the 50 ug/ml standard
with particular attention focused on the "troublesome"
compounds noted in Sections 8.9.2.5 and 8.9.2.6. Some
additional compounds in the 120 and 160 ug/ml
standards may need to be manually quantitated due to
poor chromatography at higher concentrations.
8.8.2.9 Following analysis and evaluation of the 5 calibration
standards, a table which lists each standard's
response factors, the average RF and% RSD's for all
compounds is generated using the RMA program RFAC.
Refer to Appendix E for examples of the initial
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calibration table and a continuing calibration table. The% RSD's for CCC compounds and the average response factors for SPCC compounds are then evaluated. Compounds having% RSD's greater than 30% are checked to verify accuracy of quantitation for each standard. Individual response factors which differ greatly from the compound average are also investigated.
8.8.2.10 If all CCC and SPCC criteria are met, the data are stored in an initial calibration file. This file is then referred to during continuing calibration. Quan lists are then copied to unit 1.
8.8.3 Continuing Calibration
The 50 ug/ml standard is used as the continuing calibration standard. It MUST be analyzed for each 12 hour period immediately following a successful DFTPP analysis.
The response factor of each CCC compound should be compared to the initial calibration average response factor. A table which lists the initial calibration average response factors, cont 1 nui ng ca 11 bra ti on response factor.s and % differences for all compounds is generated for comparison using the RMA procedure RFAC. See Appendix E for an example of this table. The percent difference for each CCC compound should be less than or equal to 25% for analysis to proceed. Deviations from the specified criteria for continuing calibration are allowed, provided a supervisor is informed and rationale is well documented. Response factors for all analytes should be reviewed. Any significant deviations from the initial calibration should be evaluated before analyses are continued. (e.g. deviations of greater than 50%)
All SPCC criteria should be met (i.e. RF) 0.05).
8.8.3.1 A 1 or 2 ul injection of the 50 ug/ml standard is made under the conditions specified in Section 8.7.
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8.8.3.3
8.8.3.4
8.8.3.5
8.8.3.6
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The 50 ug/ml continuing calibration standard should be
evaluated and quantitation checked as outlined in
Sections 8.9.2.2 through 8.9.2.6.
The continuing calibration standard is compared to the
initial calibration curve by generating the table
described in Section 8.9.3. The CCC and SPCC
compounds are evaluated as outlined in Section 8.9.3.
If any large percent differences between initial and
continuing calibration response factors are noted,
the peak assignment and integration for these
compounds should be checked.
If the standard evaluation criteria are NOT met, and
analyses to be performed require meeting SPCC & CCC
criteria then corrective action must be taken.
Corrective action may include replacement of injection
port liner, cutting a portion off the front end of the
column, or replacing the column. If corrective action
is taken, the instrument must be recalibrated
beginning with injection of DFTPP (See Section 8.9.1.2
through 8.9.1.3)~ Following successful analysis of
DFTPP, the 50 ug/ml continuing calibration standard is
reinjected. If deviations between initial and
continuing calibrations still exist, a new initial
calibration may need to be performed (See Section
8.9.2).
If these criteria are not met and the decision is made
to continue analysis, the rationale must be documented
by the individual making that decision. This
documentation must be kept on file with the continuing
calibration record.
If the standard evaluation criteria have been met or
the decision has been made to continue, the component
libraries are updated with the response factors and
retention times of the continuing calibration standard
just analyzed.
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8.9 Sample Analysis
8.9.1 Scheduling
8.9.1.1 Analyses are scheduled by the supervisor or a senior
operator and assigned to analysts on a daily basis.
8.9.1.2 A LIMS generated semivolatile sample backlog is used
for prioritizing sample analyses and for recording the
status of analyses, (e.g. prep completed, analysis in
progress, analysis completed). The analytical test
(i.e. target compound list) required is indicated on
the sample backlog. Modifications to the normal
analytical protocol, such as low detection limits,
special compounds or special criteria are also flagged
on the backlog and pertinent information is accessed
by the analyst or supervisor via LIMS.
8~9.2 Extract Preparation
8.9.2.1 Extracts are located in numbered trays stored in the
BNA extract refrigerator. The tray number for a given
set of samples is recorded on the project folder for
those samples.
8.9.2.2 Appropriate sample extract vials are located by the
analyst and placed in the semivolatiles hood for
aliquoting. Acid and B/N fractions are combined if
necessary and the internal standard solution (400
ug/ml) is added to each extract aliquot at a ratio of
1:10 resulting in I.S. concentration of 40 ug/ml in
the extract. The vial is then marked with the letters
"WIS" (with internal standard) to indicate the
addition of internal standard.
8.9.2.3 The syringe is rinsed with CH2Cl2 between each use.
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8.9.2.4 The prepared extracts are then transferred to the
appropriate instrument for analysis. If the samples
are to be acquired using an autosampler {rather than
being injected and acquired manually by the analyst),
the vials are placed in the autosampler (either HP or
Varian) rack as per the manufacturer's instructions.
8.9.3 Data Acquisition
8.9.3.1 Samples are analyzed using the same instrument
parameters as the calibration standards. (conditions
specified in Section 8.7)
8.9.3.2 Sample data can be acquired manually as a single run
(analysis) or as a series of runs in an automated
sequence of samples. Two custom RMA procedures
programs which utilize the Finnigan ACQU command are
used for data acquisition. The RMA procedure DOIT
allows the analyst to set acquisition parameters and
input sample header information for manual acquisition
of a single sample. The RMA procedure ATAQ enables
the analyst to set acquisition parameters and input
sample header information for a series of samples.
The ATAQ procedure automatically coordinates sample
acquisition with the autosampler, the GC ready
condition, and sample header information and filename.
The analyst is responsible for making sure extract
vials are placed in the autosampler rack in the order
intended for analysis and that sample header
information and filenames are loaded into the computer
in the correct sequence as well.
8.9.3.3 If a limited list of compounds is being used, the
analysis time may be shortened, as appropriate to the
compounds being analyzed.
8.9.3.4 Filenames, sample identification information (project
number and sample number, e.g. 6450-02), extract
dilution, analyst's initials and date of analysis are
recorded by the analyst in the instrument log book.
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8.9.4 Analysis Sequence
8.9.4.1 QC samples (refer to Section 9 for a discussion of DCS
and blank samples) should be analyzed and QC criteria
met before client samples from that QC Lot number can
be analyzed. See Section 9 for QC criteria for DCS
and blank samples.
8.9.4.2 If QC criteria are met, client samples will be
analyzed according to scheduling priority. Matrix
spikes, matrix spike duplicates, and sample duplicates
when available are analyzed in conjunction with the
associated samples.
8.9.4.3 If the QC criteria are not met, the supervisor is
informed and the decision to reprep samples from the
QC lot or to continue analysis is made and documented.
(See Section 9.)
8.10 Data Processing & Reduction & Data Package Assembly
"The analyst who generates the analytical data has the prime
responsibility for the correctness and completeness of the data."
Quote from Enseco, Inc. QAPP for Env. Chem. Monitoring, Rev. 3.3.
For a general overview of Enseco data reduction, validation and
reporting guidelines from a quality assurance standpoint refer to
Enseco, Inc. QAPP for Env. Chem. Monitoring, Rev. 3.3, Section 8.
8.10.1 Following sample data acquisition, each sample data file is 1 processed using the RMAL procedure TC which utilizes Finnigan
AUTOQUAN software and semivolatile component libraries
developed by RMAL. A number of "Library Lists" -subsets of
the semivolatile libraries -reside on each instrument computer ·•
and are selected by the analyst for use in conjunction with the
procedure TC to generate a data package for each sample that
specifically covers the target compound list (analytical test) I
requested by the client. In addition to processing one data
file at a time using TC, a batch of data files can be processed
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8.10.2
automatically using the RMAL procedure AUTOB. For more
detailed instructions on using the RMAL procedure "TC" to
process data files, refer to "RMAL GC/MS Software Manual" (Ver.
6/28/88).
The data package generated contains the following print outs:
8.10.2.1 Log Page
Included on this page are the header information, GC
conditions, scan parameters, and instrument tuning
parameters that were used at the time of data
acquisition.
8.10.2.2 Chromatogram
Included on this page is the header information and
the reconstructed ion chromatogram displaying the
range of scans used during data acquisitions.
8.10.2.3 Diagnostic Report
Included on this page is a table of library entry
numbers and chromatographic and library search
information used in the computerized target compound
evaluation. In addition, if any peak found is
saturated, this is flagged on the diagnostic report.
8.10.2.4 Quantftation Report
Included fn this section fs the list of target
compounds, internal standards and surrogate standards
used for processing the datafile and their
corresponding library entry numbers. This section
contains (1) chromatographic information such as
retention times (scan numbers) and relative retention
times and (2) quantitation information such as peak
areas, updated library response factors, and
quantitated amounts for the library entries.
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8.10.2.5 Quantitation Summary
This summary page lists the internal standards in elution order, followed by base/neutral surrogates in e 1 ut ion order, acid surrogates in e 1 uti on order,. and then all target compounds searched for by the processing routine, also in elution order. Tabulated with each compound are the library entry number, quantitation mass, indication of reference internal standard, and for those compounds with amounts calculated to be) 1.0 ug/ml, peak area, scan number (directly related to R.T.) at which peak maximized, calculated response factor and quantitated amount. Those compounds not found by the processing routine or with amounts calculated to be< 1.0 ug/mL are flagged with the words "not found".
8.10.3 For each processed data file the following steps should be taken:
8.10.3.1 Internal standard retention times should be reviewed and compared to the daily (continuing calibration) standard. No internal standard retention time should vary more than 30 seconds from the daily standard. If this occurs, the chromatographic system should be checked and corrections made as necessary. Affected samples will be reanalyzed.
8.10.3.2 Internal standard areas should be reviewed and I compared to the daily standard. An internal standard comparison report should be generated using the RMA program "ISCHK" and placed permanently into the log 1 book. The ,areas should not vary by more than a factor of two (50% to 200% of daily standard internal standard area) from the daily standard. If the areas do vary by more than a factor of two, the analyst I should first check to see if the peak has been correctly integrated. If the area is still outside
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the limits, the system should be checked and corrected
if necessary. The sample should be reanalyzed once
problems with the GC/MS system have been corrected.
If, upon verification that the instrument is operating
properly, the areas are still outside of the limits
both analyses will be submitted with the data package
and the actions taken documented by the analyst.
8.10.3.3 Surrogate standard amounts should be reviewed to
verify acceptable surrogate recoveries. If any one
acid and/or base/neutral surrogate falls outside the
acceptable recovery limits, the quantitation should be checked.
8.10.3.3.1 If the quantitation is correct, the
unacceptable surrogate recovery and
affected sample(s) should be shown to a
supervisor. Once a decision is made to
use the. data or submit for a reprep, all
action should be documented on the
anomaly sheet.
8.10.3.3.2 If more than one acid and/or base/neutral
surrogate is outside the acceptable
recovery limits, the quantitation should
be checked. If the quantitation is
correct, the analyst should inform a
supervisor and the affected sample(s) may
be submitted for repreparation. The
analyst should document all action taken
on the anomaly sheet used for analysis.
8.10.3.4 The same general guidelines outlined in sections
8.9.2.5 and 8.9.2.6 regarding "troublesome" compounds
and structural isomers should be followed whenever any
of these compounds are found in a sample by the
processing routine.
8.10.3.5 Target compound amounts should be reviewed to verify
that the quantitated amounts are within the upper
linear range of calibration (160 ug/ml +/-10%).
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8.10.3.5.1 If any target compound amounts appear to be greater than the upper limit, the quantitation should be checked by the analyst. If quantitation is correct, the sample extract must be diluted appropriately and reanalyzed for the target compound involved. The initial run may be used for any target compound data which fall within the linear range of calibration (10 ug/ml -160 ug/ml).
8.10.3.5.2 The diagnostic report (see Section 8.11.2.3) should also be reviewed for any peak saturation of target compounds. If any target compound peak is saturated, the quantitation should be verified by the analyst and the sample extract diluted appropriately and reanalyzed. 8.10.4 Spectra Verification
The data processing routine (TC) generates a "scan list" file for each data file which contains the scan numbers for all I target compounds found in the sample at amounts) 1.0 ug/ml (i.e. all target compounds listed on the data processing quantitation summary, Section 8.11.2.5). Following initial 1 processing of a datafile, the RMAL procedure NDUAL is used to hardcopy the unenhanced and enhanced spectra for all scans in the scan list. In addition to hardcopying spectra for one data file at a time using NDUAL, a batch of data files' spectra can I be hardcopied automatically using the RMAL procedure AUTOS.
Prior to qualitative identification of target compounds in a I sample, "standard" mass spectra of known identity should be obtained on the instrument(s) used for sample analysis. Hardcopies of mass spectra from a calibration standard (e.g. 50 1 ug/ml continuing calibration standard) run on the instrument under similar tuning conditions would serve this purpose.
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8.10.4.1 Each mass spectrum generated for a sample data file should be compared to the standard spectrum. EPA criteria for qualitative identification by comparison of mass spectra should be followed. The EPA criteria for comparing spectra are:
8.10.4.1.1 All ions present in the standard spectrum at a relative intensity greater than 10% of the base peak MUST be present in the sample spectrum.
8.10.4.1.2 The relative intensities of the ions specified in (1) must agree within plus or minus 20% between the standard and sample spectra. (Example: For an ion with an abundance of 50% in the standard spectrum, the corresponding sample ion abundance must be between 30% and 70%.)
8.10.4.1.3 Ions greater than 10% in the sample spectrum, but not present in the standard spectrum must be considered and accounted for by the analyst making the comparison. If the analyst can easily identify a co-eluting compound (e.g. an alkane or a surrogate spike compound) then the sample spectrum should be labeled with the contaminant.
8.10.4.2 When a spectra meets the criteria listed in Section 8.11.4.1 the compound name in the header should be circled. All spectra that do not meet the EPA criteria should have the compound name crossed out in the header, and the corresponding entries on the quantitation summary should be crossed out (line out the amounts calculated for those compounds which are not "hits") by the analyst making the judgment. If a compound cannot be verified by all of the criteria listed in 8.11.4.1, but in the technical judgment of the analyst the identification is correct, the compound should be reported. If the analyst is uncertain of an identification, a senior operator or a supervisor should be consulted.
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8.10.5 Summary Sheets
A number of summary sheets are computer generated at the instrument following data file processing and pulling (hardcopying) target compound spectra. These summaries include:
8.10.5.1 Target Compound Summary (also referred to as "sum sheets" or "sums")
This one-or two page summary is generated with the RMAL procedure "SUMI" and tabulates pertinent information about a sample analysis including header information (e.g. sample number, dilution used for analysis, sample matrix), date analyzed, analyst's initials, run factor (refer to calculations in Section 10.1.1), final reporting units, surrogate% recoveries, target compounds listed in elution order, and target compound CAS #'s when available. For those target compounds with amounts) 1.0 ug/ml in the extract the scan number, amount listed on quantitation summary (i.e. concentration in the analyzed extract ug/ml) and concentration in sample (expressed in final reporting units, usually ug/1 for waters and ug/kg for soils) are tabulated.
8.10.5.2 DCS Summary
(Refer to Section 9 for discussion of DCS QC samples)
This one-page summary is generated with the RMA procedure DCS and tabulates pertinent information about the DCS samples representing a specific QC lot. The information tabulated includes QC lot number, matrix (soil or water), date analyzed, analyst's initials, DCS data file numbers, list of samples belonging to the QC lot, names of spike components and QC limits for spike% recoveries and RPD's, calculated amount and percent recovery for each spike compound in both DCS samples, and calculated RPO between the two
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DCS recoveries for each spike component. Percent
recoveries and RPD's that fall outside the acceptable
QC limits are flagged with asterisks and require
further action by the analyst (see Section 9). When
generating the summary sheet it is imperative that the
analyst input the complete list of samples belonging
to the QC lot for QC tracking purposes. This
information can be found in the QC summary notebook
kept in the prep lab.
8.10.5.3 SCS Summary
{Also referred to as "SCS Summary"-see section 9 for
discussion of SCS QC samples)
This one page summary tabulates pertinent information
about the SCS sample representing a specific·
analytical lot {also called "QC" or "SCS" lot) of
client samples including QC lot number, matrix (soil
or water), date analyzed, analyst's initials, SCS data
file number, list of samples belonging to the SCS lot,
names of surrogates and QC limits for surrogate%
recoveries, and calculated amount and% recovery for
each surrogate. Percent recoveries that fall outside
the acceptable QC limits are flagged with asterisks
and require further action by the analyst (see Section
9). When generating this summary sheet, it is
imperative that the analyst input the complete list of
samples associated with the SCS sample for QC tracking
and data reporting (blank subtraction) purposes. This
information can be found in the QC summary notebook
kept in the sample preparations laboratory.
8.10.6 Library Searches {Optional)
Some·data packages will include mass spectral library searches
on non-target compounds (excluding internal standards,
surrogates and spikes) as outlined in contract requirements or
requested by the client. If the library searches (also
referred to as "TIC's" or Tentatively Identified Compounds) are
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necessary to the data package, the 20 largest unidentified peaks that are greater than 10% of the peak (RIC) area of the nearest uninterfered internal standard will be searched against the NBS library for possible matches.
8.10.6.1 The generation of TIC data is partially automated through the use of several RMA procedures which perform the following functions:
1.
2.
3.
4.
5.
6.
7.
Select non-target, unidentified peaks from the chromatogram for tentative identification,
Quantitate unknown peaks using RIC area of closest uninterfered internal standard as reference peak and a response factor of 1.0 (See calculations, Section 10.2.11),
Perform and generate hardcopy mass spectral library searches on the unknown peaks (searching against the NBS library of mass spectra),
Select preliminary "Best Match" spectra from the library searches and tabulate them with quantitation information for all unknowns,
Allow editing of computer's final selections for compound names,
Allow manual quantitation of unusually shaped peaks,
Generate final summary w1th amounts calculated to reflect concentration in sample (i.e., run factor applied).
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8.10.6.2 Listed below, in the order that they are generally
used by the analyst, are the RMA procedures used for
TIC generation and their main functions:
TICP -Used to verify and/or change peak selection
criteria (e.g. can specify to search all
unknown peaks )10% internal standard RIC area.
TICl -Generates TIC data (hardcopies of library
search-spectra and quantitation information
page) for one data file.
TIC -Generates TIC data (hardcopies of library
search spectra and quantitation information
page) for a batch of data files.
TICQS-Allows for manual quantitation by the analyst.
TICE -Allows the analyst to edit the names of
compounds selected and generates final TIC
summary page after input from the analyst.
8.10.6.3 After reviewing each library search spectrum, the
analyst should indicate the compound name selected by
labelling the spectrum or circling the correct name
(if it appears on the library search spectrum as one
of the computer"s selections). If the compound is to
be reported as "Unknown" (See Section 8.11.6.5) the
spectrum should be labelled as such.
8.10.6.4 The EPA criteria to be used for making these decisions
for tentative identifications are as follows:
8.10.6.4.1 Relative intensities of major ions
present in the library spectrum at a
relative intensity greater than 10% of
the base peak should be present in the
sample spectrum.
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8.10.6.4.2 The relative intensities of the ions specified in (1) must agree within plus or minus 20% between the library and sample spectra. (Example: For an ion with an abundance of 50% in the standard spectrum, the corresponding sample ion abundance should be between 30% and 70%.)
8.10.6.4.3 Molecular ions present in the library spectrum should be present in the sample spectrum.
8.10.6.4.4 Ions present in the sample spectrum, but not present in the standard spectrum should be considered and accounted for by the analyst making the comparison. If the analyst can easily identify a co-eluting compound (e.g. an alkane or a surrogate spike compound) then the sample spectrum should be labelled with the contaminant.
8.10.6.4.5 Ions present in the library spectrum but not in the sample spectrum should be reviewed for possible subtraction from the sample spectrum because of background contamination or coeluting compounds.
8.10.6.5 If in the technical judgment of the analyst, no valid 1 tentative identification can be made, the compound should be reported as "Unknown." If possible, assign additional compound class information (e.g. unknown hydrocarbon). The analyst should consult with a more I experienced analyst or a supervisor if there are questions concerning compound identification.
8.10.6.6 For more detailed instructions on the generation of TIC data using the RMA TIC procedures, refer to "RMA GC/MS Software Manual", version 6/28/88.
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8.10.7 Reconstructed Ion Chromatogram
The RIC generated by data file processing should be labelled to
identify internal standards, surrogates, spikes if applicable,
target compounds and tentatively identified compounds (if
library searches are performed -see Section 8.11.6). For
industrial, non-contract work, the abbreviations IS -internal
standard, SS -surrogate standard, SP or SC -spike compound,
TC -target compound, and TIC -tentatively identified
compound, are sufficient. In contract work the internal
standards and surrogates are usually labelled with the compound
names; the abbreviations SC, TC and TIC are normally
sufficient for contract work for spike compounds, target
compounds and tentatively identified compounds ,provided a
legend is clearly indicated on each chromatogram page. Refer
to Appendix F for more specific criteria.
8.10.8 Anomaly Sheet
Each data package submitted by the analyst for secondary review
must include an anomaly sheet summarizing any problems or
unusual circumstances incurred during sample analysis. If no
problems were encountered during analysis, the analyst must
still submit an anomaly sheet to that effect. All anomaly
sheets must be singed by a supervisor.
8.10.9 QC Summary Sheets (DCS & SCS)
Each data package submitted for secondary review must include
copies of DCS and SCS summary sheets for all QC related to the
sample set in the data package.
8.10.10 Summary of Data Package Requirements
When initial data review has been completed by the analyst, the
data package should be assembled to include the following:
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Anomaly Sheet
DCS Summary Sheet
SCS Summary Sheet
SCS Target Compound Summary Sheet, TIC Summary and Data
Out-of-Control forms
(if necessary -See Section 9) Sample Raw Data
Sample Target Compound Summaries
(Attached to sample raw data)
TIC Data & Summary (when requested)
In some cases, contract requirements or client requests will necessitate including tuning and calibration information (i.e. DFTPP), daily standard raw data and initial & continuing calibration response factor tables. Refer to Appendix F for specific data package criteria.
8.10.11 Upon completion of the data package assembly and review, the data package is passed on to the data review specialist for secondary review.
9. QA/QC Requirements (See SOP no.: M-EQA-002)
9.1 DCS. Laboratory Control Samples are extracted and analyzed for every 20 samples. DCS components and spike concentrations are given in Appendix D. For aqueous samples, DCS components are spiked into organic-free water. For solid samples, the DCS components are spiked into the extraction solvent. No solid matrix (sand or Celite) is incorporated since ·there is no true representative solid matrix.
9.2 SCS. A Surrogate Control Sample is analyzed with every analytical lot. This sample serves as the method blank. An analytical lot for extractable organics is defined as samples extracted or prepared at the same time up to a maximum of 20 samples. An SCS sample is also referred to as an SCS.
SCS components and spike concentrations are given in Appendix D.
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9.3
9.4
9.5
9.6
Blank. For this method the blank and the SCS are one and the same. In
order for data associated with an SCS to be acceptable, blank values
for target compounds must be acceptable. If the blank (SCS) contains
target compounds at values above the reporting limit, the supervisor
should be consulted.
If the blank value lies between the reporting limit and three times the
reporting limit, the reporting limit is adjusted to the level found in
the blank.
Surrogates spiked into samples. Surrogate compounds are
spiked into all samples and QC samples for this method.
spike mix concentrations are given in Appendix D.
required to be
Surrogate
Matrix specific QC. Matrix spike and matrix spike duplicates are
performed at the request of the client. Matrix spike compounds will be
the same as those used for the DCS. · See Appendix D. These compounds
will be spiked into aliquots of the sample specified by the client at
the same concentration level as the DCS.
Data acceptability is initially based upon the results of the Duplicate
Control Samples. If DCS criteria is not in control, consult a
supervisor and document any corrective action and/o~ alternative data
acceptability criteria on an Out-of Control form. QC data must fall
within established control limits in order for the laboratory to be
considered "in control" when samples from that QC lot were analyzed.
9.6.1 At least 80% of the DCS recovery data, and at least 80% of the
DCS precision data and at least 80% of the SCS recovery data
must be within established control limits in order for the
laboratory to be considered "in control". Blank values must be
acceptable. (See Section 9.3) For this method the maximum
number of values permitted outside control limits are
DCS:
SCS:
recovery
4
1
precision
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9.7 Control Limits: Control limits will be determined as described in SOP No.: M-EQA-002. At a minimum, CLP limits must be met. These limits are listed in Table D-2. Current historical limits generated by the laboratory will be available through LDMS.
10. Calculations
10.1 Calculations required to reduce data
10.1.1 Acid and B/N run factors (rf):
Vf (ml) 100% rf = ------X
(Column ----------x Clean up
Where
Vi (L or kg) (% Dilution of extract
used for analysis)
Vf = final extract volume as prepped
Factor)
Vi = initial sample volume (or weight) used for extraction
Column Volume available for clean up Clean up=
Factor Volume put through column
10.1.2 Expected (theoretic) Acid and B/N surrogate and/or spike concentrations in extract (TSC):
TSC =
Where
Cs =
Cs (Ug/mLl x Vs (ml)
Vf (ml)
(% Dilution of 1
x extract used x -------for analysis) (Column Clean
up Factor)
TSC = theoretic surrogate or spike concentration in extract
concentration of surrogate or spike in mix
Vs = volume of surrogate mix or spike mix spiked into sample during extraction procedure
10.2 Calculations required to verify automated data reduction
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10.2.1 Response factors (RF):
Ax x Cis (Ug/ml)
RF = --------
Ais x Cx (Ug/ml)
where Ax= area of characteristic (quantitation) ion for the compound to be measured
Ais= area of characteristic (quantitation) ion
for the reference internal standard
Cis= concentration of the internal standard
Cx = concentration of the compound to be
measured
10.2.2 Average Response Factor (RFavel:
10.2.3
(RF20 + RFso + RFao + RF120 + RF150)
RFave =
5
Where RFx = response factor of a compound in each of
the calibration standards
Percent Relative Standard Deviation (%RSD}:
SD
%RSD = ---X 100
RFave
Where SD= standard deviation of individual initial
calibration response factors (per
compound)
and where
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10.2.4 Percent Deviation from average response factor (%D):
RFr -RFc %D = ----X 100
RFr
where RFr = average response factor from initial calibration
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RFc = response factor from current calibration daily standard I
10.2.5 Percent Recovery (%Rec):
Spikes -
SSR (Ug/ml) -SR (Ug/ml) %Rec= -----------x 100 TSC (Ug/ml)
Where SSR = spiked sample results
SR = sample results
Surrogates -
TSC = theoretic spike concentration
%Rec=
SR (Ug/ml)
TSC (Ug/ml)
X 100
Where SR = surrogate concentration
(results in sample)
TSC = theoretic surrogate concentration
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10.2.6 Relative Percent Difference (RPO):
D1 -Dz RPO = ------x 100
(01 + Dz)/2
Where 01 = first sample value
Dz= second sample value (e.g. duplicate or
matrix spike duplicate)
10.2.7 Percent moisture
( sample ( sample
Wet wt plus dish) -Dry wt plus dish)
%moisture = ------------------x 100
Wet wt (sample plus dish)
10.2.8 Analyte concentration in an aqueous sample
ug Ax x Cis (Ug/ml) ml
Concentration (--) = -------x rf (--)
Where
L Ais x RF L
Ax = area of quantitation ion for compound being
measured
Ais = area of quantitation ion for reference internal
standard
Cis = concentration of internal standard in sample
extract
RF = response factor for compound being measured
from ongoing (continuing) calibration standard
rf = run factor (See 10.1.1)
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10.2.9 Analyte concentration in a soil sample (wet weight)
ug Ax X Cis (LIQ/ml) ml
Concentration (--) = -------x rf (-·-)
Where
kg Ais x RF kg
Ax, Ais, Cis, RF, rf = same as given for water in
10.2.8
10.2.10 Analyte concentration in a soil sample (dry weight)
ug Ax X Cis (LIQ/ml) 1 Concentration (-) =------x-----X
(1-%moi sture)
100
ml
rf(-)
kg
Where
kg Ais x RF
Ax, Ais, Cis, RF, rf = same as given for water in
10.2.8
and% moisture as defined in 10.2.7
10.2.11 Tentatively identified compound concentration in
sample
ug ug RICx X Cis (LIQ/ml) ml ml Concentration (-or -) = -------x rf (-or-)
Where RICx
l kg RICis x 1.0 l kg
= area of reconstructed ion chromatogram for
unknown compound being measured
RICis= area of reconstructed ion chromatogram for
closest uninterfered internal standard
Cis = concentration of internal standard in sample
extract
rf = run factor for sample extract as analyzed
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11. Reporting requirements
11.1
11.2
11.3
Units: Aqueous samples will be reported in ug/L. Solid and
sludge samples will be reported in ug/kg on a wet
weight basis, unless requested otherwise by the
client.
Reporting limits:
See Appendix A
Significant Figures:
All data <10 ppb will be reported with one significant figure.
All other data will be reported with two significant figures.
11.4 LDMS data entry
12. References
12.1 Method Source:
Solid Waste and
1986.
Method 8270, SW-846 Third Edition, USEPA, Office of
Emergency Response, Washington, DC 20460, September
12.2 Deviations from Source Methods
12.2.1 Daily (continuing) calibration is considered to be valid for 12
hours from time of injection of DFTPP.
12.2.2 Deviations from the specified criteria for initial and
continuing calibration are allowed, provided the rationale is
documented.
12.2.3 An internal QA/QC program has been adopted by Enseco, Inc.
This is described in Enseco's "Quality Assurance Program Plan
for Environmental Chemical Monitoring" (Rev. 3.3). Specific
elements of the QC program are described in SOP NO. M-EQA-002:
"Internal QC Checks--Laboratory Performance QC." The
·Laboratory Control Samples generated in this program are used
to monitor method performance. Matrix spikes are performed at
the request of the client.
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12.2.4.1 USEPA Contract Laboratory Program Statement of Work I 10/86 Rev:1/88, 2/88, 7/88
12.2.4.2 RMAL GC/MS Software Manual (Ver. 6/28/88) I 1
12.2.4.3 Enseco, Inc. Quality Assurance Program Plan for Environmental Chemical Monitoring (Rev 3.2). I
APPENDIX A Analytes & Detection Limits
Analyte
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzyl a lcoho 1
1,2-Dichlorobenzene
2-Methylphenol
bis(2-Chloroisopropyl)ether
4-Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
Benzoic acid
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
TABLE A-1 HSL LIST
Detection Limit
Water (09/mL) Soi 1 (Ug/mL)
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
50
10
10
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
1600
330
330
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TABLE A-1
Analyte
1,2,3-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroani line
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethyl phthalate
4-Chlorophenylphenyl ether
Fluorene
4-Nitroanil ine
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenylphenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Revision No.:
1.0
HSL LIST {Cont.)
Detection
Water (09/mL)
10
10
10
10
10
10
10
10
50
10
50
10
10
50
10
50
50
10
10
10
10
10
10
50
50
10
10
10
50
10
10
10
10
10
STANDARD
OPERATING
PROCEDURE
Page _il__ of ...§1_
Limit
Effective Date:
12/01/89
Soil (LI9/mL)
330
330
330
330
330
330
330
330
1600
330
1600
330
330
1600
330
1600
1600
330
330
330
330
330
330
1600
1600
330
330
330
1600
330
330
330
330
330
SOP No.:
LM-RMA-3013 BNA 625
Butyl benzyl phthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Revision No.:
1.0
10
20
10
10
10
10
10
10
10
10
10
10
STANDARD
OPERATING
PROCEDURE
Page __il_ of~
Effective Date:
12/01/89
330
660
330
330
330
330
330
330
330
330
330
330
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SOP No.:
LM-RMA-3013 BNA 625
TABLE A-2
Analyte
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
l,3~Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
bis(2-Chloroisopropyl)ether
N-Nitroso-d1-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
b1s(2-Chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-3-methylphenol
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2-Chloronaphthalene
Dimethyl phthalate
Acenaphthylene
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethyl phthalate
STANDARD
OPERATING
PROCEDURE
Page -2l.._ of _.&i_
Revision No.:
1.0
PRIORITY POLLUTANT LIST
Detection Limit
Effective Date:
12/01/89
Water (09/mL) Soil (LIQ/ml)
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
50
50
10
10
10
330
330
330
330
330
330
. 330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
1600
1600
330
330
330
SOP No.:
LM-RMA-3013 BNA 625
TABLE A-2
Analyte
4-Chlorophenylphenyl ether Fluorene
4,6-Dinitro-2-methylphenol
1,2-Diphenylhydrazine
N-Nitrosodiphenylamine
4-Bromophenylphenyl ether Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butyl phthalate Fluoranthene
Pyrene
Butyl benzyl phthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo. (g, h, i) peryl ene
Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page 54 of 64
Effective Date: 12/01/89
PRIORITY POLLUTANT LIST (Cont.)
Detection
Water {□9/ml)
10
10
50
10
10
10
10
50
10
10
10
10
10
10
20
10
10
10
10
10
10
10
10
10
10
Limit
Soi 1 (LIQ/ml)
330
330
1600
330
330
330
330
1600
330
330
330
330
330
330
660
330
330
330
330
330
330
330
330
330
330
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SOP No.:
LM-RMA-3013 BNA 625 Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page --22..._ of~
Effective Date:
12/01/89
APPENDIX B Standards Solutions
TABLE 8-1
Compound
Nitrobenzene -D5
2-Fluorobiphenyl
Terphyenyl -D14
Phenol -D5
2-Fluorophenol
2,4,6-Tribromophenol
TABLE 8-2
Compound
1,2,4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
N-Nitroso-Di-n-propylamine
1,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Ni tropheno l
SURROGATE STANDARD SPIKING SOLUTION
Concentration in Mix
(□9/mL)
100
100
100
200
200
200
DCS STANDARD SPIKING SOLUTION
(Matrix Spiking Solution)
Concentration in Mix
(09/mL)
100
100
100
100
100
100
200
200
200
200
200
SOP No.:
LM-RMA-3013 BNA 625
TABLE B-3
Revision No.:
1.0
GC CALIBRATION STANDARD
(for Screening)
STANDARD
OPERATING
PROCEDURE
Page --2.§__ of -..£.i__
Effective Date:
12/01/89
BNA-SCS/IS Working Solution
Component
Dichlorobenzene-D4
Naphthalene-DB
Acenaphthene-DlO
Phenanthrene-DlO
Chrysene-D12
Perylene-D12
2-Fl uorophenol
Pheno 1-DS
Tribromophenol
Nitrobenzene-DS
2-Fluorobiphenyl
Terphenyl-D14
Concentration (ug/mL)
8
8
8
8
8
8
10
10
10
5
5
5
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SOP No.:
LM-RMA-3013 BNA 625
TABLE B-4
Compound
04-1,4-Dichlorobenzene
Os-Naphthalene
010-Acenaphthene
D10-Phenanthrene
012-Chrysene
012-Perylene
1) MS-BNAHSL-CSB
Compound
Nitrobenzene-05
2-Fluorobiphenyl
Terphenyl-014
TABLE B-5
05-Phenol
2-Fluorophenol
2,4,6-Tribromophenol
N-Nitrosodimethylamine
Aniline
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzyl Alcohol
1,2-Dichlorobenzene
STANDARD
OPERATING
PROCEDURE
Page .2l._ of~
Revision No.:
1.0
INTERNAL STANDARD SOLUTION
Effective Date:
12/01/89
Concentration in Mix
(09/mL)
400
400
400
400
400
400
CALIBRATION STANDARD SOLUTIONS
Concentration in Mix
(09/mL)
50
50
50
100
100
100
50
50
50
50
50
50
50
50
50
SOP No.:
LM-RMA-3013 BNA.625
TABLE B-5
1) MS-BNAHSL-CSB
Compound
2-Methylphenol
bis(2-Chloroisopropyl)ether
4-Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
Benzoic Acid
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroanaline
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-Nitroanaline
Dimethylphthalate
Acenaphthylene
2,6-Dinitrotoluene
3-Ni troanil i ne
Acenaphthene
2,4-Dinitrophenol
Di benzofuran
Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page 2!L_ of --2.!__
Effective Date:
12/01/89
CALIBRATION STANDARD SOLUTIONS (Cont.)
Concentration in Mix
(LiY/mL)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
. 50
50
50
50
50
50
50
50
50
50
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SOP No.:
LM-RMA-3013 BNA 625
TABLE B-5
1) MS-BNAHSL-CSB
Compound
4-Nitrophenol
2,4-Dinitrotoluene
Diethylphthalate
Fluorene
4-Chlorophenyl-phenyl Ether
4-Nitroanaline
4,6-Dinitro-2-Methylphenol
N-Nitrosodiphenylamine
Azobenzene
4-Bromophenylphenyl Ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Benzi dine
Pyrene
Butylbenzylphthalate
Benzo(a)anthracene
3,3'-Dichlorobenzidine
Chrysene
bis(2-Ethylhexyl)phthalate
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo (a) pyrene
Indeno(l,2,3-c,d)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
STANDARD
OPERATING
PROCEDURE
Page~ of __..2.±.__
Revision No.: Effective Date:
1.0 12/01/89
CALIBRATION STANDARD SOLUTIONS
Concentration in Mix
(DY/ml)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
100
50
50
50
100
50
50
50
50
50
50
50
50
50
The other 4 points in the 5 pt. calibration standard set contain the above list
of compounds at 20 ug/ml, 80 ug/ml, 120 ug/ml and 160 ug/ml, with the exception
of acid surrogates, benzidine and 3,3'-Dichlorobenzidine which are in each mix
at twice the concentration. 1 or 2 uls of each standard is injected.
SOP No.:
LM-RMA-3013 BNA 625
APPENDIX C
Mass
51
68
70
127
197
198
199
275
365
441
442
443
STANDARD
OPERATING
PROCEDURE
Page 60 of 64
Revision No.:
1.0
TABLE C-1
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Ion Abundance Criteria
Effective Date:
12/01/89
30.0 -60.0 percent of mass 198
less than 2.0 percent of mass 69 less than 2.0 percent of mass 69 40.0 -60.0 percent of mass 198 less than 1.0 percent of mass 198 base peak, 100 percent relative abundance 5.0 -9.0 percent of mass 198
10.0 -30.0 percent of ·mass 198 greater than 1.00 percent of mass 198 present but less than mass 443 greater than 40.0 percent of mass 198 17.0 -23.0 percent of mass 442
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STANDARD
OPERATING
PROCEDURE
Page _§l_ of 64
SOP No.:
LM-RMA-3013 BNA 625
TABLE C-2
Revision No.:
1.0
CALIBRATION CHECK COMPOUNDS
Effective Date:
12/01/89
Initial Calibration: The percent relative standard deviation for
the each compound listed below should be ~30%.
Continuing Calibration: The percent deviation from the average
response factor determined in the initial calibration should be
~25% for each compound listed below.
Base/Neutral Fraction
Acenaphthene
1,4-Dichlorobenzene
Hexachlorobutadiene
N-Nitrosodinphenylamine
Di-n-octylphthalate
Fluoranthene
Benzo (a) pyrene
Acid Fraction
4-Chloro-3-Methylphenol
2,4-Dichlorophenol
2-Nitrophenol
Phenol
Pentachlorophenol
2,4,6-Trichlorophenol
SYSTEM PERFORMANCE CHECK COMPOUNDS
Initial calibration: The average response factor for each
compound listed below should be )0.05.
Continuing calibration: The response factor for each compound
listed below should be )0.05.
Base/Neutral Fraction
N-Nitroso-di-n-propylamine
Hexachlorocyclopentadiene
Acid Fraction
2,4-Dinitrophenol
4-Nitrophenol
SOP No.:
LM-RMA-3013 BNA 625
APPENDIX D
Revision No. :
1.0
TABLE D-1
SPIKE LEVELS FOR LABORATORY CONTROL SAMPLES
Spike Level
Aqueous Solid* DCS ( ug/L) (ug/Kg)
Pentachlorophenol 100 6,670 Phenol 100 6,670 2-Ch l oropheno l 100 6,670 4-Chloro-3-Methylphenol 100 6,670 4-Nitrophenol 100 6,670
1,2,4-Trichlorobenzene 50 3,330 Acenaphthene 50 3,330 2,4-Dinitrotoluene 50 3,330 Pyrene 50 3,330 N-Nitroso-di-n-propylamine 50 3,330 1,4-Dichlorobenzene 50 3,330
scs
Phenol-d5 200 3,330
2-Fluorophenol 200 3,330 2,4,6-Tribromophenol 200 3,330
Nitrobenzene-d5 100 1,670
2-fl uorobi phenyl 100 1,670
Terphenyl-d14 100 1,670
*Assumes 30g sample (wet weight)
STANDARD
OPERATING
PROCEDURE
Page ---2£._ of ___.2.i_
Effective Date:
12/01/89
Concentration
in mix
(ug/ml)
200
200
200
200
200
100
100
100
100.
100
100
200
200
200
100
100
100
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SOP No.:
LM-RMA-3013 BNA 625 Revision No.:
1.0
TABLE D-2
CLP RECOVERY & RPO CONTROL LIMITS
Minimum Control
WATER
DCS:
DCS RPO
Pentachlorophenol 9-103 50
Phenol 12-89 42
2-Ch l oropheno l 27-123 40
4-Chloro-3-Methylphenol 23-97 42
4-Nitrophenol 10-80 50
1,2,4-Trichlorobenzene 39-98 28
Acenaphthene 46-118 31
2,4-Dinitrotoluene 24-96 38
Pyrene 26-127 31
N-Nitroso-di-n-propylamine 41-116 38
1,4-Dichlorobenzene 36-97 28
scs WATER
Phenol-d5 10-94
2-Fluorophenol 21-100
2,4,6-Tribromophenol 10-123
Nitrobenzene-d5 35-114
2-Fluorobiphenyl 43-116
Terphenyl-d14 33-141
STANDARD
OPERATING
PROCEDURE
Page ___§l_ of -2±..._
Effective Date:
12/01/89
Limit
SOIL
DCS RPO
17-109 47
26-90 35
25-102 50
26-103 33
11-114 50
38-107 23
31-137 19
28-89 47
35-142 36
41-126 38
28-104 27
SOIL
24-113
25-121
19-122
23-120
30-115
18-137
SOP No.:
LM-RMA-3013 BNA 625 Revision No.:
1.0
APPENDIX A ANALYTICAL TEST REFERENCES
Table of Contents
1 HAZARDOUS SUBSTANCE LIST (HSL)
2 PRIORITY POLLUTANT (PP OR 625)
3 EPA/CLP
4 REFINERY
5 APPENDIX IX
6 APPENDIX VIII
7 TCLP (TOXICITY CHARACTERISTIC LEACHING PROCEDURE)
8 AFIRP VERSION 1
9 AFIRP VERSION 2
10 USGS USGS
11 PAH -PART PER BILLION/FULL SCAN
STANDARD
OPERATING
PROCEDURE
Page __..2i.._ of __..2i.._
Effective Date:
12/01/89
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•----------------,Ensem
STANDARD I s:,i ~~6~~6G~~
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Subject or Title: Page 1 of 11
Total Recoverable, Dissolved and Total Metals: ---
SOP No.:
LH-RMA-2002
Supersedes:
Acid Digestion
(Aqueous samples/EP Tox. extracts)
Revision No.:
2.0
Revision 1.0 (February 13, 1989)
1. Scope and Application
1.1 Anal ytes
Effective Date:
January 22, 1990
These acid digestion methods are used to prepare aqueous samples and
Extraction Procedure (EP) extracts for analysis of a variety of trace
metals by Graphite Furnace Atomic Absorption spectroscopy (GFAA),
Inductively Coupled Argon Plasma spectroscopy (ICP) or Flame Atomic
Absorption spectroscopy (FLAA). Mercury is not included. Refer to
the individual analysis SOPs for specific analytes.
1.2 Reporting Limits
Refer to the individual analysis SOPs.
1.3 Applicable Matrices
These methods are applicable to surface and ground water samples,
industrial and domestic waste samples and EP extract solutions.
1.4 Dynamic Range
Refer to the individual analysis SOPs.
1.5 Analysis Time
The approximate preparation time for one batch of 20 samples and
required QC is approximately 7 hours .for any of the methods. Refer
to the individual analysis SOPs for approximate analysis times.
Prepared by:
Sherman Gray/Will Pratt S~"Z. Date:
January 19, 1990
Date:./ / ,1 t'f ro
Date:
I/ \9 /ci (,,
. I
---------------------------,s....-..A=ARD £nsec6
OPERATING I' PROCEDURE
Total
Page 2 of 11
Recoverable, Dissolved and Total Metals: ---
SOP No.:
lM-RMA-2002
2. Method Surrmary
Acid Digestion
(Aqueous samples/EP lox. Extracts)
Revision No.:
2.0
Effective Date:
January 22, 1990
2.1 A representative 100 ml aliquot of sample is placed into a 250 ml
beaker. Various mineral acids are added and the sample is heated to 950c to effect dissolution:
Total/EP extract. -GFAA: Nitric acid only.
Total/EP extract. -ICP/FlAA: Nitric and hydrochloric acids.
Dissolved/Tot. Recov. -ICP/FlAA: Nitric acid only.
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I NOTE: The standard Enseco procedure for analyzing Dissolved metals
is NOT to digest them unless specifically requested by the client or 1 for other valid reasons as determined by management; as a general
rule, if a sample being analyzed for Dissolved metals is found to
analyzed and the results anomalized. contain sediment or precipitate, the sample will be filtered, ·I
2.2 All samples are cooled, filtered and diluted to a final volume of 100
ml. Anomalies are recorded on the benchsheet and transferred with I
the samples to the analysis area.
3. Corrments
3.1 Interferences I
3.1.1 The most conunon interference is laboratory contamination which I
may arise from impure reagents, dirty glassware, improper
reagent transfering, dirty work areas, etc. Be aware.of
potential sources of contamination and take appropriate I
measures to minimize or avoid them.
3.1.2 Failure to homogenize the sample well prior to removal of the 1 desired aliquot may yield erroneous results.
3.1.3 Allowing samples to boil or go dry during digestion may result
in the loss of volatile metal compounds. I
3.2 Helpful Hints
3.2.1 It is only required to bring samples to within 1% of the I
desired volume. For example, bring a sample digest to within
1 ml of the desired final volume of 100 ml. -----------1
•--------------------------~s~T~AN~D=ARD Enseco
I OPERATING
PROCEDURE
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Page 3 of 11
Total Recoverable, Dissolved and Total Metals: ---
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
SOP No.: Revision No.:
2.0
Effective Date:
LM-RMA-2002 January 22, 1990
4.
3.2.2 Teflon boiling chips should be used when digesting samples
that contain sediment to help prevent them from bumping.
Safety Issues
4.1 Proper protective gear (i.e., safety glasses, face shield, gloves,
and rubber apron) should be worn when using acids.
4.2 All sample transfers and digestions should take place in a properly
vented hood, and spills should be cleaned up imediately.
4.3 Nitric acid and hydrochloric acid are corrosive and will cause skin
irritation. Avoid contact with eyes, skin and clothing. Wash
thoroughly with copious amounts of water.
4.4 All waste generated from the test will be placed into an approved
waste container.
4.5 The RMAL safety manual should be referred to for detailed cautions
and instructions.
5. Sample Collection, Preservation and Holding Times
5.1 Samples should be collected in prewashed glass or plastic containers.
5.2 Total Recoverable and Total Metals -Samples should be acidified with
nitric acid to pH< 2 at the time of collection.
5.3 Dissolved Metals -Samples should be filtered through 0.5 micron
filter and then acidified with nitric acid to pH< 2 at the time of
collection.
5.4 The holding time for all metals analyzed by atomic spectroscopy is
180 days (6 months), except mercury. The preparation and analysis
for mercury is described in SOP LM-RMA-2005.
6. Apparatus
6.1 Hot plate, capable of 1000c.
6.2 Miscellaneous pipettes.
6.3 Miscellaneous benchsheets.
... I
---------------------------S-T-AN-D-ARD Ensec:o
OPERATING I PROCEDURE
Total
Page 4 of 11
Recoverable, Dissolved and Total Metals: ---
SOP No.:
LM-RMA-2002
6.4 Calculator.
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
Revision No.:
2.0
6.5 250 ml glass beakers with watch glass covers.
6.6 Top-loading balance, 0.01 g capability.
6.7 Miscellaneous filter apparatus.
6.8 Plastic bottles (1% HN03 rinsed).
7. Reagents and Standards
7.1 ASTM Type II water, (Milli Q or equivalent).
7.2 Nitric acid, (HN03), concentrated, trace metal grade.
Effective Date:
January 22, 1990
7.3 1% Nitric acid solution: Add 20 ml concentrated nitric acid to
2000 ml Milli Q water. Cap, mix well.
7.4 Hydrochloric acid, (HCl), concentrated, trace metal grade.
7.5 Duplicate Control Standard stock solutions (DCS):
7.5.1 Samples prepared for analysis by Graphite Furnace AAS use the
GFAA duplicate control standard solutions "A" and "8".
7.5.2 Samples prepared for analysis by Inductively Coupled Plasma
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use the ICP duplicate control standard solutions "A", "B", "C" I
and "D".
7.5.3 Samples prepared for analysis by Flame AAS use the ICP
duplicate control standard solutions "A", "B", "C", "D" and I
"E". Consult your supervisor.
8. Procedure
8.1 Instrument Set-up and Calibration
8.1.1 Turn on hot plate, set for 95°c (see SOP: lP-RMA-0053 for
calibration check procedure). Allow 1/2 hour to preheat.
8.1.2 Verify the calibration of the balance and pipettes.
'-----------------------------,s=-=T,.,..ANcc:D'"'"'-ARD £nseco
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Page 5 of 11
Recoverable, Dissolved and Total Metals: ---
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
SOP No.: Effective Date:
LM-RMA-2002
Rev i s ion No. :
2.0 January 22, 1990
8.2 General Preparation
8.2.1 Identify the test and samples to be digested using the
backlogs.
8.2.2 Check the special instructions for each sample and print a
copy if they apply.
8.2.3 Locate and sign out the samples 1n the walk-in cooler. If a
sample cannot be located, consult your supervisor.
8.2.4 Assign a QC Lot Number and fill out the appropriate bench
sheet (separate bench sheets are completed for GFAA and
ICP/FLAA digestions).
8.2.5 Update the backlog to reflect which samples are in progress.
8.2.6 Clearly label each beaker as appropriate (red stickers are
used for GFAA preps and green stickers are used for ICP/FLAA
preps).
8.2.7 Place a labelled 250 ml beaker on a top-loading balance and
tare the balance.
8.2.8 Transfer a 100 +/-1 ml (g) aliquot of homogenized sample into
the beaker. Record any anomalies or comments on the
benchsheet (see attached example).
8.2.9 Proceed to the appropriate section for the desired method:
Section Method
Total/EP Tox. -GFAA .......................... 8.3
Total/EP Tox. -ICP/FLAA •••.•..••••••.•••••••• 8.4
Tot. Recov./Dissolved -ICP/FLAA •••••••••••••• 8.5
8.3 Digestion: Total and EP Toxicity Metals for GFAA
8.3.1 Carefully add 5 ml of concentrated HN03 to the sample/extract
and cover the beaker with a watch glass. Place on hot plate.
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page 6 o 11
Total Recoverable, Dissolved and Total Metals: -
Acid Digestion
(Aqueous samples/EP lox. Extracts)
Effective Date:
mJ
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LH-RHA-2002
Revision No.:
2.0 January 22, 1990
1-
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8.3.2 Allow the sample to reflux and evaporate to low volume (15-20
ml) while swirling occasionally. NOTE: DO NOT let the sample
boil or go dry. Doing so will result in loss of analytes and
the sample must be reprepped.
8.3.3 Remove, cool and carefully add another 5 ml of concentrated
HN03 to the sample.
8.3.4 Return beaker to the hot plate and allow the sample to reflux
and evaporate for 30 minutes. NOTE: DO NOT let the sample
boil or go dry. .
8.3.5 Proceed to section 8.6.
"8.4 'Digestion: Total and EP Toxicity Metals for ICP/FLAA
8:4.1 Carefully add 5 ml of concentrated HN03 to the sample/extract
and cover the beaker with a watch glass. Place on hot plate.
8.4.2 Allow the sample to reflux and evaporate to low volume (15-20
ml) while swirling occasionally. NOTE: DO NOT let the sample I
boil or go dry. Doing so will result in loss of analytes and
the sample will have to be reprepped.
8.4.3 Remove, cool and carefully add another 5 ml of concentrated D
HN03 to the sample.
8.4.4 Return beaker to the hot plate and allow the sample to reflux I
and evaporate for 30 minutes. NOTE: DO NOT ·let the sample
boil or go dry.
8.4.5 Remove, cool and carefully add 5 ml of concentrated HCl to the I
sample.
8.4.6 Return beaker to the hot plate and allow the sample to reflux
and evaporate for 15 minutes. NOTE: DO NOT let the sample
boll or go dry.
8.4-.7 Proceed to section 8.6.
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SOP No.:
Page 7 of 11
Recoverable, Dissolved and Total Metals:
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
Effective Date:
LM-RHA-2002
Revision No.:
2.0 January 22, 1990
8.5 Digestion: Total Recoverable and Dissolved Metals for ICP/FLAA
NOTE: The standard Enseco procedure for analyzing Dissolved metals
is NOT to digest them unless specifically requested by the client or
for other valid reasons as determined by management; as a general
rule, if a sample being analyzed for Dissolved metals is found to
contain sediment or precipitate, the sample will be filtered,
analyzed and the results anomalized.
8.5.1 Carefully add 2 ml of concentrated HN03 and 5 ml concentrated
HCl to the sample, cover the beaker with a watch glass and
place on hot plate.
8.5.2 Allow the sample to reflux and evaporate to low volume (15-20
ml) while swirling occasionally. NOTE: DO NOT let the sample
boil or go dry. Doing so will result in loss of analytes and
the sample must be reprepped.
8.6 Conclusion
8.6.1 Remove and carefully add 10 ml Milli Q water, swirl to mix and
allow to cool.
8.6.2 Label plastic bottles using the available computer program.
8.6.3 Weigh each sample digest bottle and record that weight under
the bottle label. Rinse the bottle with 1% HN03.
8.6.4 Filter the cooled sample through filter paper (Whatman 41 or
equivalent that has been pre-rinsed with 1% HN03) into the
pre-weighed, acid-rinsed poly bottle.
8.6.5 Rinse the beaker, watch glass and the filter paper sparingly,
but well with Milli Q water to ensure complete sample
transfer. See your supervisor for specific technique.
8.6.6 Adjust the sample volume (mass) to 100 ml (g) with Milli Q
water.
8.6.7 Confirm that the bottle cap and bottle are labelled
identically; cap the bottle. The sample is now ready for
analysis.
. I
---------------------------S-TA_N_D-ARD Ensea5
SOP No.:
OPERATING I' PROCEDURE
Page 8 of 11
Total Recoverable, Dissolved and Total Metals: ---
Acid Digestion
(Aqueous samples/EP Tax. Extracts)
Effective Date: LM-RHA-2002
Revision No.:
2.0 January 22, 1990
8.6.8 Complete all paperwork and submit to supervisor for immediate
approval. Release prep test from "Logged" to "Done" in LIMS.
8.6.9 Place samples in a properly labelled box (see attached
example) and deliver to appropriate analysis shelf with all I
•approved" paperwork.
8.6.10 Clean all glassware and work areas thoroughly. I
9. QA/QC Requirements
9.1 QC Samples
9.1.1 A blank shall be prepared for each 20 samples digested or for
each batch, whichever is more frequent. The blank is prepared
by taking 100 ml (g) of Milli Q water and digesting it as
described in the appropriate section.
9.1.2 Duplicate Control Samples (DCS) shall be prepared for each 20
samples digested or for each batch, whichever is more
frequent. These are prepared by spiking 1.0 ml of each of the
DCS stock solutions into 100 ml (g) of Milli Q water and
digesting them as described fn the appropriate section.
NOTE: There are two separate DCS solutions for Graphite
Furnace AA, four separate DCS solutions for ICP, and five
separate DCS solutions for Flame AA digests. Each DCS
solution has its own verification number. See section 7;4.
9.1.3 Client specific sample duplicates (DU), matrix spikes (MS) and
matrix spike duplicates (SD) will be prepared only upon client
request and will then appear on the prep scheduling backlog
sheet.
9.1.4 See SOP: M-EQA-0002 and the Enseco QAPP.
9.2 Acceptance Criteria
Reier to the appropriate RMAL individual analysis SOP for each
specific analyte.
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9.3 Corrective Action Required I
9.3.1 Sample digests which have boiled or gone dry must be reprepped 1 due to the potential loss of volatile metal compounds.
'--------------~= fu5eco STANDARD
I. OPERATING
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Page 9 of 11
Total Recoverable, Dissolved and Total Metals: ---
SOP No.:
LM-RMA-2002
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
Revision No.:
2.0
Effective Date:
January 22, 1990
9.3.2 Follow the corrective actions outlined in the current Enseco
QAPP manual or consult your supervisor.
10. Calculations
The final dilution factor is calculated as follows:
DF = ------
Vi
where DF is the dilution factor, Vf is the final digest volume and
Vi is the initial sample volume.
11. Reporting Requirements
11.1 Data packages will contain the bench sheet and a copy of the special
instructions (where applicable).
11.2 The test, analyst name, prep date, QC lot number, sample number,
acknowledgment of special instructions, anomalies observed, sample
mass, final volume, dilution factor, spike solution verification
numbers and comments are recorded on the prep bench sheet (see
attached example).
12. Review Requirements
NOTE: It is the responsibility of the analyst to perform an initial
review of the prep information as a part of the analysis so as to alert
him to potential problems or difficulties.
12.1 Verify special instructions were followed.
12.2 Verify dilution factors were correctly calculated.
12.3 Verify that anomalies were correctly noted.
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STANDARD
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.PROCEDURE
Enseco
Total Page 10 of 11 Recoverable, Dissolved and Total Metals: ----
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
SOP No.: Effective Date: LM-RMA-2002
Revision No.:
2.0 January 22, 1990
13. References
13.1 Source Methods: Method 3005, "Acid Digestion of Waters for Total
Recoverable or Dissolved Metals for Analysis by FLAA or ICP
Spectroscopy"; Method 3010, "Acid Digestion of Aqueous Samples and
Extracts for Tota 1 Meta 1 s for Analysis by FLAA or ICP Spectroscopy";
and Method 3020, "Acid Digestion of Aqueous Samples and Extracts for
Total Metals for Analysis by GFAA Spectroscopy", SW-846 -Test
Methods for Evaluating Solid Waste, 3rd edition, 1986.
13.2 Related Documents
13.2.1 Method 200.7, "Inductively Coupled Plasma -Atomic Emission
Spectrometric Method for Trace Element Analysis of Water and
Wastes", Methods of Chemical Analysis of Water and Wastes
(MCAWW), EPA-600/4-79-020, March, 1983.
13.2.2 GFAA Metals analysis SOP: LM-RMA-2006.
13.2.3 ICP Metals analysis SOP: LM-RMA-2037.
13.2.4 FLAA Metals analysis SOP: Currently unavailable.
13.2.5 Enseco QAPP, most recent revision.
13.2.6 Enseco SOP: M-EQA-0002.
13.3 Deviations from Source Methods and Rationale
13.3.1 Methods 3010 and 3020 specify multiple 3 ml additions of HN03
until the digestion is "complete". The addition of two (2)
5 ml portions of HN03 has been shown to provide equally
effective digestive action and will continue to be used for
convenience sake.
13.3.2 The analysis of replicate samples (duplicates or "dupes") is
recommended at a frequency of 20% depending on the sample
load. Due to the fact the acceptance criteria have not been
established or recommended, the preparation and analysis of
replicate samples is not practiced, with the exception of DCSs
(section 9.1.2).
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'-----------------------------;S~T~AN;-;;:D=ARD Enseco
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Page 11 of 11
Total Recoverable, Dissolved and Total Metals: ----
Acid Digestion
(Aqueous samples/EP Tox. Extracts)
SOP No.: Effective Date:
LM-RMA-2002
Revision No.:
2.0 January 22, 1990
13.4 Updates to SOP (Revision 1.0 to Revision 2.0)
Revision 2.0 primarily reflects the changes brought about by SW-846,
3rd Edition.
13.4.1 The use of hydrogen peroxide as a digestion reagent has been
eliminated.
13.4.2 The preparation of samples for Total Recoverable Metals
analysis by Graphite Furnace AA (GFAA) has been eliminated.
13.4.3 Format changes including the addition of the Reporting and
Review Requirements sections were effected.
INDUSTRIAL INIJRBANIC CHEIIIBTRY PREP COYER SHEET
p .. fHCP-AT/AR
I
Ana!vst_ S GR.fly ..... Oate_/"9....//lN_9D Lot_.#_ Approved .. ~ .. Oate ........ l/11../ro I
Saaple
Nu1ber
Blan,
ocs 1
ocs 2
I Special I I Instructions? I I I I I
I y I NIA I N I
I .... i -I ...... I
I ...... I ...... I .. _ I
I ...... I ...... I ...... I ..
Anoaalies Observed
!legend belo•l
-I Saaole I Final I Dilution I I
I Nass I Volu■e I Factor I
I lgl I !all I I I {Al I (8) I (8/Al I I
I 100.0 al I 100 ■L X I
I 100.0 al I 100 al
I 100.0 al I 100 al
X I I
1 X i
I I ✓1 .:......+-------'-----~• /~O:.!olJ:.!., o~•~D~tJ;c!'~D+'...!'-i-~-ii I
I I I I
I
....,._.L.._ __________ -4-1......:!~-i·--=~-➔---l-----il I
I 150,ol5:.~.c I I
I i -----1-~--if...L.-1--+--+--!.------------+•,;;;s_;o_;._0~1...,s::::,;z.:...;._;i)_,_::i......--1' I
I I I I
I I I -I 'I -----~f------------1-----+------1'
I I I I I I
... • ---'---+---+-+--+------------+----+-----+-' ---1'1
I
1---------,'1---+-+--+'------....,.,...------+--~'1-----+---!·1 ~...-· I I I I I
.... 1 _-------+-+--+,1-➔1_-____ ' _______ --+---+---+---i11
I ( I . I
I ... -------'--+---'---+--------------1----1----1------l!I
I !
-------+-+---+-.... '-------------1-' ---f'------1':I 1111 I I I
l ! J! ! ! ! I
I I :ii::· I I I I I
Soike Solution Ver; Ii cation nu■bers: (Al .Z: .. Y-XW (8) ... Y...X. .. W..Y.... Cl .xW.. .. V.. .. Ll.... (0), w)l{b_l.. ...... I
Co11ents: .... ?C~p&..d ....... ,4-T $Q. ... ~L-s .......... f .. ~-.:S~!i:'..C.1 J4-/ I . .6!..~T..e....u C.'/l'i:,l\'.li
(!l. Liaited saaple voluae.
12). lnhoaogenous saaole.
13!. Nultiohase samole.
ANONALY LEGEND
(Sl, Laver of sedi■ent present on the bottoa of bottle.
(61. Sa■ole aliauot changed colcr on addition of acids,
17). Broken/leaking sa1ole bottle before oreoaration,
109). Oil layer on too of saaple. I
(101. Boiling stones used,
l!ll. Sa■ole is ooaoue or colored. ,
f!\ e1"w ._n fiP2r-,3ftpr-dioe;t. !El. The saniole was diaested usino a waste dioest aethod. (12!. Susnended aaterial oresent.
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·. Q
Q C LOT NlJ18ER /9 .... /AN IO It
?-Jl\,1-I C ?-AT
P,.oj•ct<s) I S.n111I• nuraiwrs ---·-------------&~Cb . : ff!y ef_;;, 0'.::?
ECD c : ,f.?¼ if 2-, ---,-------------
1 ---,-------------
' ___ , ____________ _
I ___ , ____________ _
'
"'"•• P•" foe "'d IIY S64ty
STANDARD
OPERATING
PROCEDURE
Subject or Title: Page 1 of 12
Mercury Preparation and Analysis ---
(Aqueous, Soil, Waste and Leachate Matrices)
SOP No.: Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
Supersedes: Original
ENSECO PROPRIETARY INFORMATION STATEMENT
This document has been prepared by and remains the sole property of ENSECO
INC. It is submitted to a client or government agency solely for its use in
evaluating Enseco's qualifications in connection with the particular project,
certification or approval for which it was prepared, and is to be held
proprietary to Enseco.
The user agrees by its acceptance or use of this document to return it upon
Enseco's request, and not to reproduce, copy, lend or otherwise disclose or
dispose of the contents, directly or indirectly, and not to use it for any
purpose other than that for which it was specifically furnished. The user
also agrees that where consultants or others outside of the user's
organization are involved in the evaluation process, access to these documents
shall not be given to those parties, unless those parties also specifically
agree to these conditions.
1. Scope and Application
1.1 Analytes
This method is the preparation and cold vapor analysis of aqueous
samples (dissolved & total), Cam Wet leachates, EP Toxicity
leachates (EPI & EPII), Toxicity Characteristic leaching Procedure
leachates (TCLP), soil samples, industrial waste samples, and oily
TCLP extracts for total mercury (organic and inorganic) by cold
vapor atomic absorption spectrophotometry (CVAAS).
Prepared By:
Richard M. Persichitte
Date:
June 25, 1991
Management Approval:
Dµ,,.J /3 /Z,£<,;1j£
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Mercury Preparation and Analysis
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page _1_ of __.11__
Effective Date:
LM-RMA-2005
Revision No. :
1.0 June 25, 1991
1.2 Reporting Limits
The reporting limit for mercury (Hg) in both total and dissolved
aqueous samples is 0.00020 mg/L. EP Tox, TCLP and Cam Wet leachates
are reported at 0.0020 mg/L. Soil or waste samples and oily TCLP
extracts are reported at 0.10 mg/kg.
1.3 Applicable Matrices
This method is applicable to total and dissolved aqueous samples,
leachates, soil samples and industrial waste matrices.
1.4 Dynamic Range
The dynamic range of samples reported for Hg by CVAA extends upward
from a 0.0002 ppm Hg initial concentration.
1.5 Analysis Time
The preparation and analysis time for one batch of 20 samples and
required QC is approximately 8 hours (not including instrument warm up
time).
m 2. Method Surrmary
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2.1 A representative aliquot of sample is weighed into a 300 ml biochemical
oxygen demand (BOD) bottle. Concentrated sulfuric acid (H2S04),
concentrated nitric acid (HN03), potassium permanganate (KMn04), and
potassium persulfate (K2S20R) is added. The sample is placed into a
water bath and heated to 950c.
2.1.1 Dissolved and total aqueous samples require a 100 g aliquot (lx).
2.1.2 Leachates require a 10 g aliquot that is diluted to a 100 ml
volume with Milli Q water (lOx).
2.1.3 Soil or industrial waste samples and oily extracts require a
0.2 g aliquot that is diluted to a 100 ml volume with Milli Q
water (500x).
NOTE: If a sample reading for Hg extends beyond the linear range of
the highest instrument calibration standard during the first
analysis, it must be re-prepped, diluted accordingly and re-analyzed.
Mercury Preparation and Analysis
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page 3 of 12 ---
Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
2.2 The sample is cooled and sodium chloride-hydroxylamine hydrochloride
is added.
2.3 The Hg is then reduced to ttie elemental state with stannous chloride
and aerated from the solution into a closed system. The Hg vapor is
passed through a cell positioned in the light path of an atomic
absorption spectrometer. The Hg concentration is determined as a
function of absorbance at 253.7 nm by CVAAS.
3. Co11111ents
3.1 Interferences
3.1.1 The most common interference is laboratory contamination which
may arise from impure reagents, dirty glassware, improper
sample transferring, dirty work areas, etc. Be aware of
potential sources of contamination and take appropriate
measures to minimize or avoid them.
3.1.2 Failure to homogenize the sample well prior to removal of the
desired aliquot may yield erroneous results.
3.1.3 Sea waters, brines, and industrial effluents high in chlorides
require additional permanganate. The chlorides are converted
to free chlorine, which also absorbs at 253.7 nm and may cause
a positive interference. When this interference is suspected
use up to 25 ml of additional potassium permanganate during
preparation of the sample. During analysis the head space of
the BOD must be purged before the addition of the stannous
sulfate.
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3.1.4 The recovery of Hg from spiked a sample may be affected if the I
sample contains concentrations of copper> 10 mg/L.
3.1.5 Concentrations of sodium sulfide> 20 mg/L may may interfere I
with the recovery of added inorganic Hg from ASTM Type II
water.
3.2 Helpful Hints· I
3.2.1 Bring soil samples within 0.01 g of the desired mass and
aqueous samples within 0.2 g of the desired mass. I
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Mercury Preparation and Analysis
SOP No.:
STANDARD
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Page 4 of 12 ---
Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
3.2.2 Visual inspection of the Hg vapor cell and pump tubing before
starting the instrument warm up procedure is advised.
3.2.3 DO NOT leave the aerator soaking in 1% HN03 after instrument
shutdown.
3.2.4 Leave the peristaltic pump on for 15 minutes after instrument
shutdown.
4. Safety Issues
4.1 Because mercury vapor is toxic, precaution MUST be taken to avoid its
inhalation.
4.2 Proper protective gear (i.e., safety glasses, face shield, gloves,
and rubber apron) should be worn when using acids.
4.3 Sample transfers, digestions, and analysis should take place in a
properly vented hood, and spills should be cleaned up immediately.
4.4 Sulfuric acid, nitric acid, and stannous chloride are corrosive and
will cause skin irritation. Avoid contact with eyes, skin and
clothing. Wash thoroughly with copious amounts of water.
4.5 All waste generated from the test will be placed into an approved,
correctly labelled waste container.
4.6 After analysis, allow high level samples to aerate in the hood until
the analyzer indicates the Hg level has returned to the base line.
4.7 The RMAL safety manual should be referred to for more detailed
cautions and instructions.
5. Sample Collection, Preservation and Holding Times
5.1 Samples should be collected in glass or plastic containers.
5.2 Dissolved and total aqueous samples should be acidified with nitric
acid to pH <2 at the time of collection.
5.3 For dissolved metals analyses, the samples should be filtered through
0.45 micron filter paper before acid preservation. Filtration must be
done in the field or within 24 hr of collection.
STANDARD
OPERATING
PROCEDURE
Page 5 of 12 ---Mercury Preparation and Analysis
Effective Date: SOP No.:
lM-RMA-2005
Revision No.:
1.0 June 25, 1991
5.4 Mercury has a 28 day holding-time. All other metals analyses have
180-day holding times.
6. Apparatus
6.1 Hot plate, capable of 95°c.
6.2 Miscellaneous pipettes.
6.3 Miscellaneous benchsheets.
6.4 Calculator.
6.5 300 ml Wheaton biochemical oxygen demand (BOD) bottles.
6.6 Top-loading balance, 0.01 g.
6.7 Water bath with temperature controlled at 950c.
6.8 Spectre-Products HG-3 cold vapor mercury analyzer.
6.9 Milli volt (mV) meter capable of digital voltage display.
6.10 Peristaltic air pump with variable speed control set at a flow rate
of 1 liter/min.
6.11 Aeration tube (a glass frit with coarse porosity attached to air
pump).
6.12 250 ml beaker.
7. Reagents and Standards
7.1 ASTM Type II water, (Milli Q or equivalent).
7.2 Hg standard stock solution "A": See RMAL Hg lCS + Calibration Stock
SOP lS-RMA-4501.
7.3 Hg DCS stock solution "B": See RMAl Hg lCS + Calibration Stock SOP
lS-RMA-4501.
7.4 Sulfuric acid, (H2S04), concentrated, trace metal grade.
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SOP No.:
lH-RHA-2005
Mercury Preparation and Analysis
Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page__§_ of _g_
Effective Date:
June 25, 1991
7.5 Sulfuric acid, 0.5 N: Carefully add 14 ml of concentrated sulfuric
acid to 1 liter of Milli Q water.
7.6 Nitric acid, (HN03}, concentrated, trace metal grade.
7. 7 Nitric acid, (HN03}, 1% solution (v/v): Carefully add 20 ml
concentrated nitric acid to 1980 ml water.
7.8 Potassium permanganate, mercury-free, 5% solution (w/v): dissolve 100
g of potassium permanganate in 2 liters of Milli Q water.
7.9 Potassium persulfate, 5% solution (w/v): dissolve 100 g of potassium
persulfate in 2 liters of Milli Q water.
7.10 Sodium chloride-hydroxylamine hydrochloride solution: dissolve a 240
g portion of sodium chloride and 240 g of hydroxylamine hydrochloride
in 2 liters of Milli Q water.
7.11 Stannous chloride: add 100 g stannous chloride to 1 liter of 0.5 N
H2S04. This mixture is a suspension (should appear cloudy) and
should be stirred continuously during use.
8. Procedure
8.1 Instrument Set-up and Calibration
8.1.1 Turn on hot plate, set for 95°c.
8.1.2 Verify the calibration of the balance and pipettes.
8.1.3 Turn on the Hg analyzer and warm up instrument as follows:
8.1.3.1
8.1.3.2
Turn on the mV meter (0.000 mV will
display) and depress the power switch (the
button will glow orange) of the Hg
analyzer.
Rotate the "B" lamp control clockwise
until the mV reading is 0.950 mV and stop
to allow the Fe reference lamp a 15 minute
warm up period.
Mercury Preparation and Analysis
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page _7_ of _!L
Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
8.1.3.3
8.1.3.4
8.1.3.5
8.2 General Preparation
Continue to stage the the mV reading of
the reference lamp to 1.000 mV by
increasing the previous mV reading by 50%
and a 5 minute warm up period.
With the reference lamp at 1.000 mV,
depress the AGC switch (the button will
glow green and a temporary fluctuation in
the mV reading will occur, if the mV
reading does NOT return to 1.000 mV within
1 minute consult your supervisor for
corrective action). After the mV reading
stabilizes at 1.000 mV, rotate the "A"
control clockwise until the mV reading·of
the Hg base lamp is 0.500 mV and allow a
15 minute warm up period.
Continue to stage the mV reading of the
base lamp to 0.000 mV by decreasing the
previous mV reading by 50% and a 5 minute
warm up period.
NOTE: Reverse the above steps (with
exception to the warm up periods) to shut
the instrument down. ·
8.2.1 Identify the test to be preformed by using the backlogs.
8.2.2 Check for special instructions concerning each sample.
8.2.3 Sign out samples from sample receiving.
8.2.4 Complete bench sheet.
NOTE: Aqueous samples reported in mg/L may NOT be placed on
the same bench sheet with soil, waste or oily TCLP extract
samples that are reported in mg/kg.
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Mercury Preparation and Analysis
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page~ of _R
Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
8.2.5 Update the backlog to reflect which samples are in progress.
8.2.6
NOTE: Consult your supervisor if a sample can NOT be
located.
Transfer a homogenized (well-mixed) sample aliquot into a
clean numbered 300 ml BOO bottle. Cap the BOD.
8.2.6.1
8.2.6.2
Total and dissolved water samples are
analyzed at a lx dilution and require a
100 g aliquot.
EP Tax, TClP, and Cam Wet leachates are
analyzed at a lOx dilution and require a
10 g sample aliquot brought to a 100 g
mass with Milli Q water.
NOTE: A sample spike must be analyzed on 1 sample for
each batch of EP Tox leachates prepared for Hg.
8.2.6.3 Soil or waste samples and oily TClP
extracts are analyzed at a 500x dilution
and require a 0.2 g sample aliquot brought
to a 100 g mass with Milli Q water.
8.2.7 Add 5 ml of concentrated H2S04 and 2.5 ml of concentrated HN03
and mix after each addition. Recap the BOO and allow to stand
for 5 minutes or until the acid fumes subside.
8.2.8 Add 15 ml potassium permanganate solution. Additional
permanganate may be required. Recap BOD. Shake and add
additional portions of permanganate as required until the
purple color persists for at least 15 min. Recap BOD.
8.2.9 Add 8 ml of potassium persulfate to each bottle and heat for 2
hours in a water bath at 95°C. Remove samples from water bath
and allow to cool.
8.3 Analysis
8.3.1 Add 6 ml of sodium chloride-hydroxylamine hydrochloride to the
cooled samples in the BOD bottles. This reduces the excess
SOP No.:
lM-RMA-2005
Mercury Preparation and Analysis
Revision No.:
1.0 ·
STANDARD
OPERATING
PROCEDURE
Page _J/__ of _.lL
Effective Date:
June 25, 1991
permanganate and causes the solution to decolorize. Allow the
samples to stand with the caps ajar for 5-10 minutes to allow
any chlorine gas to dissipate. Treat the samples separately
at this point.
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8.3.2 Samples are to be analyzed according to the bench sheet in the I
following order: instrument calibration standards, initial
calibration verification (ICV), initial calibration blank
(ICB), PB, 2 duplicate control samples (DCS), 10 or less
samples, followed by a continuing calibration verification I
(CCV) and a continuing calibration blank (CCB). For every
twenty (or less) samples analyzed, 2 DCS samples will be
analyzed along with a CCV and CCB for every 10 samples (or I
less) to be analyzed.
8.3.3 Insert the aerator into the sample BOO (above the fluid level) I
and purge the head space for 30 seconds.
8.3.4 Add 5 ml of stannous chloride and immediately attach the 1 aeration apparatus to the BOO bottle. As the Hg is bubbled
out of the sample, the absorbance (peak height measured in mV)
will rise to a maximum value and level off within
approximately 30 seconds. Record the mV reading of each I
sample on the bench sheet. For all samples reading above 0.05
mV, allow the apparatus to aerate with the frit tube ajar
until the reading has returned to the base line (this I
dissipates the Hg vapors into the hood).
NOTE: Samples reading above the highest instrument
calibration standard must be flagged during analysis.
Upon conclusion of the analysis, these BODs will be
flushed with hot tap water, rinsed and filled with
275 ml of DI water, and topped off with H2S04 then
allowed to stand for 1 hour. The BOD will then be
ready for routine washing procedures.
8.3.5 Place the aerator into 100 mls of 1% HN03 and allow to bubble
rinse until the next sample analysis.
8.3.6 Analyze the initial calibration standards. Construct a
calibration curve by plotting the peak height in mV versus Hg
concentration. The linear regression of these data should
produce a correlation coefficient for the curve of >0.995.
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Mercury Preparation and Analysis
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page 10 of 12 ----
Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
The initial calibration standards must then be re-analyzed if
the calibration curve does not meet the above criterion.
8.3.7 Analyze each sample (including all QC samples) and determine
the Hg concentration in ppm from the linear regression fit of
the calibration curve.
9. QA/QC Requirements
9.1 Instrument Calibration Standards Preparation
9.1.1 Prepare and analyze a 100 g Milli Q water sample per the
procedure as described in section 8.2-8.3, for the instrument
calibration blank.
9.1.2 Add, 50 ug, 100 ug, 200 ug, and 400 ug of the Hg standard stock
solution "A" to 4 separate BOD bottles, each containing 100 g
of Milli Q water, and prepare and analyze the instrument
calibration standards as described in section 8.2-8.3.
NOTE: These 5 instrument calibration standards will be used to determine
the linear regression of the standard curve. One set of instrument
calibration standards will be prepared for each batch of samples prepped.
9.2 ICBs and CCBs must be prepared and analyzed.
9.2.1 ICB: Prepare and analyze a 100 g Milli Q water sample per
the procedure described in section 8.2-8.3. One ICB is
prepared for each sample batch. It must be analyzed after
the rev sample.
9.2.2 CCB: Prepare and analyze a 100 g Milli Q water sample as per
the procedure described in section 8.2-8.3. One CCB shall be
prepared for each 10 samples digested or for each batch,
whichever is more frequent. It must be analyzed after each
CCV sample.
Mercury Preparation and Analysis
SOP No.:
STANDARD
OPERATING
PROCEDURE
Page 11 of 12 ----
Effective Date:
LM-RMA-2005
Revision No.:
1.0 June 25, 1991
9.3 ICVs and CCVs must be prepared and analyzed.
9.3.1 ICV: Add 200 ug Hg EPA rev 5 concentrate standard to 100 g
of Milli Q water. Prepare and analyze the ICV per the
procedure described in section 8.2-8.3. One shall be
prepared for each each batch of samples prepped. Recovery
must be within 90% to 11D% of the true value following QA/QC
requirements.
9.3.2 CCV: Add 100 ug Hg standard stock solution "A" to 100 g of
Milli Q water. Prepare and analyze the CCV per the procedure
described in section 8.2-8.3. One CCV shall be prepared for
each 1D (or less) samples digested. Recovery must be within
90% to 110% of the true value following QA/QC requirements.
9.4 DCS samples shall be prepared and analyzed in duplicate for each 20
(or less) samples digested. These 2 samples are prepared by adding
100 ug of the Hg DCS stock solution "B" to 100 g of Mi 11 i Q water
and digesting them as described in section 8.2-8.3. The recovery
for each DCS must be 75% to 125% and their precision must be a
relative percent difference of <20% per QA/QC requirements. If this
is not the case, tenninate the analysis and prep all the associated
samples again.
9.5 Client-specific sample duplicates and sample spikes (i.e., matrix
spikes and spike duplicates) will be prepared only upon client
request and will then appear on the prep scheduling sheet. The MS
and SD samples will be spiked with 100 ug of Hg standard stock
solution "A".
10. Calculations
Use a scientific calculator with linear regression capabilities to
calculate the standard calibration curve. Calculate from mV to
concentration of Hg in the sample as ug/L or mg/L.
11. Reporting Requirements
11.1 Total and recoverable aqueous sample results are reported as mg/L
units at 0.00020 ppm Hg.
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Mercury Preparation and Analysis
STANDARD
OPERATING
PROCEDURE
Page _lL of _lL
SOP No.: Revision No.:
1.0
Effective Date:
LM-RMA-2005 June 25, 1991
12.
11.2 Leachate sample results are reported in mg/L units at 0.0020 ppm
Hg.
11.3 Soil, waste or oily TCLP extract sample results are reported in
mg/kg units at 0.10 ppm Hg.
NOTE: Report all results with 2 significant figures if the Hg value is
less than 10 units. When the Hg value exceeds 10 units, report all
results with 3 significant figures.
Review Requirements
12.1 All data packages must be complete, signed, and dated by both the
analyst and the peer reviewer. Both the coversheet and the
benchsheet should state the analyst's name, the date and type of
analysis performed, and the instrument used.
12.2 Benchsheets must contain all calibration information, true values
for all QC solutions and recoveries for all QC and analytical
spikes.
12.3 Verify that calculations were done correctly by randomly checking a
few of them.
13. References
13.1 Methods 7470 and 7471. SW-846 -Test methods for evaluating solid
waste. 3rd edition.
13.2 U.S. Environmental Protection Agency Contract Laboratory Program
Statement of Work 787 (Rev 12/87) Exhibit D -Analytical Methods.
14. Deviations From Source Methods
14.1 Soils and wastes are digested according to section 7.2 of Method
7471 and are heated in a water bath rather than an autoclave.,
----------'-------------, Enseco I
A Coming Company I
STANDARD
OPERATING .
PROCEDURE
Subject or Title:
Total Metals: Digestion Preparation
(Soils/Wastes)
SOP No.: Revision No.: LM-RMA-2029 1.01
Supersedes: LM-RMA-2029, Revision 1.0
1. Scope and Application
1.1 Analytes
Page _l_ of -2_
Effective Date:
January 31, 1991
This method is an acid digestion procedure used to prepare a soil or waste sample for analysis by flame or Graphite Furnace Atomic Absorption Spectroscopy (AAS) or by Inductively Coupled Plasma (ICP) spectroscopy for a variety of trace metals. Mercury is not included.
1.2 Reporting Limits
Refer to the individual analysis SOPs.
1.3 Applicable Matrices
This method is applicable to soil and industrial waste matrices.
1.4 Dynamic Range
Refer to the individual analysis SOPs.
1.5 Analysis Time
The preparation time for one batch of 20 samples and required QC is approximately 8 hours. Refer to the individual analysis SOPs for approximate analysis times.
Prepared by: Date: Sherman Gray/Will Pratt January 31, 1991
Management ~pr~ 1 : . /J ~
1/~0{___ ;;{) /:f//V if / J
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SOP No.:
Total Metals: Digestion Preparation
(Soils/Wastes)
Enseco STANDARD A C=ing Company
OPERATING
PROCEDURE
Page -1.._ of _9_
Effective Date: LM-RMA-2029 Revision No.:
1.01 January 31, 1991
2. Method Summary
2.1 A representative 1 g sample aliquot is weighed into a 250 ml beaker. Dilute nitric acid is added, the beaker covered with a watch glass and the sample heated to 950c.
2.2 The sample is cooled and digested with dilute hydrogen peroxide. For GFAA analysis, no futher digestion is performed.
2.3 For FLAA or ICP analysis, the sample is cooled and digested with dilute hydrochloric acid.
2.4 All samples are cooled, filtered and diluted to a final volume of 100 ml.
3. Comments
3.1 Interferences
3.1.1 The most common interference is laboratory contamination which may arise from impure reagents, dirty glassware, improper sample transfering, dirty work areas, etc. Be aware of potential sources of contamination and take appropriate measures to minimize or avoid them.
3.1.2 Failure to homogenize the sample well prior to removal of the desired aliquot may yield erroneous results.
3.2 Helpful Hints
3.2.1 The terms "flame" and "furnace" are used frequently in this SOP. Pay particular attention to such terminology to avoid misinterpretation.
3.2.2 Samples requiring a "dry weight" analysis or calculation (as specified in special instructions) are prepared using the wet weight equivalent. See section 10.1.
3.2.3 Bring samples up to volume (mass) within 1% of the desired mass. For example, bring a soil digest to within 1 ml of the desired final volume (mass) of 100 ml.
4. Safety Issues
4.1 Proper protective gear (i.e., safety glasses, face shield, gloves, and rubber apron) should be worn when using acid or peroxide.
I
.Enseco STANDARD A Com;ng Company I
OPERATING
SOP No.:
LM-RMA-2029
Total Metals: Digestion Preparation
(Soils/Wastes)
Revision No.:
1.01
PROCEDURE·
Page _3_ of _9_
Effective Date:
January 31, 1991
4.2 All sample transfers and digestions should take place in a properly
vented hood, and spills should be cleaned up immediately.
4.3 Nitric acid, hydrochloric acid and hydrogen peroxide are corrosive
and will cause skin irritation. Avoid contact with eyes, skin and
clothing. Wash thoroughly with copious amounts of water.
4.4 All waste generated from the test will be placed into an approved,
correctly labelled waste container.
4.5 The RMAL safety manual should be referred to for more detailed
cautions and instructions.
5. Sample Collection, Preservation and Holding Times
5.1 Samples should be collected in glass or plastic containers.
5.2 Samples should be refrigerated at 40c until the time of preparation.
5.3 The holding time for all metals analyzed by atomic spectroscopy.is
180 days (6 months}, except mercury. The preparation and analysis for
mercury is described in SOP LM-RMA-2005.
6. Apparatus
6.1 Hot plate, capable of 1000 C.
6.2 Miscellaneous pipettes.
6.3 Miscellaneous benchsheets.
6. 4 Ca lcu 1 a tor.
6.5 250 ml glass beakers with watch glasses.
6.6 Top-loading balance, 0.01 g capability.
6.7 Miscellaneous filter apparatus.
6.8 Plastic bottles (1% HN03 rinsed).
7. Reagents and Standards
7.1 ASTM Type II water (Milli Q or equivalent).
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-------~-~----------~· .. ·.· .. ·· Enseco
ST ANDAfW A Coming Company
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SOP No.:
Total Metals: Digestion Preparation
(Soils/Wastes)
OPERATING
PROCEDURE
Page 4 of 9 --
Effective Date: LM-RMA-2029
Revision No. :
1.01 January 31, 1991
7.2 Nitric acid, (HN03), concentrated, trace metal grade.
7.3 Nitric acid, (HN03), 75% solution (v/v): Carefully add 1500 ml concentrated nitric acid to 500 ml water.
7.4 Nitric acid, (HNO~), 1% solution (v/v): Carefully add 20 ml concentrated nitric acid to 1980 ml water.
7.5
7.6
7.7
7.8
Hydrochloric acid, ( HC l) , concentrated, trace metal grade.
Hydrochloric acid, (HCl), 50% solution {v/v): Carefully add 1000 ml concentrated hydrochloric acid to 1000 ml water.
Hydrogen peroxide, (H202), reagent grade.
Duplicate control standard solutions (DCS).
7.8.1 Samples prepared for analysis by Graphite Furnace AAS use the GFAA duplicate control standard solutions "A" and "B".
7.8.2 Samples prepared for analysis by Inductively Coupled Plasma use the ICP duplicate control standard solutions "A", "B", "C" and 11 011
•
7.8.3 Samples prepared for analysis by Flame AAS use the ICP duplicate control standard solutions "A", "B", "C", "D" and
u E".
8. Procedure
8.1 Instrument Set-up and Calibration
8.1.1 Turn on hot plate, set for 95°c (see SOP: LP-RMQ-0053 for calibration check procedure). Allow 1/2 hour to preheat.
8.1.2 Verify the calibration of the balance and pipette.
8.2 Preparation
8.2.1 Identify the test and samples to be digested using the backlogs.
8.2.2 Check the special instructions for each sample and print a copy if they apply.
I I
.Enseco .1 STANDARD A Coming Comp.my I
SOP No.:
Total Metals: Digestion Preparation
(Soils/Wastes)
OPERATING
PROCEDURE
Page 5 of 9 -

-
Effective Date: LM-RMA-2029 Rev 1 s ion No. :
1.01 January 31, 1991
·8.2.3
NOTE: Be aware of requests for Dry Weight (prep, analysis, calculation, etc.). Consult your supervisor.
Locate and sign out the samples in the walk-in cooler. If a sample cannot be located, consult your supervisor.
8.2.4 Assign a QC Lot Number and fill out the appropriate bench sheet (separate bench sheets are completed for GFAA and ICP/FLAA digestions).
8.2.5 Update the backlog to reflect which samples are in progress.
8.2.6 Clearly label each beaker as appropriate (red stickers are used for GFAA preps and green stickers are used for ICP/FLAA preps).
8.3 Analysis
8.3.1 Homogenize the sample as much as possible with a clean plastic spoon or spatula and weigh a 1.0 g portion into a labelled 250 ml beaker. Report sample specific anomalies and/or comments on the bench sheet.
8.3.2 Carefully add 20 ml of 75% HN03 to the sample and cover the beaker with a watch glass. Heat on a hot plate to 950 and allow to reflux and evaporate to 10 ml volume (approximately 1-2 hours). Remove and cool.
NOTE: DO NOT let the sample boil or the volume reduce to less than 5 ml.
8.3.3 Add 5 ml of 30% H202, return to the hot plate and heat for 30 minutes. Remove and cool. Repeat once. Continue heating the sample until the volume is reduced to approximately 10 ml.
NOTE: DO NOT let the sample boil or the volume reduce to less than 5 ml.
8.3.4 For Graphite Furnace AAS analysis, add 10 ml Milli Q water and heat the sample for 15 minutes. Remove and cool.
8.3.5 For Flame AAS or ICP analysis, add 10 ml 50% HCl and heat the sample for 30 minutes. Remove and cool.
8.3.6 Label plastic bottles using available computer program.
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'------~-----------.Enseco
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SOP No.:
Total Metals: Digestion Preparation
(Soils/Wastes)
STANDARD A C=ing Company
OPERATING
PROCEDURE
Page 6 of 9 - -
Effective Date:
LM-RMA-2029
Revision No.:
1.01 January 31, 1991
8.3.7 Weigh each sample digest bottle and record that weight under
the bottle label. Rinse the bottle with 1% HN03.
8.3.8 Filter the sample through filter paper (Whatman 41 or
equivalent that has been pre-rinsed with 1% HN03) into the
pre-weighed, acid-rinsed poly bottle.
8.3.9 Rinse the beaker, watch glass and the filter paper sparingly,
but well, with Milli Q water to ensure complete sample
transfer. See your supervisor for specific technique.
8.3.10 Adjust the sample volume to a final mass of 100 g with Milli Q
water.
8.3.11 Check that the bottle cap and bottle are labelled identically
and cap the bottle. The sample is now ready for analysis.
8.4 Conclusion
8. 4 .1 Comp 1 ete a 11 paperwork and re 1 ease prep from "logged" to
"done" in LIMS. Consult your supervisor.
8.4.2 Place samples in properly labelled box (see attached example)
and deliver to appropriate analysis shelf.
I 9. QA/QC Requirements
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9.1 QC Samples
9.1.1 A blank shall be prepared for each 20 samples digested or for
each batch, whichever is more frequent. The blank is prepared
by taking 1.0 g of Milli Q water and digesting it as described
in section 8.3.2 through 8.3.11.
9.1.2 Duplicate control samples (DCS) shall be prepared for each 20
samples digested or for each batch, whichever is more
frequent. These are prepared by spiking 1.00 ml of each of the
DCS stock solutions into 1.0 g of Milli Q water and digesting
them as described in section 8.3.2 through 8.3.11.
NOTE: There are two separate DCS solutions for Graphite
Furnace AAS, four separate DCS solutions for ICP, and five
separate DCS solutions for Flame AAS digests. Each DCS
solution has its own verification number. See section 7.8.
. I ----------'---------------·· .. Enseco
ST ANOARD A Coming Company I
OPERATING
PROCEDURE .
SOP No.:
Total Metals: Digestion Preparation
(Soils/Wastes)
Revision No.:
Page 7 of 9 --
LM-RMA-2029 1.01
Effective Date:
January 31, 1991
9.1.3 Client specific sample duplicates (DU), matrix spikes (MS) and
matrix spike duplicates (SD) will be prepared only upon client
request and will then appear on the prep scheduling backlog sheet.
9.1.4 See SOP: M-EQA-0002 and the Enseco QAPP.
9.2 Acceptance Criteria
Refer to the appropriate RMAL individual analysis SOP for each
specific analyte.
9.3 Corrective Action Required
Follow the corrective actions outlined in the current Enseco QAPP manual or consult your supervisor.
10. Calculations
10.1 The mass of wet sample to be prepped for "dry weight" reporting is calculated as:
1.0 g
Mw = (TS/100)
Where Mw = sample mass wet and
TS= percent total solids and
assuming the desired dry mass
is 1.0 grams.
For example, a sample is 50% total solids and a "dry weight" prep is required:
1.0 g
Mw = (50/100) = 2.0 g (wet)
10.2 The final dilution factor is calculated as follows:
DF = Dilution Factor
M = Initial sample mass
V = Final volume of digest
V
OF= M
NOTE: On a "dry weight" prep, the "wet weight" equlivalent of 1.0 g
dry has no impact on the initial sample weight used in the
calculation of the final dilution factor.
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·------~~-----------.Enseco
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SOP No.:
lM-RMA-2029
Total Metals: Digestion Preparation
(Soils/Wastes)
Revision No.:
1.01
11. Reporting Requirements
STANDARD A Com;ng Comp,my
OPERATING
PROCEDURE·
Page 8 of 9 --
Effective Date:
January 31, 1991
11.1 All data packets will be compiled in the following order: Bench
sheet, total solids bench sheet copy {when applicable) and a copy of
the special instructions.
11.2 The prep analyst name, prep date, QC lot number, sample number,
acknowledgment of special instructions, anomalies observed, dry
weight equivalent mass, sample mass, final volume, dilution factor,
spike solution verification numbers and comments are recorded on the
prep bench sheet (see attached example).
11.3 Calculate and report all "dry weight" equivalents on the bench sheet {when applicable).
12. Review Requirements
12.1 Verify special instructions were followed.
12.2 Verify dilution factors were correctly calculated (including "dry
weight" preps, when applicable).
13. References
13.1 Source Method: Method 3050, SW-846 -Test Methods for Evaluating
Solid Waste, 3rd Edition, 1986.
13.2 Related Documents
Method 200.7. Inductively Coupled Plasma -Atomic Emission
Spectrometric Method for Trace Element Analysis of Water and Wastes.
"Methods of Chemical Analysis of Water and Wastes (MCAWW)", EPA-
600/4-79-020, March, 1983.
13.3 Deviations from Source Method and Rationale
13.3.1 For convenience sake, (step 8.3.2 of this document) add 20 ml
of 75% HN03 and heat for 1 to 2 hours in lieu of the
following:
Add 10 ml 1:1 HN03, reflux 15 minutes, add 5 ml concentrated
HN03 and reflux for 30 minutes.
SOP No.:
lM-RMA-2029
Total Metals: Digestion Preparation
(Soils/Wastes)
Revision No.:
1.01
Page ..1.._ of ..1.._
Effective Date:
January 31, 1991
13.3.2 For convenience sake, (step 8.3.3 of this document) add 5 ml of 30% H202 and heat for 30 minutes, then repeat once in lieu of the following:
Add 2 ml of H20 and 3 ml H202, heat until effervescence subsides, continue to add 30% H202 in 1 ml aliquots until effervescence is minimal.
13.4 Updates to SOP (Original to Revision 1.01)
13.4.1 Addition and strength of nitric acid.
13.4.2 Addition of hydrogen peroxide.
13.4.3 All other changes simplify working details of the SOP.
13.4.4 Addition of hot plate calibration SOP.
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------------------------1~\>Enseco
"-"-· A Coming Company
Subject or Title:
SOP No.:
LM-RMA-2006
Supersedes: Original
Metals: GFAA Analysis
Revision No.:
1.0
STANDARD
OPERATING
PROCEDURE
Page _l_ of ___!i_
Effective Date:
March 3, 1991
ENSECO PROPRIETARY INFORMATION STATEMENT
This document has been prepared by and remains the sole property of ENSECO
INC. It is submitted to a client or government agency solely for its use in
evaluating Enseco's qualifications in connection with the particular project,
certification or approval for which ft was prepared, and is to be held
proprietary to Enseco.
The user agrees by its acceptance or use of this document to return it upon
Enseco's request, and not to reproduce, copy, lend or otherwise disclose or
dispose of the contents, directly or indirectly, and not to use it for any
purpose other than that for which it was specifically furnished. The user
also agrees that where consultants or others outside of the user's
organization are involved in the evaluation process, access to these documents
shall not be given to those parties, unless those parties also specifically
agree to these conditions.
1. Scope and Application
1. 1 Ana lytes
The four metals most commonly analyzed by Graphite Furnace Atomic
Absorption Spectrophotometry (GFAA) are Arsenic, Lead, Selenium, and
Tha 11 i um.
Other elements that may be analyzed include (but are not limited to)
Antimony, Cadmium, Chromium, and Silver.
1.2 Reporting Limits
Reporting limits range from 0.5 to 10 ug/L and _ug/kg according to the
analyte. Instrument detection limits (IDL) are also available.
Consult the specific analyte information at the end of this SOP for
details.
Prepared by:
David B. Roberts, Jr.
Management Approval:
Oa-v)cf fJ /K,lu.,,,/1' I
Date:
March 3, 1991
Date:
{-J-7--'tl
Date:
oC-/47 & I 7 7
I _______________________ ;:;>.,£:ns"'"'O
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Revision No.:
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1.3 Applicable Matrices
This method is applicable to the analysis of metals in dissolved,
recoverable and total water samples, as well as digests of soils,
wastes and leachates.
1.4 Dynamic Range
The dynamic range is element specific. For the four most common
analytes, it extends to 100 ug/L. Higher concentrations may be
analyzed by dilution of the sample. Consult the specific analyte
information at the end of this SOP for details.
.1.5 Analysis Time
Approximately 20 samples per instrument-shift can be analyzed. It is
common practice to run two instruments simultaneously. Sample
preparation time is not included.
2. Method Summary
2.1 The sample is first digested according to the appropriate method.
Dissolved water samples are analyzed without digestion unless
specifically requested by the client.
2.2 An aliquot of the prepared samples is automatically injected into an
electrothermally heated graphite furnace which is programmed through
a series of drying and charring stages. The element of interest is
then atomized by a rapid increase 1n the temperature of the furnace.
2.3 Radiation from a hollow cathode lamp {HCL) or an electrodeless
discharge lamp (EDL) is focused through the graphite furnace. The,
lamp radiates light at the wavelengths specific to the element bE!ing
analyzed; atoms of the e 1 ement in the furnace absorb 11 ght at thEi
characteristic wavelength. The absorbance is measured
electronically.
2.4 The concentration of the element is calculated by comparing the
sample absorbance to the absorbances measured for standards
containing known concentrations of the element. This calculation is
performed by the instrument.
3. Comments
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________________________ .f.f;E ,_~,, nseco
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3.1 Interferences
Any substance which alters the atomization or absorption
characteristics of the sample or absorbs light at the same wavelength
as the metal being analyzed is a potential interference. Specific
interferences are discussed in the individual element procedures.
3.1.1 Chemical and physical interferences are prevalent when
analyzing samples using these methods.
3.1.2 Many substances produce non-specific background absorption
which must be compensated for by the use of a background
correction system, either Deuterium Arc or Zeeman.
3.1.3 Samples are highly subject to contamination at the trace
levels of interest in this method. Deionized water and high-
purity acids are to be used unless otherwise specified.
3.1.4 Autosampler trays are to be kept covered during analysis.
3.1.5 All work areas used to prepare standards and spike samples are
to be cleaned before and after each use.
3.2 Helpful Hints
A summary of the operating conditions used is given in a table at the
end of this SOP. For more detail, consult the procedures for the
individual elements. Instrument-specific infonnation can be found in
the instructions for the instrument being used.
4. Safety Issues
4.1 All employees are expected to be familiar with and follow the
procedures outlined in the Enseco/RMAL safety plan. Lab coats and
safety glasses are required in all laboratory areas at all times. If
you have any questions or safety concerns, see your supervisor or
safety officer.
4.2 Wear. gloves and apron when handling concentrated acids. Transport
only in approved carriers. Avoid breathing fumes and vapors; handle
in a fume hood. Neutralize and clean up any spills immediately. In
case of skin contact, flush affected area with water for at least 15
minutes. Notify your supervisor or safety officer of any spills or
exposures.
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4.3 The graphite furnace reaches EXTREMELY high temperatures. Be sure
that it has cooled sufficiently before removing the tube.
4."4 Radiation emitted by the tube during the atomization step is harmful
to the eyes. DO NOT look at the tube during atomization.
4.5 The furnace should be properly vented with an exhaust hood directly
over the furnace chamber.
4.6 Samples and other solutions containing high concentrations of toxic
materials must not be flushed down the sinks, but are to be disposed
of in suitable waste containers.
4.7 Refer to the RMAL safety manual for additional precautions and
instructions for working in the metals lab.
5. Sample Collection and Preservation
5.1 Dissolved water samples should be filtered at the time of collection,
preserved with nitric acid to a pH of less than 2 and stored in clean
glass or plastic bottles.
5.2 For collection and preservation information of other matrices,
consult the appropriate prep SOPs. See section 8.1.
5.3 The holding time for all metals described by this SOP is 6 months.
6. Apparatus
5;1 Atomic absorption spectrophotometer equipped with graphite furnace,
background correction system, autosampler and printer. Examples
include:
6.1.1 Perkin Elmer Model 2380 with HGA 400 Graphite Furnace and AS
40 Autosampler.
6.1.2 Perkin Elmer Model 5000 Zeeman with HGA 500 Graphite Furnace
and AS 40 Autosampler.
6.1.3 Perkin Elmer 5100 Zeeman with HGA 600 Graphite Furnace and.AS
60 Autosampler and Epson computer.
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6.2 Electrodeless discharge lamps and power supply, or hollow cathode
lamps, specific to the element(s) being analyzed.
6.3 Oxford and Eppendorf pipettors, various sizes, with disposable tips.
6.4 Autosampler cups.
6.5 Graphite tubes, platforms, and other supplies.
6.6 Miscellaneous laboratory apparatus and glassware.
7. Reagents and Standards
7.1 Standards
7.1.1 Preparation of standard solutions is element specific.
Consult the individual element SOPs for details.
(See Attachment 1)
7.2 Matrix modifiers
All elements require the addition of a matrix modifier to the sample
in order to control interferences. (See Attachment 1 and 3)
7.3 EPA ICV Solution
This solution is used for the Initial Calibration Verification (ICV).
It is analyzed immediately following standardization. This solution
is obtained from the EPA through EMSL (Las Vegas) by request.
7.4 CCV Solution
This solution is used for Continuing Calibration Verification (CCV).
It is analyzed at a frequency of at least 10% (one every 10 samples)
during an analytical run. This solution is usually the mid-range
standard and prepared daily.
7.5 ICB/CCB Solution
This solution is used for the Initial Calibration Blank (ICB) and the
Continuing Calibration Blank (CCB). It is analyzed after the ICV at
a frequency of at least 10% (one every 10 samples) during an
analytical run. This solution consists of 1% nitric acid plus any
matrix modifier used and is prepared daily.
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8. Procedure
8.1 Preparation
8.1.1 Total waters, Total Recoverable waters, EP Tox extracts and
TCLP extracts are digested using SOP: LM-RMA-2002.
8.1.2 Soils and Wastes are digested using SOP: LM-RMA-2029.
8.2 Instrument Set-Up and Calibration
Instructions vary according to instrument and element. General
instructions are given here; consult the appropriate procedures and
manuals for the specific analyte being measured and instrument used.
8.2.1 Turn on the main power, cooling water, ·and argon.
8.2.2 Install the proper lamp and adjust to the proper power
setting.
8.2.3 Set the correct wavelength and slit for the element being
analyzed.
8.2.4 CAREFULLY inspect and clean the quartz windows of the graphite
furnace.
8.2.5 After warming up for 10 minutes, optimize the instrument
energy throughput.
8.2.6 Make sure that the energy can be turned up past the autogai,n
energy. If problems are encountered achieving the proper
energy level, re-optimize the instrument. If this fails to
help, then the lamp probably needs to be replaced or the
furnace realigned.
8.2.7 Observe the baseline and re-optimize the instrument if it is
unstable. If the baseline is still unstable, the lamp
probably needs to be replaced.
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8. 2. 8 Turn on the background corrector if using a 02 background 1-
correct ion system. Readjust the lamp power setting, and allow
to warm up for 10 minutes.
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8.2.9 Observe the baseline again. If it is unstable, re-optimize
the instrument. If this fails, check the furnace alignment
and readjust if necessary. If the problem persists, turn up
the EDL power supply 1 to 2 watts. The deuterium lamp may
also need to be replaced.
8.2.10 Inspect the graphite tube and platform, replace if necessary.
Clean the contact rings, injection tip and outside of the
graphite furnace.
8.2.11 Program the autosampler, furnace, and AA according to the
procedures for the instrument being used and the metal being
analyzed.
8.2.12 Blanks and calibrations standards must contain any matrix
modifier in the same concentration as is in the samples. This
is usually added by the instrument using the "Alternate
Volume" function or equivalent.
8.2.13 A Calibration Blank and three standards are analyzed.
8.2.2.1 Run blanks successively until the baseline is stable.
8.2.2.2 Calibrate the instrument using the standards
indicated for in the procedure for the given
instrument and element.
8.2.14 Analyze the EPA !CV, CCV and !CB solutions. If these are not
within 10% of the expected value, corrective action must be
taken before proceeding.
8.3 Analysis
8.3.1 Add the matrix modifier to all samples
8.3.2 Before analyzing any samples, run the Prep Blank (if
applicable) and DCS's. If these are not within acceptable
limits, corrective action must be taken before proceeding.
8.3.3 An analytical spike is to be performed on EACH sample. See
section 9.2 for acceptance criteria.
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8.3.4 Samples exceeding the highest standard are to be diluted and
reanalyzed or the results taken from the ICP. Oil ut ions must
be made in such a way that the diluted sample contains the
same concentration of acid and any matrix modifier as the
undiluted sample.
8.3.5 A Blank (CCB) and standard check (CCV) must be performed after
every 10 or less samples. If these are not within 10% of the
true value, corrective action must be taken and all samples,
analyzed since the previous "in control" CCV must be
reanalyzed.
8.3.6 A final CCB and CCV should be run.
8.4 Conclusion
8.4.1 After completing the analytical run, follow the .shut-down I
procedure for the specific instrument used. This will include
removing and storing the lamp, placing the autosampler,
graphite furnace and spectrophotometer on stand-by and turning I
off the gas and water.
8.4.2 Complete ALL paperwork neatly and in a timely manner. Data I
packages should include: a cover sheet with a 11 samples and QC
information listed, a review checklist filled out by the
analyst, all special instructions, an anomaly form describing 1 the analysis, and all benchsheets with samples and results to
be entered into LIMS highlighted and a 11 instrument printouts.
9. QA/QC Requirements
9.1 QC Samples
9.1.1 A Prep Blank is required with every batch of 20 or less
samples. Dissolved samples will not have a prep blank.
9. 1. 2 Two DCS samples are required with each batch of 20 or less
samples.
9.1.3 A blank (CCB) and standard check (CCV) are required after
every 10 or less samples.
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9.1.4 Duplicates may be required for project specific QC.
9.1.5 Matrix Spikes may be required for project specific QC.
9.1.6 Analytical spikes are to be performed on ALL samples.
9.2 Acceptance Criteria
9.2.1 Method blanks should be less than the reporting limit. If the
method blank is more than two times the reporting limit the
supervisor should be notified for corrective action.
9.2.2 Average DCS recovery must be 75 -125%.
9.2.3 The RPO for the DCS must be less than or equal to 20%.
9.2.4 The EPA ICV and all standard checks must be within 10% of the
expected value.
9.2.5 There are no acceptance criteria for project specific QC.
9.2.6 Analytical Spike Recovery
(See Flow diagram)
9.2.6.1 Sample reads below the reporting limit (RL)
Recovery
( 40%
)=40% and (80%
)=80% and (=120%
Recovery )120
Action
Dilute, reanalyze
Report ND at 2x RL
Report ND at RL
Report ND at 2x RL
9.2.6.2 Sample reads at or above the reporting limit (RL)
Recovery
( 40%
)=40% and (80%
)=80% and (=120%
) 120%
Action
Dilute, reanalyze
Dilute, reanalyze
Report result at RL
Dilute, reanalyze
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9.2.7 Dilutions
NOTE: MSA = Method of standard addition -i.e. be
applied under supervisor discretion.
(See Attachment 2)
When a sample must be diluted the dilution chosen will be
determined by the analyst's best judgement and should place
the analyte concentration in the optimum range of the
calibration curve. The sample should not be over-diluted.
9.3 Corrective Action Required
9.3.1 Corrective action taken when the acceptance criteria are not
met may include: reanalysis of samples not bracketed by
acceptable QC, restandardization of the instrument and
reanalysis, or repreparation of the samples.
9. 3. 2 Fo 11 ow the corrective actions out 1 i ned in the current Enseco
QAPP Manual.
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10. Calculations I
10.1 The instrument automatically calculates sample concentrations from 1 the absorbances.
10.2 Multiply the concentration from the instrument by any dilution
factors made during sample.preparation and analysis.
10.3 To convert from ug/L (ppb) to mg/L, divide by 1000.
11. Reporting Requirements
11.1 Units
Reporting units are mg/L for aqueous samples and mg/kg for non-
aqueous samples. As a convenience, units of ug/L (ppb) may used
during analysis.
11.2 Limits
Samples less than the reporting limit are reported as N.D.
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11.3 Significant Figures
0,0001-0.001-0.01-
Element ReQ. Limit 0:0009 0.009 0.09 i 0.10
Arsenic 0.005 mg/L -1-2 2
Lead 0.005 mg/L 1 2 2
Selenium 0.005 mg/L 1 2 2
Thallium 0.005 mg/L 1 2 2
Antimony 0.01 mg/L 1 2
Cadmium 0.0005 mg/L 1 2 2 2
Chromium 0.005 mg/L 1 2 2
Silver 0.0005 mg/L 1 2 2 2
11.4 LIMS Data Entry
The usual standards for data entry apply.
11.5 Anomalies
11.5.1 Samples that contain high levels of soluble salts may form
crystals upon drying in the furnace and require dilution to
obtain acceptable spike recoveries.
11.5.2 High concentrations of non-target compounds may cause poor
spike recovery. These samples must be diluted until the
spike recovery is acceptable and the reporting limit raised
accordingly.
11.5.3 Samples containing significant concentrations of organic
material may not pipette smoothly into the furnace or be
deposited on the platform properly. These samples must
also be diluted or digested before analysis.
11.5.4 Samples requiring large dilutions due to the presence of
high concentrations of analyte may be reported using
alternate techniques, ie. Flame AA or ICP.
12. Review Requirements
12.1 All data packages must be complete, signed and dated by both the
analyst and the peer reviewer. Both the coversheet and the
benchsheet should state the analyst's name, the date and type of
analysis performed and the instrument used.
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12.2 Benchsheets must contain all calibration information, true values
for all QC solutions and recoveries for all QC and analytical
spikes.
12.3 Verify that calculations were done correctly by randomly checking a
few of them.
13. References
13.1 Source Method: USEPA SW-846, "Test Methods for Evaluating Solid
Waste", Chapter 3, 7000-series methods, 3rd Edition, 1986.
13.2 Related Documents
13.2.1 Methods for Chemical Analysis o·f Water and Wastes, EPA 600
Methods, revised March 1983.
13.2.2 Instruction manuals for Perkin Elmer Model 2380, Zeeman
5000 and Zeeman 5100
13.3 Deviations from Source Method and Rationale
Consult individual element procedures.
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I SOP No.: Revision No.: Effective Date:
LM-RMA-2006 1.0 March 3, 1991
I ATTACHMENT 1
I STANDARD OPERATING CONDITIONS FOR METALS
(GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROPHOTOMETRY)
I
Matrix
Element EPA Ref. SOP Ref. Wavelength Slit Modifier
Arsenic 7060 LM-RMA-2007 193.7 nm 0.7 Ni(N03)2
I Lead 7421 LM-RMA-2013 283.3 nm 0.7 (NH4)2HP04
I Selenium 7740 LM-RMA-2019 196.0 nm 0.7 Ni(N03)2
Thallium 7841 LM-RMA-2026 276.8 nm 0.7 H2S04
I Antimony 7041 LM-RMA-2005 217.6 nm 0.2 Ni(N03)2
I Cadmium 7131 LM-RMA-2011 228.8 nm 0.7 (NH4)2HP04
Chromium 7191 LM-RMA-2036 357.9 nm 0.7 Mg (N03)2
I Silver 7761 LM-RMA-2023 328.1 nm 0.7 P03
I Standard Analytical
Element Rep. Limit Concentrations Spike(ug/L)
I Arsenic 0.005 mg/L 0, 20, 50, 100 20
Lead 0.005 mg/L 0, 20, 50, 100 20
I Selenium 0.005 mg/L 0, 20, 50, 100 20
Thallium 0.005 mg/L .o, 20, 50, 100 20
I Antimony 0.01 mg/L 0, 20, 50, 100 20
I Cadmium 0.0005 mg/L 0, 1, 2. 5 I 5 1
I Chromium 0.005 mg/L o, 20, 50, 100 20
Silver 0.0005 mg/L 0, 1, 2 • 5 I 5 1
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SOP No.:
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1.0
ATTACHMENT 2
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SOP No.:
lM-RMA-2006
Element
Sb z
As z
Cd
D2
Cr
D2
Pb
D2
Ag
D2
Se z
Tl
D2
SW846
(7041)
0.1% NiN03
(7060)
0.1% NiN03
(7131)
?x40% (NH4)2 HP04
(7191)
?xl.18% Ca(N03)2
4 H20
(7421)
0.85% HP04
(7761)
Uses a different
prep
(7740)
0 .1% Ni
(7841)
?x0.025% PdCl2
and ?x1% HN03
Revision No.:
1.0
ATTACHMENT 3
MATRIX MODIFIERS
MARCH 1991
RMAl
0.1% Ni
0 .1% Ni
1% P04
0.025%
Mg (N03)2
1% P04
1% P04
0.1% Ni
and 0.125%
Mg(N03)2
0.01% H2S04
Page --12__ of -12_
Effective Date:
March 3, 1991
Concentrations
20 ul of 7.5% NiNO} to
1.5 ml sample (cup
20 ul of 7.5% NiNO~ to
1.5 ml sample (cup
20 ul of 75% (NH4)2
to 1.5 ml sample (cup)
20 ul of 1.87% Mg(N03)2
in 1.5 ml sample (cup)
20 ul of 75% (NH4)2 HP04
to 1.5 ml sample (cup)
20 uL of 75% (NH4)2 HP04
to 1.5 ml sample (cup)
20 ul of 7.5% NiN03 and
9.4% Mg(N03)2 to 1.5 ml
sample (cup)
20 ul of 0.75% H2S04 to
1.5 ml sample (cup)
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STANDARD A Coming C=p,nyl
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Subject or Title: Page 1 of 20
Analysis: Inductively Coupled Plasma (ICP)-----Metals
(Industrial Metals)
SOP No.: Revision No.: Effective Date:
LM-RMA-2037 1.0 July 1, 1991
Supersedes: Original (February 1, 1990)
1.
ENSECO PROPRIETARY INFORMATION STATEMENT
This document has been prepared by and remains the sole property of
Enseco, Inc. It is submitted to a client or government agency solely for
its use in evaluating Enseco's qualifications in connection with the
particular project, certification or approval for which it was prepared,
and is to be held proprietary to Enseco. ·
The user agrees by its acceptance or use of this document to return it
upon Enseco's request, and not to reproduce, copy, lend or otherwise
disclose or dispose of the contents, directly or indirectly, and not to
use it for any purpose other than that for which it was specifically
furnished. The user also agrees that where consultants or others outside
the user's organization are involved in the evaluation process, access to
these documents shall not be given to those parties unless said parties
also specifically agree to these conditions.
Scope and Application
1.1 Ana lytes
This method is applicable to the determination of
Enseco-RMAL Jarrell-Ash ICAP 61 instrumentation.
specific analyte list which is subject to change.
1:2 Applicable Matrices
trace metals using
See Appendix 1 for
This method is applicable to a variety of environmental matrices
including dissolved, recoverable and total water samples, as well as
digests of soils, wastes, and leachates.
Prepared by: Date:
Fred Velasquez July 1, 1991
Management Approval:
Op.v:Jl!J £k4 /
Date:
oB/or/91 T 7
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I 1.3 Reporting Limits
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Standard Enseco reporting limits range from 0.002 to 5 mg/Lin
aqueous samples. Soil, waste and leachate limits are 10-lOOx higher.
All limits are subject to elevation upon dilution due to analytes
exceeding linear range of specified instrument. Method detection
limits (MDL's) are also available. Consult Appendix 1 for specific
analyte information which is subject to change annually.
1.4 Dynamic Range
The dynamic range is element specific. For most analytes it extends
to 100 mg/Lin solution. Higher concentrations may be analyzed by
dilution of the sample. Consult Appendix 1 for specific analyte
information.
1.5 Analysis Time
Approximately 40 samples can be analyzed per instrument-shift. This
includes all QC samples and entry into the LIMS system. Sample
preparation time. is not included.
2. Method Su11111ary
2.1 Aqueous and digested samples are nebulized into a spray chamber. A
stream of argon gas carries the sample aerosol through the quartz
torch and into the plasma. The plasma of ionized argon is sustained
at a temperature as high as 10,000°K by a Radio Frequency (RF)
generation source.
2.2 Once the aerosol reaches the plasma, the sample is desolated
(decomposed), the elements are excited and emit radiation at their
characteristic wavelength. See Appendix 6.
2.3 The emitted light energy is then directed through the exit slits and
projected on photo multiplier tubes (PMT) specific for each element.
The PMT's convert the light energy to an electrical signal that is
digitized a_nd processed by the instrument's computer.
3. Co11111ents
3.1 Interferences
3.1.1 Background emission may be caused by, among other things,
continuing emission and viscosity differences. Background
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correction points are required for each element. (See ICAP 61 I
operator's manual).
3.1.2 Interelement interferences occur when elements in the sample 1 emit radiation and wavelengths so close to that of the analyte
that they contribute significant intensity to the analyte
channel. If such conditions exist, the intensity contributed
by the matrix elements will cause an excessively high (or I
sometimes low) concentration to be reported for the analyte.
Inter Element Corrections (IEC's) must be applied to the
analyte to remove the effects of these unwanted emissions. To I
calculate an IEC, standardize the ICP, set analysis made to
Standardize intensity ratio and analyze the "interfering
element" at its upper linear range. Divide the concentration 1 of the analyte by the concentration of the "interfering
element." That number is the value entered in the IEC for the
analyte.
3.2 Helpful Hints
3.2.1 Use correct digest for ICP "HCL/HN03" green sticker.
3.2.2 When not using a print out, draw one line through printout
diagonally. Write not used, initial, and date.
3.2.3 Use correct ICP Method (SW-846 #6010), run dilutions
immediately after the sample if running manually or at the end
of the run if using an autosampler.
3.2.4 Saturated Element
3.2.4.1 Zinc, when saturated aspirate with 10% HN03 acid.
3.2.4.2 Cadmium, when saturated aspirate with 10% HN03 acid.
3.2.4.3 Molybdenum, when saturated aspirate with 10% HCL acid.
3.2.4.4 Calcium, when saturated aspirate with 10% HN03 acid.
3.2.4.5 Chromium, when saturated aspirate with 10% HCL acid.
3.2.4.6 Iron, when saturated aspirate with 10% HCL acid.
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3.2.4.7 Sodium, when saturated aspirate with 10% HN03 acid.
3.2.4.8 Barium, when saturated aspirate with 10% HN03 acid.
3.2.4.9 Boron, when saturated aspirate with 10% H2S04 acid.
4. Safety Issues
4.1 All employees are expected to be familiar with and follow the
procedures outlined in the Enseco-Rocky Mountain Analytical
Laboratory Safety Plan. Lab coats and ·safety glasses are required in
all laboratory area at all times. If you have any questions or
safety concerns, see your supervisor or safety officer.
4.2 Many of the metals determined by this method are extremely toxic
and/or carcinogenic. Care should be taken when preparing·standards
from concentrated stock solutions. Wear safety glasses, gloves, and
lab coat. ·
4.3 All of the samples may contain unknown contaminants at unknown levels
other than the analytes being tested. Appropriate care should be
taken when handling samples.
4.4 The plasma emits strong UV light and is very harmful to vision.
AVOID LOOKING DIRECTLY AT THE PLASMA.
5. Apparatus
5.1 Thermo Jerrell Ash ICAP 61 Simultaneous Plasma Emission Spectrometer
which consists of a 0.75 meter polychromator that accepts up to 63
channels, an RF generator, an inductively coupled argon plasma (ICAP)
excitation source and an IBM compatible data acquisition system.
5.2 Rainin Rabbit Peristaltic Pump
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I 5.4 Oxford 1-5 ml and 5-10 ml adjustable pipettors
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6. Reagents, Standards, and Supplies
6.1 Calibration standards prepared monthly by Environmental Resource
Associates. These are verified against EPA standards before use.
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6.2 ICV concentrate solutions are prepared by EPA Las Vegas/UNLV.
Working solutions are prepared daily according to the dilution
instructions accompanying the concentrates.
6.3 Interference check solutions A and Bare prepared by EPA Las Vegas.
6.4 IND CCV SOLN's 1-3 are prepared by Inorganic Ventures and diluted and
run daily. Verified against EPA ICV standards before use.
6.5 Approximately 8 ppm Ba profiling solution prepared at RMAL.
6.6 1000 ppm yttrium stock solution
6.7 Ind. ICP analytical spike A, 8, C prepared by the standards prep
analyst. Verified against EPA standards before use.
6.8 Five dram snap cap vials
6.9 Disposable .45 um syringe filters and syringes (Gelman or
equivalent).
7. Sample Collection ,Preservation and Holding Times
7.1 See SOP #LP-RMA-0056 "Bottle Prep and Cooler Shipping"
8. Procedure
8.1 Preparation
8.1.1 Consult SOP's; LM-RMA-2002 Total,Recoverable,Dissolved,
and Total Metal:Acid Digestion for Water,
EP TOX and TCLP Extracts.
8.2 Instrument Set-up
LM-RMA-2029 Total Metals Digestion Prep-
aration.: Acid Digestion for Soil/Waste
samples.
8.2.1 Turn on coolant water, argon, and exhaust fan.
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8.2.2 Confirm that the argon supply is sufficient.
8.2.3 Turn computer, printer on.
8.2.4 Turn mass flow controller on.
8.2.4.1 Channel 3 should be set at 600 and read 600 + 10.
Channel 4 should set and read 15.
8.2.5 All switches on gas flow panel should be on or in up position.
8.2.6 Turn on peristaltic pump and introduce DI H20 to torch for
approximately 1 minute.
8.2.7 Push RF button on.
8.2.8 Turn power knob up to 75-100 (bottom of yellow on meter).
8.2.9 Turn sample switch off to stop H20 from entering the torch.
(Make sure auxiliary torch switches are on.)
8.2.10 Press ignition button while turning power knob up slowly all
the way. Torch should be on, if not stop·and try again.
8.2.11 Turn sample switch on while turning auxiliary switch off at
same time, slowly.
8.2.12 Aspirate 1000 ppm yttrium. The torch will be blue and pink.
Check the plasma. The pink and blue should be highly visible.
The work coil should sit on the Y line of the polychrometer.
The blue and pink should meet one line below the X line. See
Appendix 7.
I 8.3 Instrument Profiling
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8.3.1 Aspirate the 8 ppm Ba profiling solution
8.3.2 From the analysis screen on the computer, press the
appropriate function keys to initiate manual instrument
profile. Follow the step by step instructions that appear on
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the computer monitor. (Note: The directions given for
turning the micrometer are backwards so turn the micrometer in
the opposite direction.) Hit the F-9 key to keep your
profile.
8.4 Instrument Calibration
8.4.1 From the analysis screen press the calibration key. The
calibration screen will appear on the monitor. Aspirate ERA
calibration standard #1 (blk). Make sure the standard is in
the torch before telling to monitor to expose. (20 seconds).
Hit F-1 to initiate exposure of standard calibration #1. Wait
until the results have printed before pulling it out. Rinse
with DI HN03 for approximate one minute. Hit the F-9 key to
keep standard #1. Continue this procedure with the rest of
the calibration standards in the order which they appear on
the monitor. Make sure you F-9 (done/keep) after ·each
standard. F-9 to keep all standards. The stop/intercept
screen should appear. Hit F-2 to print screen. F-9 ~our way
out to operation screen and hit enter. You are now at the
analysis screen.
8;5 Sample QC Set-up
8.5.1 An ICV-1/3, ICS-A/B, Ind. CCV must be made up daily from the
concentrate solutions.
8.5.1.1 EPA ICV-1/3: Aliquot 1 ml of ICV-1 and one ml of ICV-
3 in a 30 dram vial. Bring to 10 mls with 8 mls of 1%
HN03.
·8.5.1.2 EPA-ICS-A/B: Aliquot 1 ml.of EPA ICS-A and 1 ml EPA
ICS-B into a 30 dram vial and add 8 mls of 1% HN03.
8.5.1.3 Ind. CCV: Use 0.2 mls of each Inorganic Ventures
solutions CCV-1, CCV-2, CCV-3 in a 30 dram vial. Add
19.4 mls of 10% HCl.
8.6 Data Package Set-up
8.6.1 Find the project or projects you will be working on.
8.6.1.1 If running an aqueous total, recoverable, soil/waste,
EP-1, EP-2, or TClP use the QC lot number from the
bottle. (These are digested samples.)
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8.6.1.2 If you are running an aqueous dissolved, use the date
of analysis for QC lot number.
8.6.2 Write the project number and sample numbers on the ICP cover
sheet. Write the project QC lot number (see 8.5.1.1/8.5.1.2).
Write the analysis test (see daily JAK list). For special
instructions go into LIMS. Type LIMSMENU and hit the enter
key. Project/Data Maintenance should be highlighted. Hit the
enter key, go to Group Code and hit the enter key, type the
project number and hit the enter key. This screen will let
you know if there are any special instructions. If no special
instructions mark the N column on the cover sheet. If there
are special instructions hit F-5 (Test List), hit F-5 (More
Functions), hit F-7 (Group Instructions). The Group
Instructions should appear on the screen. Print the special
instructions by hitting the Ctrl key and the P key
simultaneously. Mark the Y column on the cover page. If
instructions appear but are not applicable to ICP metals, mark
Y/NA column. Instructions need not be printed.
8.6.3 Hit the F-1O key, go down to Test Request by sample, and hit
the enter key. Type the project number and hit the enter key.
Choose correct sample number and find the correct ICP test.
Hit F-1 (Result Detail) and hit F-1 (Add/Edit Results). This
screen will show you the analytes you will need. Circle
analytes on the cover sheet. Hit the F-1O key. The monitor
will ask you if you wish to cancel the operation. Hit the "Y"
key for yes. Get a "Data Review Program Level l Review
Checklist", and "ICP DCS Sheet" for each QC lot number, and a
"Comment Anomaly Form." The Data Review Checklist is to be
filled out before handing the package to the supervisor for
reviewing. The DCS sheets should be filled out after running
each DCS. The anomaly form should be filled out when anything
out of the norm is seen, e.g. dilution, viscosity, color,
odor.
8.7 Sample Analysis
8.7.1 From the ICP monitor screen hit F-1. This should bring you to
the "Sample Information Screen." Type the QC name or project
and sample number under "Sample Name", hit the enter key.
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9.
This will bring you to the "Comment" section. Type the QC I
number and/or any pertinent information that is needed.
(Note: No DCS lot number for QC.)
8.7.2 Hit the enter key, this will bring you to the "Operator ID." I
Type your initials. Hit the enter key. This will bring you
to the "Corr. Factor." Type your dilution factor, example: lX
for H20 and lOOX for soil/waste and any other dilution factor I
that may be required. Aspirate the sample for 20 seconds and
hit the F-1 key to start exposure. Wait until second exposure
is complete before rinsing in DI H20. When the sample is done 1 printing, repeat procedure for next sample. (Note: See QC
requirements before running ICV, CCV, DCS, ICB, and CCB.)
QA/QC Requirements I
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9.1 QC Order
9 .1.1 ICV-1/3
9.1.2 ICS-A/B
9.1.3 CCV
9.1.4 ICB
9.1.5 Prep Blank (if a digited project)
9 .1.6 DCS-1
9.1.7 DCS-2
9.1.8 Seven samples
9.1.9 CCB
9 .1.10 CCV
9.1.11 Ten samples, etc.
9.1.12 CCB
9.1.13 CCV
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9.2 QA/QC Explanations
9.2.1 Initial Calibration Verification 1/3
9.2.1.l The ICV-1/3 must be within 10% of the true value.
(See Appendix 2.) To make the ICV, see Section
.8.5.1.1. The 1 ICV-1/3 is used as an independent
source to verify that the lCP is correctly calibrated.
The ICV-1/3 is also used to verify standards made at
RMAL.
9.2.2 Interference Check Solution A/B
9.2.2.1 The ICS-A/B must be within 20% of true value. (See
Appendix 3.) To make ICS-A/B, see Section 8.5.1.2.
The ICS-A/B is used to check interelement corrections.
9.2.3 Continuing Calibration Verification
9.2.3.1 ln the CCV all elements that are needed must be within
10%. (See Appendix 5.) The CCV is used to verify
that the instrument is still in calibration.
9.2.4 Initial Calibration Blank
9.2.4.1 The ICB must be less than Enseco reporting limit for
elements being used. (See Appendix 1.) The ICB is
used to check for contamination and carryover. Use
the ERA calibration standard 1 for ICB's and CCB's.
9.2.5 Prep Blank
9.2.5.1 The prep blank must be less than the Enseco reporting
limit and for elements being used. (See Appendix 1.)
The prep blank is used to show if any contamination
was introduced during the digestion process. The prep
blank showing contamination can be used if
contamination does not exceed two times the Enseco
reporting limit at which time an anomaly must be
included with data.
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9.2.6 Duplicate Control Sample
9.2.6.1 The DCS's must be within 25% of true value.
Appendix 4.) The DCS is used to verify that
samples were properly digested.
(See
the
9.2.7 Continuing Calibration Blank
9.2.7.1 Same as ICB. See Section 9.2.4.1.
9.2.8 Sample Duplicates
9.2.8.1
9;2.8.2
Duplicates are to be run only when a certain
project specifically asks for it. There is no
acceptance criteria for project specific QC. If
bad RPD, pl ease inform your super'vi sor.
The sample duplicate is run to show
reproducibility.
9.2.9 Sample Matrix Spike
9.2.9.1 Matrix spikes are to be run one in every 20
samples. The matrix spike is used to show if there
are any interferences in the sample and also to see
if you are losing anything during the prep.
9.2.10 Sample Matrix Spike Duplicate
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9.2.10.1 Matrix spike duplicates are to be run one in every 1 20 samples. The MSD is to show reproducibility
with matrix interferences.
9.3 Corrective Actions
9.3.1 Follow the corrective actions outlined in the current Enseco
QAPP Manual.
9.3.2 If the prep blank for any element being used is more than two
times the reporting limit the supervisor/coordinator should be
notified.
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10. Calculations
10.1 See ICAP 61 Operators Manual
11. Reporting Requirements
11.1 Units
11.1.1 All units will be reported in mg/Lor mg/kg. Unless otherwise
specified by client.
11.2 Limits
11.2.1 If there is no blank contamination or dilution required report
ND for anything reading less than the reporting limit. See
Appendix 1.
11.2.2 If the blank shows contamination, (but is less than two times
the reporting limit), the reporting limit is raised to the
blank value.
11.2.3 If dilutions were required due to insufficient sample,
interferences, or other problems, the reporting limit is
multiplied by the dilution factor.
11.3 Significant Figures
11.3.1 Reporting Limits
Results will be reported to two significant figures if less than
ten and three significant figures if more than ten. (When
entering into LIMS, enter all significant figures up to 5, LIMS
will automatically round to appropriate amount of significant
figures.)
11.4 LIMS Data Entry
11.4.1 For manual entry refer to Enseco QAPP.
11.4.2 For auto entry refer to Enseco Incorporated Automated Data
Upload Program for Instrument Results. Revision 2.0 July 1989.
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11.5 Anomalies
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11.5.1 Anything that does not meet normal standards. Some examples
are: high viscosity dilutions due to interferences, high
concentrations, color, and blank contamination. These must be
documented and added to the data package.
12. Review Requirements
12.1 See SOP #LP-RMA-0064 "Metals Data Review for Industrial Inorganics."
13. References
13.1 ICAP 61 Operators Manual-Thermo Jarrell Ash corporation, January, 1988
Copyright 1987.
1'3.2 Test Methods for Evaluating Solid Waste. USEPA sw~846 Third Edition
1986.
13;3 Methods for Chemical Analysis of Water and Wastes. United States
.Environmental Protection Agency. EPA-600/4-79-020 Revised March 1983.
13.4 Enseco QAPP Manual
13.5 Enseco Incorporated Automated Data Upload Program for Instrument
Results Revision 2.0 July 1989.
13.6 M-EQA-0002 Internal QC Checks-Laboratory Performance QC
13.7 Enseco SOP #LM-RMA-2029 "Metals Prep Digestion for Soils"
13.8 Enseco SOP #LM-RMA-2002 "Metals Prep Digestion for Aqueous"
13. 9 Enseco SOP #LP-RMA-0064 "Metals Data Review for Industrial lnorganics"
13.10 Enseco SOP #LP-RMA-0056 "Bottle Prep and Cooler Shipping"
13 .11 Enseco Safety Manual
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Revision No. :
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APPENDIX 1
INDUSTRIAL INORGANIC CHEMISTRY
METALS DEPARTMENT
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Effective Date:
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ICP INSTRUMENT DETECTION LIMITS -MARCH 1991
MDL* Enseco ILL*
Element (mg/L) Reporting Limit (mg/L)
Aluminum 0.009 0.1 500
Antimony 0.02 0.06 100
Barium 0.003 0.01 100
Beryllium 0.002 0.002 40
Cadmium 0.003 0.005 100
Ca lei um 0.03 0.2 500
Chromium 0.006 0.01 100
Cobalt 0.004 0.01 100
Copper 0.004 0.02 100
Iron 0.007 0.1 500
Lead 0.01 0.05 100
Magnesium 0.008 0.2 500
Manganese 0.003 0.01 100
Molybdenum 0.005 0.02 100
Nickel O.OQ.4 0.04 100
Potassium 0.2 5 500
Silver 0.002 0.01 100
Sodium 0 .1 5 800
Vanadium 0.004 0.01 100
Zinc 0.002 0.02 100
Additional analytes and levels available
Arsenic 0.02 0.1 100
Boron 0.005 0.1 100
Lithium 0.002 0.05 500
Phosphorus 0.09 0.3 400
Selenium 0.05 0.2 100
Silica as Si02 0.2 0.5 500
Strontium 0.02 0.05 100
Thallium 0.5 2 100
Tin 0.03 0.1 100
Titanium 0.003 0.005 100
*MDL= Method Detection Limit (subject to change)
ILL= Instrument Linear Limit
SOP No.:
LM-RMA-2037
ICV-1 {0489)
ICV-2 (0989):
ICV-3 (0189):
ICV-4 {0389):
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Revision No.:
1.0
APPENDIX 2
(after 10-fold dilution)
Value
Element (ug/L)
Al
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Ni
K
Ag
Na
V
Zn
2010
1960
483
502
48700
510
502
515
2040
4800
24600
504
48D
49000
500
49600
488
3100
(after 10-fold dilution)
Value
Element (ug/L)
As
Se
52.6
52.6
(after 10-fold dilution)
Value
Element (ug/L)
Sb 978
(after 10-fold dilution)
Value
Element (ug/L)
Cd
Pb
Ag
Tl
95.8
97.5
98.6
97.0
All ICV's subject to change due to different lots.
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Revision No.:
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APPENDIX 3
PROCEDURE
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This material was prepared by the University of Nevada, Las Vegas,
Quality Assurance Laboratory. If there are any questions regarding this
reference material, please call [phone].
TABLE 1. "TRUE VALUE" CONCENTRATIONS FOR THE ELEMENTS IN INTERFERENCE CHECK
SAMPLE PART A (1287) MIXED WITH PART B (0387)
Element
Al
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Ni
Ag
V
Zn
Soln A
511000
476000
48
219000
513000
Concentration ug/L
Solutions subject to change due to different lots
Soln AB
508000
483
474
909
470000
513
478
534
211000
4850
513000
470
916
993
475
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APPENDIX 4
Industrial Metals
DCS Values
Enseco DCS (Duplicate Control Samples)
All values are in mg/L
Aluminum (Al)-
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Calcium (Ca)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Magnesium (Mg)
Manganese (Mn)
Nickel (Ni)
Potassium (K)
Silver (Ag)
Sodium (Na)
Vanadium (V)
Zinc (Zn)
Concentration
2.0
0.5
0.5
2.0
0.05
0.05
100
0.2
0.5
0.25
1.0
0.5
50
0.5
0.5
100
0.05
100
0.5
0.5
For soil values multiply by a factor of 100.
For leachate values multiply by a factor of 10.
I Effective Date:
July 1, 1991 I
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--------------------------'-· l>--1-AfflJARDl='nseco OPERA TING""'coming Comp,nv
PROCEDURE .
SOP No.:
LM-RMA-2037
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium "Lo"
Calcium "Hi"
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium "Lo"
Magnesium "Hi"
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silica
Silver
Sodium
Strontium
Tin
Thallium
Titanium
Vanadium
Zinc
Rev1s1on No.:
1.0
APPENDIX 5
INDUSTRIAL CCV LEVELS
1.0
1.0
1.0
1.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
1.0
1.0
1.0
10
1.0
1.0
1.0
1.0
10
1.0
21.4
2.0
10
1.0
10
10
1.0
1.0
1.0
Inorganic Ventures CCV-1 Lot #G-MEB0439
Inorganic Ventures CCV-2 Lot #G-MEB05007
Inorg_anic Ventures CCV-3 Lot #G-MEB04041
Page 18 of 20 -----
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Effective Date:
July 1, 1991
Stock solutions made daily by an analyst using lOOx dilution.
I ---------------------------5-ifAffflARDEnseco
0 PERA TI NG Coming Company I
PROCEDURE
Page 19 of 20 --I
SOP No.: Revision No.: Effective Date:
LM-RMA-2037 1.0 July l, 1991 I
APPENDIX 6 I
CALIBRATION PARAMETERS
I
Element Wavelength
Ag 3280.68x2 I
Al 2373.12x2
As 1936.96x2 I Au 2675.92x2
B 2496.78x2
Ba 2335.27x2 I Be 3130.42x2
Ca 3158.97x2
Cd 2288.02x3 I Co 2286.16x2
Cr 2677 .16
Cu 3247.54x2
Ca 3933.66x2 I Fe 2714.41
Fe 2599.40x2
K 7664.91 I Li 6707.84
Mg 2790.79
Mg 2795.53x2 I Mn 2949.20
Mo 2020.30x2
Na 3302.37x2
Ni 2316.04x2 I Os 2255.85x2
p 2149.14x3
Pb 2203.53x2 I Pt 2036.46x3
Tl 1908.64x3
Ti 3349.41x2
Sb 2068.38x2 I Se 1960.26x2
Si 2881.58x2
Sn 1899.90x2 I Sr 2152.84x2
V 2924.02x2
Na 5895.92 I Zn 2138.56x2
y 3710.29x2
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STANDAR[c __ --------------------------~0:--;:P';:;cERATI~r,eco
PRQCEDURE°om;ng C=p,my
SOP No.:
LM-RMA-2037
Revision No.:
1.0
APPENDIX 7
y
0
Page _1Q_ of 20
Effective Date:
July 1, 1991
.. ... ... ·' CONFIDENTIAL I
BUSINESS
INFORMATION I
Sf Pl 1 3. Q' STANDARD , I OPERATING
PROCEDURE
Subject or Title, Pagel of 22
The Determination of Volatile Organics (VOCS)
in Ambient Air by GC/MS -Scan Mode
SOP NO: Revision No.: 2.0 Effective Date: CRL-LM-7D01 March 1, 1990
supercedes: Revision 1.0
1. Scope and Application
1.1 Analytes (See Table 1)
1.2 Detection limit
' (See Table 1)
1.3 Applicable matrices -air -
1.4 Dynamic range (See Table 1)
1.5 Approximate analytical time
4 min. -cool down of cryo trap
2 min. -flush of inlet system on trap
10 min. -collection of 500 mL sa~ple on trap
2 min. -flush of inlet eyetP.m with internal etd.
2 min. -collec"tion of 100 mi~ of internal etd on trap
2 min. -flush of trap with IIP Helium
32 min. -GC run time
When running multiple eample1J, etepe can be overlapped
to reduce run time to 40 min.
Prepared ~ / str:,,ve;}/arrie
.LJ u1!,C,., ..JI 1ca
Managem~prov~ -~P~ QA Officer Approval,
<fJauL~-
Date:
0;/0'1110
Date\/./
6/ $'/"I"
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STANDARD
OPERATING
PROCEDURE
Page _2_ of
The Determination ol Volatile Orqanioa (VOCa)
in Ambient Air by oc/MS -ecan Mode
22
SOP N01
CRL-LM-7001
Revision No.1 2.0 Effective Date,
March 1, 1990
TIIDLE l. voe Target Compounds
Detection Limits Dynamic
Compound R.T. MDL (ppbv) Range (ppbv)
2) Dichlorodifluoromethane (Freon 12) 1.49 0.87 0.87-300
3) Chloromothane 2.48 1.2 1.2-300
4) 1,2-Dichloro-l;l,2,2-
tetrafluoroethane (Freon 114) 2.52 1.0 1.0-300
5) Vinyl chloride 2.86 1.2 1.2-300
6) Bromomethane 3.58 1.5 1.5-300
7) Chloroethano J.93 2.5 2.5-JOO
8) Trichlorofluoromethano ( 11) 4.54 0.55 0.55-JOO
9) cie-1,2-Dichloroethene s.63 0.84 O.D4-JOO
10) Carbon disulfide 5.63 6.2 6.2-1200
11) 1,1,2-Trichloro-1,2,2-
bifluoroethane (Freon llJ) 5.87 0.96 0.96-JOO
12) Acetone 6.10 6.6 6.6-300
14) Methylene chloride 6.89 l.'ll 1.9-JOO
15) trane-1,2-Dichlorootl,ene 7.36 1.9 1.9-JOO
16) Hexane 7.98 4.0 4.0-300
17) 1,1-Dichloroethane 0.22 1.2 1.2-300
18) Vinyl Acetate 8.71 1.3 1.3-300
19) 1,1-Dichloroethene 9.43 1.1 1.1-300
20) 2-Butanone 9.68 1.4 1.4-300
21) Chloroform 10.27 1.1 1.1-300
22) 1,1,1-Trichloroethano 10.27 0.45 0.45-300
23) Carbon tetrachloride 10. SJ 0.55 0.55-300
24) Benzene 11.00 1.6 1.6-300
25) 1,2-Dichloroethane 11.19 0.53 0.53-300
26) Trichloroethane 12.44 1.2 1.2-300
27) 1,2-Dichloropropane 12.07 3.9 J.9-300
28) 1,4-Dioxane 13.34 3.5 3.5-300
29) Bromodichloromethane 13.68 0.90 0.90-300
30) cis-1,3-Dichloropr.opene ·14.61 1.5 1.5-300
31) 4-Methyl-2-pentanone 15.14 1.6 1.6-300
32) Toluene 15.16 1.5 1.5-300
JJ) trane-1,3-Dichloropropene 16.00 1.6 1.6-300
34) 1,1,2-Trichloroethane 16.34 1.4 1.4-JOO
JS) Tetrachloroethene 16.28 1.4 1.4-JOO
36) 2-Hexanone 17.10 3.0 J.0-300
37) Dibromochloromethane 17.06 1.4 1.4-300
38) 1,2-Dibromoethane 17.00 1.0 1.0-JOO
39) Chlorobenzene 10.28 1.3 l.J-300
40) Ethylbenzene lR. 73 1.3 l.J-300
41) 1,4-and 1,3-(p,m) Xylene 19.04 2.6 2.6-600
The
CONFIDENTIAL
BUSINESS I
INFORMATION
Page
Determination ol' Volatile Organic ■ (VOCa)
in Ambient 1.ir ·by OC/MS -Bean Mode
_J_
STANDARD
OPERATING
PROCEDURE
of _22 -
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SOP N01
CRL-LM-7001
Revioion No,, 2.0 Effective Date,
March 1, 1990
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42)
43)
44)
45)
46)
47)
48)
49)
SO)
51)
52)
SJ)
54)
2.
·',· TIIBl,E l. voe Target Compounds
(Continued) I
Detection Limits
Compound R.T. MDL (ppbv)
Dynamic I Range
1,2-(ortho) Xylene 19,94 1.1 Styrene 20.02 J.S Dromoform 20.37 1.0 1,1,2,2-Tetrachloroethane 21.99 1.9 Benz:yl chloride 21.90 1.0 4-Ethyltoluene 22.Jl 2.0
1,J,5-Trimethylbenzene 22.40 l.J
1,2,4-Trimethylbenzene 23.37 1.5
l,J-Dichlorobenzene 23.04 1.7 1,4;Dichlorobenz:ene 24.lJ 2.2
1,2-Dichlorobenzene 24,97 2,4
1,2,4-Trichlorobenzene 29.28 J.6
Hexachlorobutadiene 29.93 .2.4
1.1-JOO I 3,5-JOO
1.0-JOO
1,9-JOO
1.0-JOO I 2,0-JOO
1.3-JOO
1.5-JOO I 1.7-JOO
2.2-JOO
2.4-_J00 I 3.6-300
2,4-JOO Summary of Method
2,1 A pressurized air sample io metered through a maee flow controller .I onto a cryogenically cooled trap. llfQer 500 mL of the sample has
been trapped, a valve lo owitchcd and tho trap ie heated to purge the
trap•e contente onto the gae chromatography column. Tho target I
compoundo aro analyzed with a maee spectrometer operated in the scan
mode. ·
3. Comments I 3.1 Interferenceo
J.1.1
J. 1.2
Gao regulatoro are clean·ed by the manufacturer using Freon 1 113,.which le one of the target compounds, Before using ultra
high purity (UIIP) Nitrogen (N, ), llydrocarbon (IIC) free air,
Internal Standard (I.S.), or a target compound standard mix,
each regul.etor should bo purged a minimum of three times with
the appropiriate gaa.
Contaminnt·ion may occur in tho oampllng system if
nre not properly clnaned prior to uoe. Canletere
collect uo_urce aamp).ee nhould not be used for the
canisters
used to
collection
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CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
The
Page _4_ of _22_
Determination of Volatile OrqanicB (VOCe)
SOP NOi
CRL-LM-7001
in Ambient Air by oc/Ms -Bean Mode
Revision No., 2.0 Effective Date,
March 1, 1990
of ambient air eamplee until a blank analyols indicates that no target
compounds ere present above tho MDI,. /Ill other uempling equipment including
pumps, flow controllers end filtoro must be thoroughly cleaned to ensure that
the filling apparatus will not contaminate samplee.
3.2 Helpful Hints
None
4. Safety Ieeue~
4.1 In order to prevent contem.lnntion of the lab air by the samples, the
vent line muet be connected to the eyetem outlet and the fume hood
muet Ua on.
4.2 While 'making etanrlardo, thrJ fume hood must be running. When finished
valves muot bo clooed and .!.inee vented.
I
4.3 All compreeaerl gao cylindo:ce muot be oecurely fastened to a bench or
wall.
4.4 Normal procautiono should bo ueod in the handling of liquid nitrogen
(LN2) (do not touch tranofer .llneo ns bnrne can reoult).
4.5 Sampling canioters ohoultl never be prcouurized over 40 psig.
s. Sample Collection, Prcocrvation, ~ontaincro and Holding Times
5.1 Sampleo ohould be collected in precleaned and batch analyzed SUMMA
passivated caniotero. JI 7 n,icron filter ottPuld be placed on the
inlet of the can to proto=t tho valve from 1'articulatea. Canisters
should never be prcaaurized over 40 polg. ·
5.2 The absolute pressure of ~he canioter must be recorded before end
after sample collection.
5.3 Samples must be kept at <25°C.
5.4 Sampleo should bo analyzed within 14 days of collection.
6. · Apparatus and Materials
6.1 Gao chromat0<Jrnph -capablo of eubambient temperature programming for
the oven and wil:h the jot ucparator option (llowlett Packard 5090).
6. 2 Haoo-eolect lvo ctr1tcctor. -£tquippod wlth coraputer and appropriate
software (Hewlett Packard !i97011 with IIP-1000 R'i'E-11 data system).
. ' ! •
'.
CON Fl DE NTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
Page _5_ of _22_
The Determination of Volatile Orc;janice (VOCe)
in Ambient Air. by GC/MS -Boan Mode
BOP N01
CRL-LM-7001
Revieion No., 2.0 Effective Date,
March 1, 1990
6.3 Cryogenic trap with temperature control aeeembly (Nutech 8533).
See Figure 1.
6.4 Electronic maee flow controller -for maintaining conetant sample
flow (Unit Inotrumento)
6.5 Chromatographic grade otainleou otool tubing and etainleee eteel
plumbing fittingH.
6.6 Chromatographic column -011-624 0.53 ID, JO meter length (J&W
Scientific;.
6. 7 · Stainleee oteel vacuum/preaf',tre gauge capable of measuring from JO•
of mercury (llrt) to 40 pnl.g. (Span Inotrumente)
6.8 High preciel.on vacuum gau<Je -for making daily etandarde. (Wallace
_Tiernan Pennwalt)
'6.9 Preeeure regulatoro for cai:ricr gao and otaridarde -.2 etage,
etBinleeo ateel dla91·am.
6.10 SUMMA paeoivated caniotero 6 L (Scientific Inetrumentation
Specialieto)
6.11 7 micron filtore (Nupro), or equivalent,
7. Reagents and Standardo
7.1 4-bromofluorobenzene, 50 ng/mL in methanol (for tuning of maee
opectrometer),
7,2
7.3
7,4
lligh purity helium for carrier gao.
Standards at a nominal co~centration of 1 ppmv (CS, ie not ae stable
and eo the concentration io 5 ppmv). Standards are prepared in a
balance gao of nitrogen a,1d are analytically certified by the
supplier (Scott-Marrin and Scott Specialty). To facilitate
certification by vendor, ·che standards were divided into 5 cylindere.
(See Tables 2-7.)
Internal standard mix of bt·omochloromethane, 1,4-difluorobenzene,
and chlorobenzene-d5 at 1000 ug/ml each in methanol (Supelco).
(See Table 6.)
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CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
Page 6 of 22
The Determination of Volatile Organic& (VOCe) ---
SOP NO,
CRL-LM-7D01
INJ. PORT 1
in Ambient Air by oc/MS -seen Mode
Revision 110.1 2.0
P'IOURE 1. Nutech :JS".3 Flow Diagram
!NJ. PORT 2
CAI GA
SAH? EL O? ~ """' _ __,
INJSCj VZ:N
V .... "T'" i I ,·· '""' . ... V
.__ ____ L I
.Su""f\' "j 1J.,l--r .. ,., r~,, .. \£1
' I
COLUHN
Effective Date,
March 1, 1990
CARRIER 2
YALVC:S•
RIGHT(C(
·············· LEFT (c.'
- - -~v.~ ----LIN£.J
TRAP PURGC:
[N
'------C-A_,J'f R DG-....
H O PURGC:
2
....
COLUMN
wf c.ryo ··~ VOST ANALYZER FL□V
',--------~----'' ,._ ______ C.rye p..,r_,.:. ,
DIAGRAM <FRONT VIEV)
,.
SOP N01
CRL-LM-7001
-
CONFIDENTIAL I
BUSINESS
INFORMATION I
STANDARD
OPERATING
PROCEDURE
Page
Determination~; Volatile Organics (VOCa)
in Ambient Air'by OC/MS -Bean Mode
_7_ of 22 --The
TABLE 2.
Revision No., 2.0
Cyll.ndar No. CC72069
Effective Data,
March l, 1990
Component Concentration (v/v)
Chloromethane 0.98 + 0.05 ppm
Rromomethane 1.00 + 0.05 ppm
Chloroethane 0.96 + 0.05 ppm
Dichloromethane 1.08 + 0.05 ppm
trane-1,2-Dichloroethylene 1.08 + D.05 ppm
Trichloroethane 1.07 + 0.05 ppm
l,2-Dichloroethane 1.10 + 0.05 ppm
1,1,1-Trlchloroeth•ne 0.99 + 0.05 ppm
Tetrnr.hlnrnmot:hnr\o 1.01 + 0.05 ppm
1,2-Dichloropropane 1.08 + 0.05 ppm
cie-1,3-Dlchloropropcne 1.03 + 0.05 ppm
trane-1, J-dichlorop1:-ot..t·me 1.20 + 0.06 ppm
Dibromochloro,net:hano 1.13 + 0.05 ppm
Tetrachloroethyleno 1.14 + D.05 ppm
Ethylbenzene 1.20 + D.06 ppm
p-Xylcne 1.20 + 0.06 ppm
styrene 1.25 + 0.06 ppm
1,1,2,2-Tetrachlor.oethane 1.24 + 0.06 ppm
Dromodlchloroinethane 1.08 + 0.05 ppm
Trichloroethane 0.82 + o.os ppm
Acetonitrile 1.00 + 0.05 ppm
Nitrogen DalanCe
TABLE J. Standard Cylinder No. CC72058
Component Conoantration (v/v)
Carbon Disulfide 4.86 + 0.1 ppm
Nitrogen Balance
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SOP N01
CRL-LM-7001
-
CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
The
Page__!!_ of _22_
Determination of Volatile Organioe (VOCe)
in Ambient Air by OC/MS -Boan Mode
Revision No.i 2.D
TABLE 4. Stand.rel Cylinder No. CC72063
Effective Date,
March 1, 1990
Component Concentration (v/v)
Vinyl Chloride 1.00 + 0.05 ppm
1,1-Dichlcroethene 1.08 + 0.05 ppm
1,1-Dichloroethano .1.06 + 0.05 ppm
2-Dutanone 1.02 + 0.05 ppm
cie-1, 2-Dichloroet:.,ene 1.07 + o.os ppm
Benzene 1.07 + o.os ppm
4-Hethyl-2-pentanono 1.0.9 + 0.05 ppm
1,1,2-Trichloroothane 1.06 + D.05 ppm
Toluene 1.08 + 0.05 ppm
2-Hexanone 1.18 + 0.05 ppm
Chlorobenzene 1.08 + 0.05 ppm
m-Xylene 1.11 + O.DS ppm
a-Xylene 1.12 + 0.05 ppm
1,2-Dichlorobenzone 1.25 + 0.05 ppm
Acetone 0.99 + 0.05 ppm
1,4-Dichlorobenzene 1.04 + o.05 ppm
Nitrogen Balance.
TABLE 5. Standard Cylinder No. CC12390
Component Concentration (v/v)
Freon-12 1.015 + 0.05 ppm
Freon-114 0.95 +-o.05 ppm
Freon-11 0.94 + 0.05 ppm
Freon-113 0.99 + 0.05 ppm
n-llexane 1.02 + 0.05 ppm
1,2-Dibromocthane 0.99 ... 0.05 ppm
4-Ethyltoluene 0.89 + 0.05 ppm
1,3,5-Trimethylbenzene 0.95 + 0.05 ppm
1,2,4-Trimethylben:eene 0.92 + 0.05 ppm
Nitrogen BalanCe
TABLE 6. Intern,d Standard Liquid Hix
Component Concentration (ug/ml)
Bromochloromethane
1,4-Difluorobenzene
Chlorobenzene-d5
1000
1000
1000
The
CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
Page _9_ of
Determination of Volatile Organics (VOCa)
22 - -
in Ambient Air by OC/MS -Scan Mode
SOP N01
CRL-LH-7001
Revision No., 2.0 Effective Date,
March l, 1990
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8.
TABLE 7. Standard Cylinder No. ALM 002636
Component
Benzyl chloride
1,3-Dichlorobenzene
1,4-Dioxane
Hexachloro-1,3-butadiene
Bromoform
1,2,4-Trichlorobenzene
Vinyl acetate
Nitrogen
Procedure
Concentration (v/v)
0.737
0.768
o.895
0.804
0.84
0.898
0.838
ppm
ppm
ppm
ppm
ppm
ppm
ppm
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8.1 -Semple Preparation
The prooeure of the oample canioter ie checked and recorded by I
attaching a vacuum/.oreaaure gauge to the top valve of the
8. l. l
8.1.2
canister (the gaug-, ehould be rinsed for few eeconde with !IC
free air by phyoically holding againet the air outlet and
flushing). 1'he canioter valve ie opened briefly and the
presoure is recorded. If the pressure ie less than 10 peig,
preosurize the canioter to 10 poig with IIC free air.
If the canister preooure is increased, a dilution factor (DF)
ie calculated and recorded.
y. DF C
x.
Where, x. = absolute canieter preseure abeolute before dilution
Y. a absolute caninter preesure absolute after dilution
8.2 Daily GC/MS Tuning
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8.2.l At the beginning o:c each day or prior to a calibration, the
GC/HS eyetcm muot he tuned to verify that acceptable
performance criteria ar.e achieved. If any of the key ions I
fail the abundance criteria lieted in Table 8, the eyetem must
be retuned using 4--nromofluorobenzene (DFO).
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CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPl!:RATINO
PROCEDURE
Page __!Q_ of _22_
The Determination of Volatile Organlce (VOCe)
in Ambient Air by oc/MS -Scan Mode
SOP N01
CRL-LM-7001
Revlelon No., 2.0 Effective Date,
March 1, 1990
B.2.2 For dally tuning, th,, relayo on the Nutech controller
(eee Figure l) ohoulcl be in the right hand position, with
the cryo trap at 150°C (alternatively valves 2 and 6 could
be placed in the left hand position with the auxiliary He
flow eet at 10 ml/min or greater). The GC program le
initiated by using the Datac command in file manager (FHGR).
The GC program le named "GCDFDl." Thie downloads the
program from the dat& eyetem to the GC. Once the oven hae
etabllh:ed·, the remote start light will turn on and the
system le ready for i.njectlon.
l uL of a 50 ng/uL •l-bromofluorobem:ene (BFD) standard le
injected into inje~tlon port 2 of the Nutech 8533 and the
remote otart button ie activated.·
TABLE B. 4-Bromofluorobenzene Key Ione and Ion Abundance Criteria -Maee
50
75
95
96
173
174
175
176
177
Ion Abundance Criteria
15 to 40\ of maoe 95
30 t0 60\ of maee 95
naue Peak, 100, Relative Abundance
5 to 9\ of maee 95
<2\ of. maee 174
>50\ of maee 96
S to 9\ of maoe 174
>95\ but <101\ of maee 174
5 to 9\ of mane 176
8.2.3 Once the tuning run J.o complete c-8 mlnuteo), review a ocan
cloao to tho centar of the f)li'll peak. If it looks close to
paoelng, type in the command TR~', TUNVOl\, data file. Thlo
will start a program that will find a scan that will paee the
tuning and print o:Jt the required information automatically.
If the DFD tuning c:rlterla cannot be met on 2-J lnjectlone,
retuning the lnotr•Jment with PFTDA may be required.
. '
SOP N01
CRL-LH-7001
The
CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
Page _!.L of
Determination of Volatile Organics (VOCe)
22 - -
in Ambient Air by OC/HS -Bean Hodo
Revision No., 2.0
TABLE 9. BFn Tuning Method
Effective Date,
March 1, 1990
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Enter the name of the method file: CCBFDl I
HE T II O D
Method file, CCBFBl CC type1
Column:
Temperature, Inj. P
90.0
CC/DIP LEVEL A
Temp.l 30 •. 0 100.0
Time l l.O 15.0
Rate -35.0 0.0
Temp 2 100.0 o.o
"Time 2 15.0 o.o
.oven equilibration Time .10 min
Run time, 6,00
Scan Start time, 2.50
Splitleee valve time, .BO
Relay 111
Relay 121
Triac 101
Triac 111
ON
327.0
327,0
327.0
327.0
F I
5890
Cap
J:nt fc
250.0
Scan Parameteres Hase Range JS to 260
L E L I s T
LEVEL D
o.o
0.0 o.o o.o o.o
OFF
327.0
327.0
327.0
327.0
Run type, SCAN, cc, El I
Splitleee, Yee
Source I o.o
POST RUN
o.o I o.o
ON
327,0
327,0
327.0
327.0
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OFF •.
327.0
327.0 D 327.0
327.0
Multiplier voltage, 2244 Number of A/D samples, 8 I
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cc Peak.threshold, 20000 counts
Threshold: 100 counts
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CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
The
Page _!L of _22_
Determination of Volatile Organioe (VOCe)
in llmbient Air by OC/HS -Bean Mode
SOP N01
CRL-LM-7001
Revision No., 2.0 Effective Date,
March 1, 1990
TABLE 10. Analytical Method
Enter the name of the method file, GCT014
H E T II O D
Method file, GCT014
Temperature, Inj.P
90.0
GC/DIP
Temp 1 -50.0
Time 1 2.0
Rate 70.0
Temp 2 -20.0
Time 2 # 0.0
Oven equilibration Time
Run timer 32.10
Scan Start timer .10
Splitlees valve timer
Relay flr
Relay 121
Triac tor
Triac flr
Scan Parametore1
o.oo
GC type,
Column,
LEVEL II
-20.0
0.1)
5.1)
127.0
20.0
.10 min
ON
327.0
327.0
327.0
327.0
F I L E L I S T
5890
C!ap
Intfc ;:so. o
LEVEL D
127.0
20.0 o.o
o.o o.o
OFF
327.0
327.0
327.0
327.0
Run typer SCAN, GC, El
Splitless1 Yes
source
o.o
POST RUN
o.o
o.o
ON
327.0
327.0
327.0
327.0
OPP
327.0
327.0
327.0
327.0
Haen Rango 35 to 260
Multiplier voltage: 2244 Number of A/D samplesr 8
GC Peak threshold: 20000 counte
Threoholdr 10 counte
B.3 Calibration
8.3.1 A etatic dilution of the etock otandard gas mixtures is made
in a 6 liter canister. The high precision vacuum gauge is
flushed with IIC froo air and attached to the top valve of a
clean, evacuated cnnioter. After recording the absolute
pressure, 2 pei of each of the 5 standard mixtures ie added to
the canioter (each regulator and the transfer line must be
Tho
CONFIDENTIAi
BUSINESS
INFORMATIOt.8
STANDARD •· OPERATING
PROCEDURE
Page _!L of _22_
Dotormination of Volatile Organics (VOCa)
I
in Ambiont Air by OC/MS -9oan Mode
SOP N01
CRL-LM-70D1
Revision No.1 2.0 Effective Data,
March 1, 1990
I
8.4
8.3.2
8.3.J
-e.J.4
flushed oeveral timeo before transfer of otandard to the
canioter). Close the canister valves and replace the high
precision gauge with a vacuum/pressure gauge. Pressurize the
can with IIC free air to 30 peig. Thie will yield a standard
with a nominal concentration of 44 ppbv for most compounds
( BOO Table 11).
An initial 5 point curve ie run in the linear working
range of the oyetmn. The nominal concentration of the
5 etandardo will ba 18 ppbv, 67 ppbv, 90 ppbv, 224 ppbv
and 287 ppbv.
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On a daily baeie, a one point midrange standard (500 ml of
44 ppbv) le run to v.orify the~ polnt curve. 90\ of the
target compounds munt. be within 30\ of the 5 point curve,
or a new r:: point m~nt: be run. The daily, one point check
standard 1.e used t,~ calculate the concentration of the
samples.
After the calibration runo and•the QA/QC sample rune, an HC I
free air blank ie run. Thio muot be< the MOL for each target
compound.
Analysis I
0.4.1 Tho dally check standard and tho QA/QC samples are analyzed
tho same /JB eamploe. The IIC freo air blank le a eyetem blank I
and differs only in that it ie not transferred to a canister,
but run directly from the cylinder regulator to the sample
inlet oyetem.
8.4.2 Tho oamplo caniater io connected to the oample inlet eyetem. I
The Nutech controller ohould liave valves 2 and 6 in tho left
hand position, while valves 1 ·and 3-5 should be in the right
hand pooition. The auxiliary lie flow should be eet at 40 ml/ I
minute. The canister valve ie opened and the pressurized
sample ie allowed to flow through the maee flow controller
(eet at 50 ml/min) and out the vent line.
0.4.3 The cryogenic trap iE cooled to ite lower eet point of -170•c. I
When the cryo trap reacheo -170°C, the Nutech valve 12 ie
owitched to the right hand position and a timer ie started.
After 10 minuteo ( ;oo ml,) valve 12 ie switched back to the I
left hand position, Thus 500 ml of blank, standard or sample
ie concentrated on the cryo trap.
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CONFIDENTIAL
BUSINESS
INFORl'w1ATION
STANDARD
OPERATING
PROCEDURE
Page _!L of 22
Determination of Volatile Organics (VOCa)
in Ambient Air by OC/MS -Scan Hoda
SOP NOt
CRL-LM-7001
Revieion No., 2.0 Effective Date,
March 1, 1990
-
0.4.5
The valvo on the earnple canister ie closed and the remaining line
preeeuro lo allowed to drop to ambient. The 3-way valve is then
ewitched to the internal standard canister and the I.S. canister
valve is opened and allowed to flush for at leaet 2 minutes. (The
internal standard le made by injecting 20 ul of the liquid mix into
an evacuated canieter and pressurizing to 30 psi(44.6 psia). Valve:
is then switched to the right hand position and.a timer is started.
After 2 minutes, Valve 2 le switched back to the left hand position.
Thus 100 ml of 200 ppbv nominal internal standard mix is injected 01
the cryotrap with each blank, standard or sample.
The CC ie cooled to ite• initial sot point of -50°C by using
Datac in file manager. The name of the GC program ie
"GCT014." Thie takeo about 2.5 minutes. During this time
valves 2 and 6 remain in the left hand position, allowing He
to sweep the trap and remove most oxygen, nitrogen and other
permanent gaeee.
0.4.6 When the GC has roar:hed equilibrium tho red remote start light
will turn on. Switch valve 16 to the right hand position ..
Wait at leaot 10 eer:onde to allow flow through the trap to
equilibrate. 1"he blue "cool" button on the Nutech controller
and remote start button should be pressed simultaneously~
Thie will heat the cryo trap to l50°C and etart the oc
program.
9. Data Interpretation
9.1 Qualitative Analyeee
9.1.1 An anRlyte (e.g., thane lioted in Table l) ie identified
by comparioon of tho sample mane opectrum with the mass
spectrum of a standard of the ouepected compound (standard
reference spectrum). Mase epectra for standard reference
ehould be obtained on the ueer•e CC/HS within the same
12 hours ae the sample analysis. These etandard reference
epectra may he obtained through analyeie of the calibration
etandarde. Two criteria muet be eatiefied to verify
identification. (l) elution of eample component at the
oame cc relative rgtention time (RRT) ae thoee of the
etandard component, and (2) correepondence of the eample
component and the atandard component maee epectrum.
SOP N01
CRL-LH-7001
-
i CONFIDENTIAi.ii
BUSINESS •
INF0~·~1ATIONI
STANDARD
OPERATING
PROCEDURE
Page ....!L of
The Determination ot Volatile Or.ganioa (VOCa)
22 - -
I
in Ambient Air by oc/MS -Scan Mode
9.1.1.l
9.l.l.2
Revision No., 2.0 Effective Date,
March 1, 1990
The sample component RRT must compare within I
± 0.06 RRT unite of the RRT of the etandard
component. For reference, the standard must be I
run within the eame 12 houre as the sample. If
coelution of interfering components prohibits
accurate assignment of the sample component RRT
from t~o total ion chromatogram, tho RRT should I
be aaelgnod by using extracted ion current
profil,,e for ions unique to the component of
intereat.
(1) All ions preeent in the standard maea
epectra &ta relative intensity greater than
10\ (moat abundant ion in the spectrum equals
100\) mu"t be preoent in the sample spectrum.
(2) Th" ,·elative intensities of ions
specified in (1) muet agree within plue or
minus 20\ between the standard and sample
epectra. (Example: For an ion with an
abundance, of 50\ in the standard spectra,
the correepondin sample abundance must be
muot be between 30 and 70 percent.
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9.1.2 For oampleo containl.ng componente not aeeoclated with
the calibration etandarde, a library Search may be
made for the purpoee of tentative identification. The
neceeeity to perfor;-, t.hle type of identification will
be determined by the type of analyses being conducted.
Guidelines for making tentative identification are, D
(l) Relative lntcnoltleo of major lone in the reference
opectrum (lone >lO'l of the moot abundant ion) should be
present in the aample opectrum.
(2) The relative lnteneltleo of the:major lone should
agree within± 20\. (Example, For an ion with an
abundance of 50\.ln tho etandard spectrum, the
corresponding sample ion abundance must be between,30
and 70\).
(3) Molecular lonn preeent in the reference spectrum
should be preeent J.n the sample spectrum.
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SOP Nor
CRL-LM-7001
CONFIDENTIAL
BUSINESS
INFORiv'IATiON
STANDARD
OPERATING
PROCEDURE
Page ...lL of
The Determination of Volatile Organioa (VOCa)
in Ambient Air.by OC/MS -Scan Mode
22 --
Revision No.r 2.0 Effective Dater
March 1, 1990
(4) Iona present in the aample spectrum but not in
the reference epectrt1m should be reviewed for poeeible
background contamination or presence of coeluting
COffl[>OUnde.
(5) Iona present ln the reference spectrum but not in
the sample spectrum ehould be reviewed for poeelble
subtraction from tile sample epectrum becauee of back-
ground contamination or coelutlng peake. Data eyetem
library reduction programo can eometlmee create these
discrepancies.
Computer generated lJ.brary aearch routines should not
uee normalization ~outinee that would misrepresent the
library or unknown epectrn when compared to each other.
Only after visual comparison of sample with the nearest
library searcheo will the maee opectral interpretation
opecialiot aooign" tentative identification.
9.2 Quantitative Analysis:
When a compound hao been identified, the quantification of
that compound will be baaed on the inte<Jrated abundance from
the EICP of the primary charateriotic ion. Quantification
will take place uoing the internal otandard technique.
.. CONFIOENTl1
BUSINESS
INFORMATl01 STANDARD
. OPERATING
SOP NOr
CRL-LM-7001
PROCEDURE:
Page _u_ of
The Determination or 11ol11tile Orcj11nioa (VOCa)
22 - -
in Ambient Air by oc/MB -Scan Mode
Revision No., 2.0 Effective Dater
March 1, 1990
10. QA/QC Requirements
10.l The maee spectrometer must meet the tuning criteria described in
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Sect ion 8. 2 • I
10.2 After tuning, a single point check etandard muet be analyzed. Ninety
percent of the target compound concentratione must be within± JOI of f~u the~ potnt calibrati~n curve. If the check etandard faile to I
meet thla criterion, a ne11 t~ point calibration curve must be run.
10.J A laboratory control sample (LCS) muot be analyzed after the check
standard. 'l'hio eample will coneiet of the target VOCe prepared in a
eeparate canieter at a conc~ntration that differe from that of the
check standard. Five compounds will be ueed to aeeeee control for
the LCSt methylene chloride, 1,1-dichlOroethene, trichloroethane,
toluene and l, 1, 2, 2-tetra·::hloroethane. 'l'he percent recovery for the
five control compoundo must: be within a window of 80-115\.
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10.4~or each lot of 20 oampleo· analyzed, a duplicate control eample (DCS)
muet be analyzed after th<> LCS. The DCS eample le identical to the
LCS in compooition and eo,JJ:ce. The 80-115\ recovery criterion must IJ
· be met. In addition, the r.e,lative percent difference (RPD) for the IJ
LCS and DCS muet be~ 20\.
10.5 A eyetem blank of IIC free nir muet be analyzed after the LCS or DCS, 0
The blank reeulte muet indicate that there are no target compounds .
present above ~:ho MDI~-
10.6 If any of the above crito, I.a are not mot, corrective actions must be II
implemented before analyoee can proceed. fl
11. Calculations
11.1 The IIP data eyetem automatlc.ally quantitatee
on a 500 mL eample size. The results are in
wae pressurized before analysis, the reeulte
the dilution factor DF (eee section 8.1.2).
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the sample reeulte baaed I
ppbv, If the canister
must be multiplied by
11.2 If a sample size other th~n 500 mL wae used, the result must be
adjueted ae shown below:
I
I reeult ppbv x sample volume injected
500 mL
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CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
Page ....!.!L of _22_
The Determination \lf Volatile Organioa (VOCa)
SOP N01
CRL-LM-7001
12. Reporting
in Ambient Air :·•:r GC/MS -Soan Mode
Revision No., 2.0 Effective Date,
March 1, 1990
12.l Reporting unite aro ppbv. If reoulte are to be reported in ng/L
uee the following equation:
Ppbv X .Molecular weight of compound reeult
24.5
a ng/L
Note:; 24.5 ie the etandard volume of ideal gae at 25 degreee
Centigrade and 1 atm,
12.2 Reporting limite
See Table 12
12.3 Significant figureo
12.3.1 All reeulte ehould bn reported to two significant figuree.
-12.3.2 Only report reeulte below detection limit ae ND(DL).
12.4 No cQnyereiQn of the analytl.cal reeults to the etandard
condlt one le made.
13. References
13.1 Method source
"EPA Compendium Method T0-14. The Determination of Volatile Organic
Compounds (VOCe) in Ambient Air ueing SUMMA Paesivated Canieter
Sampling and Gao Chromatog,-aphic Analyeie.•
13.2 Deviatione from Method
13.2.1 Dry !IC free air lo ueed for the daily blank and for
dilution purpooeo.
13.2.2 T0-14 recommende tho uee of a .32 mm column coupled directly
to the MSD. With the IIP eyetem, the MSD can only handle flow
of 1 mL/min or leee. The .32 mm column provides -3 mL/min.
Eneeco ueee a .SJ mm column through a jet separator.
13.2.3 T0-14 deecribee on inlot oyetem that ueeo a vacuum to pull a
elip otream sample through the trap. Eneeco ueee the pree'aure
of the eamplo caninter to drive the eample through the trap.
CONFIDENTIAi
BUSINESS
IN FORs~r.!~? Nt
The Page
Determination nf Volatile Organics (VOCs)
in Ambient JI.!.::-hy OC/MS -Bean Mode
OPERJ\TINO
PROCEDURE I
_!2_ of _22_
I SOP N01
CRL-LK-7001
Revision No., 2.0 Effective Date1
March 1, 1990
TABLE 11. i Concentration of Daily Check Standard
compound
2) Dichlorodifluoromethane (Freon 12)
·J) Chloromethane
4) l,2-Dichloro-1,1,2,2-
tetrafluoroethane (Freon 114)
5) Vinyl chloride
6) Bromoethane
7) Chloroethane
B) Trichlorofluoromethane (11)
9) cis-1,2-Dichloroethene
10) carbon disulfide
11) 1,1,2-Trichloro-1,2,2-
trifluoroethane (Freon 113)
12) Acetone
14) Methylene chloride
15) trane-1,2-Dichloroethene
16) Hexane
17) 1,1-Dichloroethene
18) Vinyl T\cetate
19) 1,1-Dichloroethene
20) 2-Butenone
21) Chloroform
22) 1,1,1-Trichloroethene
23) Carbon tetrachloride
24) Benzene
25) 1,2-Dichloroethene
26) Trichloroethane
27) 1,2-Dichloropropane
2B) 1,4-Dioxene
29) Bromodichloromethene
JO) cis-1,3-Dichloropropene
31) 4-Methyl-2-pentanone
32) Toluene
33) trans-1,3-Dichloropropene
34) 1,1,2-Trichloroethane
35) Tetrachloroethene
36) 2-Hexanone
37) Dibromochloromethane
3B) 1,2-Dibromoethane
39) Chlorobenzene
40) Ethylbenzene
41) 1,4-and 1,3-(p,m) Xylene
Concentration
(ppbv)
45.42
43.B4
42.50
44.74
44.74
42.96
42.06
47.BB
217.44
44.30
'( 44.30
48.32
4B.32
45.64
47.42
37.50
4B.32
45.64
47.B2
44.30
45.20
47.82
49.22
36.6B
4B.32
40.04
4B.32
46.08
48.76
4B.32
53.70
53.70
51.00
52.BO
50.56
44.30
4B.32
53.70
103.36
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CONFIDENTIAL
BUSINESS
INFORMATION
STANDARD
OPERATING
PROCEDURE
Page ...lQ.._ of _22_
Tha Determination of Volatile Organloe (VOC■)
in Ambient Air by oc/MS -Scan Meda
SOP Nor
CRL-LM-7001
Revision No.r 2.0 Effective Dater
March 1, 1990
TABLE 11. Concentration of Dally Check Standard
compound
42) 1,2-(ortho) Xylene
43) styrene
44) Bromoform
45) 1,1,2,2-Tetrachloroethane
46) Benzyl chloride
47) 4-Ethyltoluene
48) 1,3,5-Trlmethylbenzene
49) 1,2,4-Trlmethylbenzene
50) 1,3-Dlchlorobenzene
51) 1,4-Dlchlorobenzene
52) 1,2-Dlchlorobenzene
53) 1,2,4-Trlchlorobenzene
54) Hexa1':hlorobutadlene
Concentration
(ppbv)
50.12
55.92
37.58
55..48
32.98
39.82
42.50
41.16
34.36
46.54
55.92
40.18
35.98
Tho
CONFIDENTIAi
BUSINESS
INFORMA1l0'
STI\NDIIRD
OPEIII\TINO
PIIOCEDUIIE I
l'a90 21 of _22_
Doterminatl.on ot Vol11tilo Orqanice (VOCa) --I ln llmblent llir by oc/Hs -Boan Hoda
SOP N01
CRL-LH-7001
nev~elon No., 2.0 Effective Date,
March 1, 1990 I
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2)
J)
" I
5)
6)
7)
8)
9)
10)
11)
12)
H)
15)
16)
17)
18)
19)
20)
21)
22)
23)
2<1)
25)
26)
27)
28)
29)
JO)
Jl)
32)
33)
34)
JS)
36)
37)
JO)
39)
4D)
41)
Table 12. voe ne~ortlnq Llmite
Compound
Dichlorodlfluoromothanc (Freon 12)
Chloromothano
l,2-Dlct,loro-1,1,2,2-
tetrafluoroethano (Freon 114)
Vinyl chlorido
Dromoethano
Chloroethane
Trlchlorofluoromothnno ( 11)
cio-1,2-Dichlorootheno
Carbon disulfide
1,1,2-Trlchloro-1,2,2-
tl:"1.fluoroethano (~'roan 113)
Acetone
Methylene chlorido
trane-l,2-Dlchloroetliene
llexane
1,1-Dlchloroethano
Vinyl l\cetato
1,1-Dichloroothone
2-nutanono
Chloroform
1,1,1-Trichloroethano
Carbon tetrachloride
llenzene
l,2-0lchloroct:h11ne
•rr lchloroothono
1,2-Dlchloropropane
1,4-Dloxane
Bromodlchloromothnno
cle-1,3-Dlchloropropeno
<1-Hethyl-2-pentanone
Toluene
trane-1,J-Dichloropropono
1,1,2-Trlchloroothano
Totrachloroothene
2-llexanone
Dlbromochloromothone
1,2-Dlbromoethane
Chloroben:i:eno
Ethylben:i:ene
1,4-and 1,3-(p,m) Xylono
Reporting Limits
(ppbv)
2.0
2.5
2.0
2.5
3. 0 s.o
1.0
2.0
10
2.0
10
4.0
4.0 e.o
2.5
2.5
2.0
3.0
2.0
2.0
2.0
J.O
2.0 2.s o.o
7.0
2.0
3.0
J •. ci
J.O
J.O
J.O
3.0 s.o
3.0 t.o t.s
2.5
f;.O
0
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CON FIDE NTIAL
BUSINESS
INFORMA.TION
ST/\ND/\RD
Ol'Ell/\TINO
rnoc1munE
ra90 JL of _22_
The Datermlnatlon of VolatUa Or9anloe (VOCe)
ln Ambient /\lr by OC/HS -Haan Hoda
SOP NO1
CRL~LM-7001
Revlelon No., 2.0 Effective Date,
March l, 1990
',42)
: 43)
44)
45)
46)
47)
40)
49)
50)
51)
52)
53)
54)
Table 12. voe Reporting Limits
Compound
1,2-(ortho) Xylono
Styrene
nromoform
1 1 1,2,2-Tetracl,loroothano
Denzyl chlorlde
4-Ethyltolueno
l,J,5-Ttlmett1ylbenzeno
1,2,4-Trlmethylbenzono
1,3-Dichlorobonzono
1,4-Dlchlorobonzone
1,2-0.Lchlorobonzeno
1,2,4-Trlchlorobenzono
llexachlorobutadlono
Reporting Limits
(ppbv)
2.0
·,. 0
2.0
4,0
2.0
4.0
2.5
3.0
3.0
4.0
5,0
7.0
5.0
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ATTACHMENT B-3
DATA REDUCTION, VALIDATION AND REPORTING
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Enseco QA Program Plan
10. DATA REDUCTION, VALIDATION, AND REPORTING
Data Reduction and Validation
Section No.
Revision No.
Date
Page
)0
3 4
4/91 30 of 62
All analytical data generated within Enseco laboratories are
extensively reviewed prior to report generation to assure the validity
of the reported data. The data validation process consists of data
generation, reduction, and three luvels of docu111ented review, as
described below (also see Figure 10-1). In each stage, the review
process ls documented by the signature of the reviewer and the date
reviewed.
The analyst who generates the analytical data has the prime
responsibility for the correctness and completeness of the data. All
dak are generated and reduced following protocols specified in
laboratory SOPs. Each analyst reviews the quality of his or her work
based on an established set of guidelines. The analyst reviews the
data package to ensure that:
Sample preparation information is correct and complete;
Analysis infonnatfon 1s correct and complete;
The appropriate SOPs have been followed;
Analytical results are correct and complete;
QC samples are within established control 11m1ts·;
Blanks are within appropriate QC limits;
Special suple preparation and analytical requirements have been met; and
Documentation is complete (e.g., all anomalies in the preparation and analysis have been documented, anomaly fonns are complete; noldlng ti111es are documented, etc.).
Enseco QA Program Plan Section No. IQ Revision No.
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The data reduction and validation steps are documented, signed and dated by the analyst. This initial review step, performed by the analyst, is designated Level 1 review. The analyst then passes the data package to an independent reviewer, who performs a Level 2
review.
Level 2 review 1s perfonned by a supervisor or data review special.1st whose function is to provide an independent review of the data
package. This review is also conducted according to an established set of guidelines and Is structured to ensure that:
...
Calibration data are scientifically sound, appropriate to the method, and completely documented;
QC samples are within established guidelines;
Qualitative identification of sample components Is correct;
Quantitative results are correct;
Documentation 1s complete and correct (e.g., anomalies in the preparation and ana lys Is have been documented; anoma 1 y forras are complete; holding times are docu11ented, etc.);
The data are ready for incorporation into the final report; and
The data package is complete and ready for data archive.
Level 2 review is structured so that all ca11bration dat, and QC sample results are reviewed and all of the analytical results from 10% of the samples are checked back to the bench sheet. If no problems are found with the data package, the review is complete. If any problems are found with the data package, an additional JOS of the samples are checked to the bench sheet. The process continues until no errors are found or until the data package has been reviewed in its entirety.
An important element of Level 2 review is the documentation of any errors that have been identified and corrected during the review
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Enseco QA Program Plan Section No. Revision No.
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process. Enseco believes that the data package submitted by the
analyst for Level 2 review ~hould be free of errors. Errors that are
found are documented and transmitted to the appropriate supervisor.
The cause of the errors is then addressed with additional training or
clarification of procedures to ensure that quality data will be
generated at the bench.
Level 2 data review 1s also documented and the signature of the
reviewer and the date of review recorded. The reviewed data are then
approved for release and a final report is prepared.
Before the report is released to the client, the data are reviewed for
completeness and to ensure that the dtta meet the overall objectives
of the project. This review is labeled Level 3 review and is
typ,ically done by the Program Administrator.
Each step of this review process involves evaluation of data quality
based on both the results of the QC data and the professional judgment
of those conducting the review. This application of technical
knowledge and experience to the evaluation of the data is essential in
ensuring that data of high quality are generated consistently.
In addition to the three levels of review discussed above, the
Divisional QA department randomly audits 5% of all projects reported.
The QA audit includes verifying that holding times have been met,
calibration checks are adequate, qualitative and quantitative results
are correct, documentation is complete, and QC results are complete
and accurate. During the review, the QA department chec~s the data
from 20% of the samples back to the bench shoet. lf no problems are
found with the data package, the review is complete. If any problems
are found with the data package, an additional 10% of the samples are
checked to the bench sheet. The process continues until no errors are
found or until the data package has been reviewed ln its entirety.