NCD980602163_19970109_Warren County PCB Landfill_SERB C_Sampling Plan Summary for Measurement of Fugitive Atmospheric Emissions of PCBs from the Warren Co Landfill-OCR

I ,
State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Solid Waste Management
James B. Hunt, Jr., Governor
Jonathan B. Howes, Secretary
William L. Meyer, Director
SAMPLING PLAN SUMMARY FOR:
.NA-··
DEHNR
MEASUREMENT OF FUGITIVE ATMOSPHERIC EMISSIONS OF
POLYCHLORINATED BIPHENYLS FROM THE PCB LANDFILL
WARREN COUNTY, NORTH CAROLINA
Sampling Plan Date: January 9, 1997
Sampling Plan Preparer: Pierre Lauffer @?
Health and Safety Coordinator
Division of Waste Management
Raleigh, North Carolina 27605
Project Participants:
Pierre Lauffer, HWS-Health and Safety Coordinator (Project Manager and Sampler)
John Kirby, HWS-Environmental Chemist (Project Chemist and Sampler)
Projected Sampling Dates: February, 1997
Site History:
Between June, 1978 and August, 1978, over 30,000 gallons of industrial waste material
identified as polychorinated biphenyls (Arochlor 1260 and 1262) were discharged deliberately
along the shoulders of approximately 210 miles of North Carolina highways. In June, 1979,
EPA approved a tract of land (previously used for agriculture) in Warren County, North Carolina
as the disposal site for the PCB-contaminated roadside soil. The landfill ( constructed in 1982-
1983 and permitted under the Toxic Substances Control Act (TSCA) contains about 40,000 cubic
yards of soil contaminated with PCBs. The concentration of PCBs in the landfill range from 150
to almost 900 part per million (ppm), averaging about 350 ppm (1), based on 1994 subsurface
soil sampling results (these were retrieved from the bottom of the vent).
P.O. Box 27687, Raleigh, North Carolina 27611-7687 Telephone [phone] FAX [phone]
An Equal Opportunity Affirmative Action Employer 50% recycled/ 10% post-consumer paper
Polychlorinated Biphenyls (PCBs):
PCBs are a family of aromatic compounds consisting of two benzene nuclei bonded with
two or more chlorine molecules. The PCBs of concern in this study (the type existing in the
landfill) are the Aroclors.
Aroclors are characterized by four digit numbers. The first two (the number 12) indicate
that the mixture consists of biphenyls. The second two digits state the percentage by weight of
chlorine in the mixture (2).
They tend to be colorless to light yellow oily substances with a specific gravity of 1.4-1.5
(3). Due to their stability and nonconductive properties, PCBs had many industrial uses
including use as insulation coating in electrical capacitors. PCBs possess, as a whole, high open
cup flashpoints (348-356° F.-Aroclor 1242, none for Aroclor 1254 and 1260), but do readily
distill at temperatures above 325°F. The distillation range for Aroclor 1242 is 325-366°F; for
Aroclor 1254, 365-390°F; Aroclor 1260, 385-420°F (4).
Toxic effects from exposure to PCBs in human include chloracne, pigmentation of skin
and nails, excessive eye discharge and swelling of eyelids, and gastrointestinal disturbances.
PCBs are considered carcinogenic (5).
Because of their high toxicity, detrimental harm to the environment and stable molecular
structure (structure remains intact in the environment for long periods oftime) PCB manufacture
was discontinued in 1976.
Objective:
The objective of this study is to determine if there are uncontrolled PCB emissions
originating from the Warren County PCB Landfill. This study will involve ambient air sampling
to determine if PCB contaminated air particulate matter and vaporized PCB (Aroclors 1242,
1254, and 1260) emissions are present. Retrieved samples will be analyzed by an independent
American Industrial Hygiene Association accredited laboratory. Southern Testing and Research
Laboratories, Inc. of Wilson, North Carolina has been selected for conducting the sample
analysis. The results of the analysis will be submitted directly to the workgroup and DWM. A
risk assessment will be requested from the DEHNR Epidemology Division to determine if the
PCB emissions (if found) are a risk to the surrounding community.
Materials and Methods:
Air sampling will be performed with low-volume (L V) and high-volume (HV) constant
air-flow sampling systems. The components of the sampling systems consists of battery operated
constant air-flow pumps (LV or HV) (Gilair Pump by Gilian™, Models: Gilair3(LV) and
Gilair5(HV)), 13 mm Gelman Swinney filter cartridges with 13mm, lµm pore-sized glass fiber
filters manifolded to ORBO™-60 100150mg, 6 x 70mm florisil sampling tubes.
The pumps will be calibrated by the Gilian Gilibrator (digital calibrator) prior to and after
each sampling period. The glass fiber filters will be precleaned prior to loading filter cartridges
by the North Carolina Public Health Laboratory and loaded at the laboratory by laboratory
personnel. The sampling head will consist of glass fiber filter cartridge followed by the florisil
tube. The two will be manifolded together by tubing. The purpose for this sampling system is to;
1) catch any possible PCB contaminated particulates from the air, 2) to filter PCBs which may
have vaporized. This system will then be manifolded to the sampling pump with plastic tubing.
There will be three sampling periods of eight hours. The sampling sessions will begin at
roughly 1 0:00am, 6:00pm and 2:00am. Each sampling period will be separated by one day.
The reason for this delay between sampling events is to provide time to recharge the air-flow
pumps (they require 16 hours ofrecharge time). Each sampling period will consist of seven air-
flow pumps and sampling units. One unit will be located inside the vent on top of the landfill.
Two more units will be located two meters downwind from the vent (these will be seperated
from each other by one meter). Two other units will be located diagonally downwind at the
landfill fence line. One unit will be located 200 meters straight downwind from the vent. The
air-flow rate will be calibrated to NIOSH guidelines. NIOSH Sampling Method #5503:
Sampling for Polychlorobiphenyls states that air-flow rate should be 50-200cc per minute. The
flow-rate per unit will correspond to its distance from the vent-the further the pump is from the
vent, the greater its flow-rate. Another sampling unit will be located 200 meters upwind and will
act as a background sampler. Approximately fifty samples will be obtained. Prior to each
sampling event, the wind direction and temperature will be indicated by a portable weather
station established on the east side of the landfill.
Funding from the DWM operations budget rather than the PCB detoxification budget will be
funding this project.
NOTE: Please see attached diagram of the landfill showing sampling locations and a copy
of the NIOSH lab procedure.
PKL/H&S/HWS/Dec96.
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PCB LANDFILL-WARREN COUNTY
d
* background
16 7 .5 meters
183 yards
0 I weather station
sampling point -*
200yds* >
-. POL YCHLOROBIPHENYLS 5503
mixture: C12H,o-,CI,
[where x = 1 to 10]
MW: ca. 258 (42% Cl ; C12H7Cl;J;
ca. 326 (54% Cl ; C12H5Cls)
CAS: Table 1 RTECS: Table 1
METHOD: 5503, Issue 2 EVALUATION: PARTIAL Issue 1: 15 February 1984
Revision #1: 15 August 1987
Issue 2: 15 August 1994
OSHA : 1 mg/m3 (42% Cl);
0.5 mg/m3 (54% Cl)
NIOSH: 0.001 mg/m3/10 h (carcinogen)
ACGIH: 1 mg/m3 (42% Cl) (skin)
0.5 mg/m3 (54% Cl) (skin)
PROPERTIES: 42% Cl: BP 325 to 366 °C; MP -19 °C;
d 1.38 g/mL @ 25 °C;
VP 0.01 Pa (8 X 10'5 mm Hg;
1 mg/m3) @ 20 °C
54% Cl: Cr' 365 to 390 °C; MP 10 'C;
d 1.54 g/mL @ 25 °C; VP
0.0004 Pa (3 x 10·8 mm Hg;
0.05 mg/m3) @ 20 °C
SYNONYMS: PCB; 1, 1 '-biphenyl chloro; chlorodiphenyl, 42% Cl (Aroclor 1242); and 54% Cl (Aroclor 1254)
SAMPLING
SAMPLER: FILTER + SOLID SORBENT
(13-mm glass fiber + Florisil,
100 mg/50 mg)
FLOW RATE: 0.05 to 0.2 L/min or less
VOL-MIN:
-MAX:
1 L@ 0.5 mg/m3
50 L
SHIPMENT: transfer filters to glass vials after sampling
SAMPLE
STABILITY:
BLANKS:
unknown for filters;
2 months for Florisil tubes (1]
2 to 10 field blanks per set
ACCURACY
RANGE STUDIED: not studied
none identified
not evaluated
not determined
BIAS:
OVERALL PRECISION (~rT):
ACCURACY:
MEASUREMENT
TECHNIQUE: GAS CHROMATOGRAPHY, ECO t 3Ni)
ANALYTE: polychlorobiphenyls
DESORPTION: filter + front section, 5 ml hexane; back
section, 2 ml hexane
INJECTION
VOLUME: 4-µL with 1-µL backflush
TEMPERATURE-INJECTION:
-DETECTOR:
250 to 300 °C
300 to 325 °C
180 °C -COLUMN:
CARRIER GAS: N2, 40 ml/min
COLUMN: glass, 1.8 m x 2-mm ID, 1.5% OV-17/1.95%
QF-1 on 80/100 mesh Chromosorb WHP
CALIBRATION: standard PCB mixture in hexane
RANGE: 0.4 to 4 µg per sample (2]
ESTIMATED LCD: 0.03 µg per sample [2]
PRECISION (Sr): 0.044 (1]
APPLICABILITY: The working range is 0.01 to 10 mg/m3 for a 40-L air sample (1]. With modifications, surface wipe samples
may be analyzed (3,4].
INTERFERENCES: Chlorinated pesticides, such as DDT and DOE, may interfere with quantification of PCB. Sulfur-containing
compounds in petroleum products also interfere (5).
OTHER METHODS: This method revises methods S120 (6] and P&CAM 244 (1). Methods S121 [7] and P&CAM 253 [8] for
PCB have not been revised.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
POLYCHLOROBIPHENYLS: METHOD 5503, lssue-2, dated 15 August 1994 -Page 2 of 5 -----------------------------------~.;--:. ·-
REAGENTS:
1. Hexane, pesticide quality.
2. Florisil, 30/48 mesh sieved from 30/60 mesh.
After sieving, dry at 105 °C for 45 min. Mix
the cooled Florisil with 3% (w /w) distilled
water.
3. Nitrogen, purified.
4. Stock standard solution of the PCB in
methanol or isooctane (commercially
available).*
* See SPECIAL PRECAUTIONS.
EQUIPMENT:
1. Sampler: 13-mm glass fiber filter without
binders in a Swinnex cassette (Cat. No. SX
0001300, Millipore Corp.) followed by a glass
tube, 7 cm long, 6-mm OD, 4-mm ID
containing two sections of 30/48 mesh
deactivated Florisil. The front section is
preceded by glass wool and contains 100 mg
and the backup section contains 50 mg;
urethane foam between sections and behind
the backup section. (SKC 226-39, Supelco
ORBO-60, or equivalent) Join the cassette
and Florisil tube with PVC tubing, 3/8" L x
9/32" OD x 5/32" ID, on the outlet of the
cassette and with another piece of PVC
tubing, 3/4" L x 5/16" OD x 3/16" ID,
complete the union.
2. Personal sampling pump, 0.05 to 0.2 L/min,
with flexible connecting tubing.
3. Tweezers.
4. Vials, glass, 4-and 7-mL, with aluminum or
PTFE-lined caps
5. Gas chromatograph, electron capture
detection t 3Ni), integrator and column (page
5503-1 ).
6. Volumetric flasks, 10-mL and other convenient
sizes for preparing standards.
7. Syringe, 10-µL.
SPECIAL PRECAUTIONS: Avoid prolonged or repeated contact of skin with PCB and prolonged or
repeated breathing of the vapor [9-11].
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler in line.
2. Break the ends of the Florisil tube immediately before sampling. Connect Florisil tube to
Swinnex cassette and attach sampler to personal sampling pump with flexible tubing.
3. Sample at an accurately known flow rate between 0.05 and 0.2 L/min for a total sample size of 1
to 50 L.
NOTE : At low PCB concentrations, the sampler was found to be efficient when operated at flow
rates up to 1 L/min, for 24 hours [4]. Under these conditions, the limit of detection was
0.02 µg/m3•
4. Transfer the glass fiber filters to 7-mL vials. Cap the Florisil tubes with plastic (not rubber) caps
and pack securely for shipment.
SAMPLE PREPARATION:
5. Place the glass wool and 100-mg Florisil bed in the same 7-mL vial in which the filter was stored.
Add 5.0 ml hexane.
6. In a 4-mL vial, place the 50-mg Florisil bed including the two urethane plugs. Add 2.0 ml
hexane.
7. Allow to stand 20 min with occasional agitation.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
POlYCHlOROBIPHENYlS: METHOD 5503, Issue 2, dated 15 August 1994 -Page 3 of 5
CALIBRATION AND QUALITY CONTROL:
8. Calibrate daily with at least six working standards over the range 1 O to 500 ng/ml PCB.
a. Add known amounts of stock standard solution to hexane in 10-ml volumetric flasks and
dilute to the mark.
b. Analyze together with samples and blanks (steps 11 and 12).
c. Prepare calibration graph (sum of areas of selected peaks vs. ng PCB per sample).
9. Determine desorption efficiency (DE) at least once for each lot of glass fiber filters and Florisil
used for sampling in the calibration range (step 8). Prepare three tubes at each of five levels
plus three media blanks.
a. Remove and discard back sorbent section of a media blank Florisil tube.
b. lnjJct known amounts of stock standard solution directly onto front sorbent section and onto
a media blank filter with a microliter syringe.
c. Cap the tube. Allow to stand overnight.
d. Dosorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12).
e. Prepare a graph of DE vs. µg PCB recovered.
10. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration
graph and DE graph are in control.
MEASUREMENT:
11 . Set gas chromatograph according to manufacturer's recommendations and to conditions given
on page 5503-1 . Inject sample aliquot manually using solvent flush technique or with
autosampler.
NOTE 1: Where individual identification of PCB is needed, a procedure using a capillary
column may be used [12].
NOTE 2: If peak area is above the linear range of the working standards, dilute with hexane,
reanalyze and apply the appropriate dilution factor in calculations.
12. Sum the areas for five or more selected peaks.
CALCULATIONS:
13. Determine the mass, µg (corrected for DE) of PCB found on the glass fiber filter 0N) and in the
Florisil front (W,) and back (Wb) sorbent sections, and in the average media blank filter (B) and
front (B,) and back (Bb) sorbent sections.
NOTE: If Wb > Wi/10, report breakthrough and possible sample loss.
14. Calculate concentration, C, of PCB in the air volume sampled, V (l):
c = ( w + w, + wb -B -01 -Bb ) 3 V , mg/m.
EVALUATION OF METHOD:
This method uses 13-mm glass fiber filters which have not been evaluated for collecting PCB. In Method
S120, however, Aroclor 1242 was completely recovered from 37-mm glass fiber filters using 15 ml
isooctane [8,13,14). With 5 ml of hexane, Aroclor 1016 was also completely recovered from 100-mg
Florisil beds after one-day storage [1 ]. Thus, with no adsorption effect likely on glass fiber filters for
PCB, 5 ml hexane should be adequate to completely extract PCB from combined filters and front
sorbent sections. Sample stability on glass fiber filters has not been investigated. Breakthrough volume
was >48 l for the Florisil tube at 75% RH in an atmosphere containing 10 mg/m3 Aroclor 1016 [1].
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
POLYCHLOROBIPHENYLS: METHOD 5503, Issue 2, dated 15 August 1994 -Page 4 of 5
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 2nd ed., V. 1, P&CAM 244, U.S. Department of health,
Education, and Welfare, Publ. (NIOSH) 77-157-A (1977).
[2] User check, Southern Research Institute, NIOSH Sequence #4121-U (unpublished, January 25,
1984).
[3] Kaminsky, J. Applied Ind. !::!Yg. 1 (4), R-6 (1986).
[4] NIOSH Health Hazard Evaluation Report, HETA 85-289-1738 (unpublished, 1986).
[5] Hofstader, R. A., C. A. Bache, and D. J. Lisk. Bull. Environ. Contam. Toxicol., 11, 136 (1974).
[6] NIOSH Manual of Analytical Methods, 2nd ed., V. 4, S120, U.S. Department of Health, Education,
and Welfare, Publ. (NIOSH) 78-175 (1978).
[7] Ibid, V. 2, S121, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-B
(1977).
[8] Ibid, Vol. 1, P&CAM 253
[9] Criteria for a Recommended Standard ... Occupational Exposure to Polychlorinated Biphenyls,
U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-225 (1977).
[10] Current Intelligence Bulletin 7, Polychlorinated Biphenyls (PCBs), U.S. Department of Health and
Human Services, Publ. (NIOSH) 78-127 (1975).
[11] Occupational Diseases, A Guide to Their Recognition, revised ed ., 255-256, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-181 (1978).
[12] Dunker, J. C. and M. T. J. Hillebrand. Characterization of PCB Components in Clophen
Formulations by Capillary GC-MS and GC-ECD Techniques, Environ. Sci. Technol., 17 (8), 449-
456 (1983}.
[13] Backup Data Report for S120, prepared under NIOSH Contract 210-76-0123, available as 'Ten
NIOSH Analytical Methods, Set 2," Order No. Pb 271-464 from NTIS , Springfield, VA 22161.
[14] NIOSH Research Report-Development and Validation of Methods for Sampling and Analysis of
Workplace Toxic Substances, U.S. Department of Health and Human Services, Publ. (NIOSH)
80-133 (1980}.
[15] Hutzinger, 0., S. Safe, and V. Zitko. The Chemistry of PCBs, CRC Press, Inc., Cleveland, OH
(1974).
METHOD REVISED BY:
James E. Arnold, NIOSH/DPSE; S120 originally validated under NIOSH Contract 210-76-0123.
Table 1. General Information.
Compound
Polychlorinated Biphenyls
Chlorobiphenyl
Aroclor 1016 (41% Cl}
Aroclor 1242 (42% Cl)
Aroclor 1254 (54% Cl)
CAS
1336-36-3
27323-18-8
12674-11-2
53469-21-9
11097-69-1
RTECS
TQ1350000
DV2063000
TQ1351000
TQ1356000
TQ1360000
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
' \
POLYCHLOROBIPHENYLS: METHOD 5503, Issue 2, dated 15 August 1994 -Page 5 of 5
Table 2. Composition of some Aroclors [15].
Major Components Aroclor 1016 Aroclor 1242 Aroclor 1254
Biphenyl 0.1% <0.1% <0.1%
Monochlorobiphenyls 1 1 <0.1
Dichlorobiphenyls 20 16 0.5
Trichlorobiphenyls 57 49 1
Tetrachlorobiphenyls 21 25 21
Pentachlorobiphenyls · 1 8 48
Hexachlorobiphenyls <0.1 1 23
Heptachlorobiphenyls none detected <0.1 6
Octachlorobiphenyls none detected none detected none detected
01/09/1997 15:06 91 ':H::451 Bl 3 EEC IHC
. EEC, Inc.
l 07 WIND CHIME COURT, RALEIGH, NC 27615
January 8, 1996
Mr. Piere Lauffer ·
Division of Solid & Hazardous Waste
Solid Waste Section
Raleigh, NC
Re: PCB Analytical Cost
Dear Mr. Lauffer:
F'AGE 01
9 I 9-846-l O 1 6
FAX 9 l 9-846-1 8 1 3
As per our discussions, we will be glad to provide analysis of PCB air samples
using the NIOSH 5503 method. The cost of analysis for each sample will be $
70.00/sample. This cost is for a 5-7 days tum-around time of analytical services.
All samples will be analyzed by an AIHA accredited laboratory. We understand
that there may be as many as 17 samples per day to be analyzed. After you collect
the samples, we can pick up the samples at your office or you can drop the
samples by our office.
If you need additonal information, please call.
Thank You.
Sincerely, ·-•--••-••• •••·-••·• ••·-•·---• ·•·-••-•· ·••••••-• ----·--••••• ·r -.. ••• •••• •• .. • •------
·· .... _
Mike Shrimanker, CIH, CSP, PE
President
Post-Ir Fax Note 7671
Co. Ee
01-10-1997 08=27AM FROM Southern Tes ting TO 17007153605 P.01
Soutliern Testing & Researclz Labor<,tories, Inc ..
3809 Airport Drive [phone] " Fax: [phone] Wilson, NC 27896
FAX TRANSMITTAL
Date January 10, 1997
The following pages are for:
Name Pierre Lauffer
Location NC Hazardous \Vaste Section
Fax No 919-715-3605
From_-=Kc=··=im=-=B=-a-=t=-1g~l=1m=an=---
Total Number of Pages Sent (Including Cover Sheet) __ l __
Pierre,
Our LOD for NIOSH Method 5503 is 0.025 µg. Our analysis fee for this method is
$75/sample. This includes five point standard calibration curves and two analyses for every
sample (The backup Florisil section is analyzed separately to evaluate break-through.) We hope
to work with you on this project.
Sincerely,
~aur-J~, PhD"/
Technical Director