I-2_City of Durham Ambient WQ Monitoring QAPP_10.21.2014

DURHAM
N
CITY OF DURHAM
1869
CITY OF MEDICINE
AMBIENT WATER CHEMISTRY MONITORING
PROGRAM
QUALITY ASSURANCE PROJECT PLAN
City of Durham
Stormwater & GIS Services
October 20, 2014

PART A: PROJECT MANAGEMENT
1. Signature and Approval Sheet
Ambient Water Chemistry Monitoring Program
Project Name
City of Durham Stormwater & GIS Services
Responsible Agency
October 20, 2014
Date
Role
Si nature Date
Project Manager; Ambient Monitoring
Coordinator
Brick Raber
Water Quality Specialist, City of Durham,
Stormwater & GIS Services
Asst. Project Manager
ames Pflaum
Senior Water Quality Technician, City of Durham,
Stormwater & GIS Services
QA Officer
Michel e Woolfolk
Asst. Water Quality Manager, Stormwater & GIS
Servic
Laboratory Manager
Jarros Blake
La 'oratory Manager, City of Durham, Water
Management
Laboratory Project Manager
_� Digitally signed by Stephanie
t-1.•__ —, Franz
Date: 2014.10.21 09:30:08-04'00'
Stephanie Franz
Laboratory Project Manager, ENCO Laboratories

2. Table of Contents
PARTA: PROJECT MANAGEMENT.........................................................................................
2
1. Signature and Approval Sheet.........................................................................................
2
2. Table of Contents............................................................................................................
3
3. Distribution list.................................................................................................................
5
4. Project Organization........................................................................................................
5
5. Problem Definition and Background.................................................................................
5
6. Project Description...........................................................................................................7
7. Data Quality Objectives...................................................................................................
8
Data Precision, Accuracy, Measurement Range..................................................................
8
Data Representativeness....................................................................................................
9
DataComparability..............................................................................................................9
DataCompleteness.............................................................................................................9
8. Training Requirements and Certification........................................................................
10
9. Documentation and Records..........................................................................................
10
RecordKeeping.................................................................................................................
10
DataStorage.....................................................................................................................
10
Reporting...........................................................................................................................
11
PART B: DATA GENERATION AND ACQUISITION...............................................................
11
10. Sampling Process Design..........................................................................................
11
11. Sampling Method.......................................................................................................12
12. Sample Handling and Custody...................................................................................
16
13. Analytical Methods.....................................................................................................
18
14. Quality Control...........................................................................................................
18
LaboratoryQC Checks......................................................................................................
19
15. Instrument/Equipment Testing, Inspection, and Maintenance .....................................
19
16. Instrument Calibration and Frequency........................................................................19
17. Inspection/Acceptance Requirements for Supplies.....................................................19
18. Data Acquisition.........................................................................................................
20
19. Data Management......................................................................................................20
PART C: ASSESSMENT AND OVERSIGHT...........................................................................
22
20. Assessments and Response Actions..........................................................................
22
21. Reports......................................................................................................................
22
PART D: DATA VALIDATION AND USABILITY......................................................................
23
22. Data Review, Verification, and Validation...................................................................
23
23. Validation and Verification Methods............................................................................
23
24. Reconciliation with Data Quality Objectives................................................................
23
REFERENCES.........................................................................................................................
25
3

LIST OF FIGURES
Figure 1. City of Durham location map.
Figure 2. Documented site information, field measurements, and parameters analyzed from
water samples collected at ambient water chemistry monitoring sites.
Figure 3. City of Durham's ambient water chemistry monitoring locations.
Figure 4. Bottleware used for ambient water chemistry monitoring.
Figure 5. Flow chart of field measurements and laboratory data.
LIST OF TABLES
Table 1. City of Durham watersheds.
Table 2. Field parameters measured during ambient water chemistry monitoring.
Table 3. Watersheds monitored during odd and even years in the City of Durham.
Table 4. Field parameters methods requirements.
Table 5. Laboratory analysis methods requirements.
Table 6. SDWRF Analytical Methods, Method Detection Limits, and Reporting Limits for parameters
evaluated for the City's ambient water chemistry monitoring program.
Table 7. Data qualifier codes (flags) used for ambient water chemistry monitoring data.
LIST OF APPENDICES
Appendix A. Ambient water chemistry monitoring field form.
Appendix B. Field meter calibration/post check log form.
Appendix C. Chain of custody form.
Appendix D. Equipment maintenance log.
Appendix E. City of Durham Water and Sediment Quality Data Management Standard Operating
Procedures
ACRONYMS AND ABBREVIATIONS
BOD
Biochemical Oxygen Demand
COC
Chain of Custody
DO
Dissolved Oxygen
EPA
United States Environmental Protection Agency
MS4
Municipal Separate Storm Sewer System
NCDWR
North Carolina Division of Water Resources
NH3
Ammonia
NO2+NO3
Nitrate + Nitrite
NPDES
National Pollution Discharge Elimination System
QA
Quality Assurance
QAPP
Quality Analysis Project Plan
QC
Quality Control
SDWRF
South Durham Water Reclamation Facility
SOP
Standard Operating Procedures
TKN
Total Kjeldahl Nitrogen
TMDL
Total Maximum Daily Load
TP
Total Phosphorus
TSS
Total Suspended Solids
UNCW
University of North Carolina at Wilmington
USGS
United States Geological Survey
4

3. Distribution list
Project team:
• Maverick Raber, Water Quality Specialist
• Michelle Woolfolk, Civil Engineer III
• James Pflaum, Sr. Water Quality Technician
• Travis Marion, Water Quality Technician
• Derek Routhier, Water Quality Technician
• Claire Tipton, Water Quality Technician
Others:
• Jonathan Baker, Water Quality Specialist
• John Cox, Stormwater Quality Supervisor
• James Blake, South Durham Water Reclamation Facility Laboratory Manager
• John Dodson, North Durham Water Reclamation Facility Plant Superintendent
• Reginald Hicks, Water Management Regulatory Compliance Superintendent
4. Project Organization
Staff in the Stormwater & GIS Services Division's Water Quality Unit performs activities associated with
the City of Durham's Ambient Water Quality Monitoring Program. In general, Water Quality Technicians
and Senior Water Quality Technicians perform all fieldwork (in -situ measurements and sample
collection). The Water Quality Specialist that oversees the City's ambient monitoring program generally
performs project management, QA, data management, data analysis, and reporting. The QAPP QA
officer is not directly involved in data generation, but is responsible for providing direction on purpose
and type of data needed, and assisting the Project Manager for maintaining the official, approved QAPP.
The South Durham Water Reclamation Facility (SDWRF) laboratory performs the majority of the water
chemistry analyses. The City's contract laboratory may also perform sample analyses as needed. Field
and laboratory data associated with ambient monitoring activities are uploaded by Water Quality Unit
staff to the City's water quality web portal. This data can be accessed online by Stormwater & GIS
Services staff to support federal and state reporting requirements and general watershed planning
activities.
S. Problem Definition and Background
The City of Durham (City) is located on the ridge line between the Neuse River and Cape Fear River
Basins (Figure 1). By area, approximately half the City drains to the Cape Fear River Basin and the other
half drains to the Neuse River Basin. Five watersheds drain portions of the City in the Cape Fear Basin
and seven watersheds drain portions of the city of the Neuse River Basin (Table 1). Because Durham is
5

located along a ridge line, streams in both river basins generally originate within the City. Thus, the City
controls the hydrology and water quality of these streams. All five watersheds in the Cape Fear River
Basin in the City drain to B. Everett Jordan Lake (Jordan Lake), a local water supply reservoir. Jordan
Lake discharges to the Cape Fear River that flows into the Atlantic Ocean near Wilmington, NC. Six of
the seven watersheds in the Neuse River Basin in the City drain to Falls of the Neuse Reservoir (Falls
Lake), also a local water supply reservoir. Falls Lake discharges to the Neuse River that flows to the
Albemarle -Pamlico Sound (with the exception of Stirrup Iron Creek, which flows into Crabtree Creek and
the Neuse River). Jordan and Falls Lakes are drinking water sources for Durham and surrounding
communities.
I � -
Ii
. � Flat River
i tiv 4
little River
F Little River
+ Frio ~Poser f -.-
Panther Creek
I4 '�eE 9l erbe Creek
f"hAud Creek
- Sandy rate lick Creek
`l 1 Creek
I i
Third Falk
j New Hope Creek--" _ l Lick Creek -
Creek
Norfie as[ !~Brier Creel",
i Creek
Q1O ere f I
Little .� -�i'. j C
Creek 7d{
l
1 0 1 2 4 Miles
I I �
DJRHAM
Data Source:
Legend
Water Bodies- NCCGIA 2002
City Limits, Watershed Boundaries- City of Durham 2013
Q River Basin Boundaries
Streams NHD 2013
River Basin Boundaries USDA 2006
Watershed Boundaries
8 6 9
Information displayed isfor reference purposes only and the
- City Limits
City of Durham assumes no responsibility for errors from use
Streams
or misuse of this map.
Figure 1. City of Durham location map.
L

Table 1. City of Durham Watersheds.
Cape Fear River Basin Watersheds Neuse River Basin Watersheds
New Hope Creek
Eno River
Little Creek
Ellerbe Creek
Third Fork Creek
Panther Creek
Crooked Creek
Little Lick Creek
Northeast Creek
Little River
Lick Creek
Stirrup Iron Creek
The City of Durham received its first National Pollution Discharge Elimination System (NPDES) permit for
the discharge of stormwater to the municipal separate storm sewer system (MS4) in 1994. The original
permit required screening of all stormwater outfalls in the city, wet weather monitoring, and water
quality investigations. The permit has since evolved to require a water quality assessment and
monitoring program. In response, the City developed an ambient monitoring program that is modeled
after the NCDWR ambient monitoring system. Three different types of monitoring are conducted for
City of Durham streams: water chemistry, stream biology, and stream hydrology. These three different
types of monitoring allow the City of Durham not only the opportunity to evaluate streams
independently of the State, but also to verify results obtained by the State. This QAPP addresses the
water chemistry portion of the City's ambient monitoring program. The City's ambient water chemistry
monitoring program also allows the City to evaluate streams that are listed on the State's 303(d) list of
impaired waters. Additionally, water chemistry data allow the City to evaluate progress towards
meeting nutrient or other pollution reduction requirements.
The main objectives of the City's ambient water chemistry monitoring are to:
1. Characterize waters and identify changes or trends in water quality over time.
2. Identify specific existing or emerging water quality problems.
3. Gather information to design specific pollution prevention or remediation programs.
4. Determine whether program goals, such as compliance with pollution regulations or
implementation of effective pollution control actions are being met.
6. Project Description
The ambient water chemistry monitoring program consists of a network of monitoring sites strategically
located inside orjust outside the City limits (Figure 2). These sites are at fixed locations to allow for
specific short and/or long-term water quality information at a given location or for a given drainage
area. Sites rotate by calendar year depending on the watersheds targeted for monitoring. Sites are
monitored once per month. Most sites are monitored every other year. A few select sites, however, are
monitored every year regardless of the targeted watersheds. These sites have significant strategic
importance, such as the calculation of pollutant loads or evaluation of specific pollution sources. All
monitoring dates are pre -scheduled to eliminate bias in sampling conditions. Sample days are typically
Tuesday and Wednesday of the second and third full weeks of the month (up to four days total per
month). All sites in a given watershed are monitored on the same sample day. Pre -scheduled sample
days change due to holidays and staff availability. Any changes in sample dates must be pre -approved
by the Project Manager and Laboratory Manager. A sufficient number of samples over time should
represent a variety of flow conditions during each season.
7

Water samples collected at water chemistry monitoring sites for analysis by the SDWRF laboratory
generally need to be delivered by 12:00 PM, or within 4 hours of fecal coliform sample collection. This
allows laboratory staff enough time to process samples with short hold times. The number of sites that
can be visited and sampled in a day is limited because of these samples with short hold times. Roughly
40 sites per month, or 10 sites per day, can be sampled for ambient water chemistry monitoring based
on four field days (not accounting for blanks and duplicates).
Water chemistry monitoring sites generally fall into one of two categories; fecal and comprehensive. At
fecal sites, field parameters are measured for temperature, DO, specific conductivity, and turbidity and a
fecal coliform sample is collected. At comprehensive monitoring sites, field parameters for
temperature, DO, specific conductivity, and turbidity are measured and water samples are collected for
nutrients, total suspended solids (TSS), total metals, dissolved metals, and fecal coliform. Additional
site -specific parameters may be measured or samples may be collected to evaluate other pollutant
indicators. On occasion, a site may be sampled for ambient water chemistry concurrently with a special
study. The methods and results for additional measurements and samples collected for the special
study will be included in the QAPP for that project and are not covered as a part of this QAPP. Field
observations are recorded during all site visits.
Stormwater & GIS Services Water Quality Unit staff will perform all field and office activities outlined in
this QAPP. At the end of the calendar year (December), Water Quality Unit staff reevaluates the
ambient monitoring program, including water chemistry monitoring. Monitoring sites are reviewed to
determine the value of continued monitoring of existing sites, the need to include additional sites, or
unusual occurrences at a site. Newly proposed sites are evaluated in the field prior to being added to
the program to ensure the site can be safely monitored and there is sufficient year-round access.
Data collected from ambient water chemistry monitoring are uploaded to the City's online Water
Quality Web Portal. The monitoring results of the calendar year are reported in the NPDES Annual
Report and the State of Our Streams report.
7. Data Quality Objectives
All analytical chemistry and microbiological analyses are performed at the SDWRF laboratory located in
Durham, NC or the contract laboratory, ENCO Laboratories, located in Cary, NC and Orlando, FI. The
certification number for the SDWRF laboratory is 176. The ENCO certification numbers are 591 at the
Cary location and 424 at the Orlando location.
Data Precision, Accuracy, Measurement Range
A YSI Pro Plus with the Quatro multi -parameter bulkhead is used to measure the majority of in -situ
parameters (temperature, DO, conductivity, pH) at ambient water chemistry monitoring sites. Turbidity
is measured with a Hach 2100P Turbidimeter. The range of measurement, resolution, and accuracy for
parameters measured with each instrument are included in Table 2.
N

Table 2. Field parameters measured during ambient water chemistry monitoring.
Parameter
Equipment Used
Range of Measurement
Resolution
Accuracy
YSI Pro Plus w/ Quatro
Temperature
Cable
-5 to 70°C
±0.1°C
±0.2°C
Dissolved oxygen (%)
YSI Pro Plus w/ Quatro
0 to 500%
0.1%
±2%
Cable (galvanic sensor)
YSI Pro Plus w/ Quatro
±2% of the reading
Dissolved oxygen (mg/L)
0 to 50 mg/L
0.01 mg/L
or 0.2 mg/L,
Cable (galvanic sensor)
whichever is greater
YSI Pro Plus w/ Quatro
0.5% of reading or
Conductivity
0 to 200 mS/cm
0.001 MS/Cm
0.001 mS/cm,
Cable
whichever is greater
YSI Pro Plus w/ Quatro
pH
Cable
0 to 14 units
0.01 units
±0.2 units
Turbidity
Hach Model 2100P1
0 —1000 NTU
± 2%
0.01 NTU
1 This meter meets EPA Method 180.1 specifications.
Data Representativeness
Stream data collected from the ambient water chemistry monitoring program will be representative of
conditions in low to mid -order Piedmont streams in Triassic and Slate Belt soils. All data will be
collected by established standard methods when available and when applicable. Sampling sites are
carefully selected to be representative of the stream reach or area being evaluated.
Data Comparability
The goal of the City's Ambient Water Quality Monitoring Program is to generate water chemistry data
that is comparable between sites within the ambient water chemistry monitoring network, comparable
to water chemistry data collected by the NCDWR, and comparable to water chemistry data collected by
the Upper Cape Fear River Basin Association. These data are comparable because of fixed station
locations, standard operating procedures, and standard analytical methods. Field and laboratory
methods generally follow standard operating procedures and methods used by the NCDWR.
Data Completeness
To meet completeness goals, at least 90% of the data from ambient water chemistry monitoring are
collected and are usable for various analyses. Problems that may result in missing or non -usable data
include:
• Inclement weather
• Insufficient flow/dry site conditions
• Temporary station inaccessibility
• Equipment malfunctions
• Blank or sample contamination
• Inadequate laboratory capacity or availability
• Staff availability

8. Training Requirements and Certification
Initial training for new staff includes meter calibration, safety procedures, required documentation,
sampling methods, sample handling, and other field activities. The Project Manager, Assistant Project
Manager, or other experienced staff member will perform all ambient water chemistry monitoring
training. Experienced field staff will accompany all new field staff during sampling activities until the
new staff member exhibits proficiency in the field (as determined by the trainer's observations). The
ambient monitoring coordinator also performs a minimum of one audit of each monitoring team each
year to evaluate monitoring performance. Audit results will be provided to all staff performing ambient
water chemistry monitoring for the City. Audited staff members will be required to sign and date the
audit signifying they have read and understand the audit results.
9. Documentation and Records
Record Keeping
Staff will record pertinent field data (e.g. sample time, physical parameters, weather observations) on
field data forms (Appendix A). Applicable field data recorded on this form will be transposed into an
excel spreadsheet template for upload to the City's online Water Quality Web Portal.
Laboratory analytical data will be received electronically in a format suitable for upload to the City's
online Water Quality Web Portal. The analytical results reports describe the sample date, parameter
analyzed, and data flag/qualifier. These reports are provided to the Project Manager within 28 business
days of sample receipt. The SDWRF laboratory or contract laboratory will notify the Project Manager if
any samples are sub -contracted to another laboratory. All electronic files will be saved according to the
Water Quality Unit's electronic data filing system (City of Durham, 2013). Electronic files will also be
printed so that a hard copy can be retained and filed.
Instrumentation performance and calibration will be recorded on a Field Meter Calibration/Post Check
log sheet (Appendix B). Following post checks at the end of the field day, each sheet will be given to the
Project Manager to review. Sample bottles will be labeled with a designated laboratory number. This
number will represent a specific site or specific QA sample. A chain of custody form will be completed
for each sample day. An example chain of custody form is included in Appendix C.
Documentation associated with ambient water chemistry monitoring (i.e. field sheets, field Meter
Calibration/Post Check forms, chain of custody forms, and analytical reports) and electronic data files
from the laboratory will be filed in the Water Quality Unit filing cabinet on the third floor of City Hall and
retained a minimum of five years following monitoring.
Data Storage
Data from the ambient water chemistry monitoring program are published to the web through the
water quality web portal. The link to the web portal is available on request. Once the user sets up an
account, that person can view and download ambient water chemistry data, as well as water chemistry
and sediment chemistry data from other Water Quality Unit projects.
10

Reporting
Data from ambient water chemistry monitoring are used in a variety of reports. Data are used to
calculate the City's water quality index (WQI). This index is a reported performance measure for the City
and is also published on the web portal. WQIs are also published in the annual State of Our Streams
report, a report generated for Durham residents that describes local stream quality. Ambient water
chemistry data summaries are also reported to the NCDWR in the City's NPDES Municipal Discharge
Permit Annual Report. Various special studies, studies performed by the Water Quality Unit to evaluate
specific pollutant sources or answer specific questions, may also report ambient water chemistry data.
PART B: DATA GENERATION AND ACQUISITION
10. Sampling Process Design
Parameters analyzed in the laboratory are selective based on analytical costs and available resources.
During the initial phases of the stormwater program in the 1990s, a large number of pollutants were
analyzed in surface water and storm water samples. This included chemical compound classes of
volatiles, semi-volatiles, metals, and organophosphate pesticides. Only subsets of pollutants in these
classes of chemicals were detected in surface water or stormwater. Regular analysis of many of these
chemicals was not needed based on the results of this initial monitoring. Special studies may include
some of these chemical classes on an infrequent basis. State assessments and management strategies
are integral to parameter selection. Parameters included on the North Carolina 303(d) list of impaired
waters (NCDWR, 2012) are highlighted for inclusion in the ambient water chemistry monitoring
program. Other explanatory parameters are also included in order to determine potential sources,
degradation rates, and support toxicity analysis. Dissolved oxygen, turbidity, fecal coliform bacteria,
copper, zinc, total nitrogen and total phosphorus are parameters of concern based on current and
previous 303(d) listings.
Ambient water chemistry monitoring consists of documenting site conditions and site information,
measuring in -situ field parameters, and collecting water samples (Figure 3). Based on the number and
types of samples collected, monitoring sites are classified as fecal monitoring sites or comprehensive
monitoring sites. Fecal sites are screening sites for sewage inputs. At fecal sites, one water sample is
collected to screen for fecal contamination only. Comprehensive monitoring sites include collection of
water samples for a core group of parameters. These sites may also include additional indicator
parameters to address site -specific concerns.
A number of criteria are considered in selecting monitoring site locations. In general, sites are located in
watersheds that drain lands within City Limits. Site names are characterized by an abbreviation which
designates the watershed, stream mile, and creek name. For example, EN4.9ER is the Eno River
Watershed, 4.9 stream miles upstream of Falls Lake, and is located on the Eno River. The lower the
stream mile, the lower the position the site is in the watershed. Monitoring sites are selected based on
the following criteria:
• Locations of historical monitoring or locations monitored by other agencies
Historical monitoring sites offer a unique perspective of how conditions have changed over
time. It is important for any monitoring program to establish a subset of sites for this purpose.
These historical locations may be associated with City monitoring programs or state monitoring
programs.
11

• Accessibility and safety
Generally, monitoring locations are selected near road crossings or at sites within public lands
(e.g., parks). Locations that place City staff on crowded highways generally receive a lower
priority.
• Locations of stream flow monitoring
The U.S. Geological Survey maintains multiple stream flow monitoring locations in the City of
Durham. Combining water quality data with stream flow data provides a more complete picture
of water quality.
• Historical, existing, or suspected sources of pollution
Monitoring locations are typically located in areas where sanitary sewer overflows and spills
frequently occur or where other suspected sources of pollution exist.
• City special studies or initiatives
Special studies initiated within Stormwater Services may include the establishment of long or
short-term ambient monitoring locations.
• State management strategies
State nutrient management strategies for the Neuse River Estuary, Falls of the Neuse Reservoir,
and B. Everett Jordan Lake, influence the location of monitoring. Additionally, future and
existing TMDLs influence monitoring locations. Those TMDLs that attribute stormwater from
the City of Durham as a source of pollution are particularly considered.
Monitoring locations may be modified each calendar year. A map of the City's ambient water chemistry
monitoring locations is provided in Figure 2.
Monitoring is performed monthly throughout the calendar year (January through December) on a pre -
scheduled basis to eliminate sampling bias due to weather. This helps ensure a variety of weather and
flow conditions are monitored at long-term monitoring sites. Properly trained Water Quality Unit staff
perform all monitoring. It is preferable to conduct monitoring at all sites within a watershed on the
same day.
Most sites are monitored on odd or even years based on the watershed the station is located in (Table
3). Watershed monitoring is performed on a rotational basis due to limitations on the number of
samples the SDWRF laboratory can accept. However, there are a handful of sites that are monitored
every year if there is a cooperative agreement with another group or agency to monitor a station(s)
annually, the site is utilized for strategic purposes (i.e. calculating pollutant loads, evaluating pollutant
sources), and/or the laboratory has capacity to analyze the samples.
Data are used to calculate pollutant loads from watersheds draining the City, perform trend analysis to
evaluate long term trends, compare to NCDWR water quality standards, and calculate the City's Water
Quality Index. Data may also be used for other types of graphical and statistical analyses as needed.
11. Sampling Methods
In -situ parameters (DO, pH, specific conductivity, temperature) are measured with a YSI Pro Plus
Quattro or similar approved water quality instrumentation. Instruments with galvanic or polarographic
probes have flow requirements for use (e.g. yellow cap on YSI Pro Plus requires 6 in/sec flow). If flow is
insufficient at a sampling location, artificial flow must be created by swaying the probe in the water
above the required flow rate. Care should be taken to not to swing the probe harshly enough to
12

Z2.
Flat River
a ZJ Pi 0jj e d C . ation/
)little River
Eno River `—r
P er
eek
Blerbe Creek
fJtld Creek
4. San# Lrd- Li Creek
�*eek *. I*'
Lj,4. -reek
Third Fork
0 'reek�AL Creek H Brier Creek -
Creek.
Stirrup Iron
eyeCreek
cokek
'Cree);
Creek
Lake Crabtree
0 1.25 2.6 6 Miles
DURHAM Data Source:
Water Bodies, Streams - NHD 2010 Legend Ambient Monitoring sues
City Limits,
Watershed Boundaries, Ambient Monitoring Sites- Sample Year
City of Durham 2013 Streams
River Basin Boundaries- U SDA2008 Even Years
=Watershed Boundaries
Information displayed is for reference purposes only and the Even and Odd Years
1869 City of Durham assumes no responsibility for errors from use City Limits
COYOF MMONt or misuse ofthis map. Odd Years
Figure 2. City of Durham's ambient water chemistry monitoring location
13

ALL SITES
Documented Site Conditions and Information
Sample Site ID
Laboratory ID
Sample Collectors
Sample Date
Sample Time
Collection Method
Air Temperature (C)
Cloud Cover (%)
Flow Severity
Distance Sample Collected From Thalweg
Precipitation During Last 24 Hours
Other Site Observations
FECAL SITES
Water Sample Analysis
Fecal Coliform (cfu/100 ml)
Field Measurements
Water Temperature (C)
pH (units)
Dissolved Oxygen (mg/L)
Dissolved Oxygen (%)
Specific Conductivity (uS)
Turbidity (NTU)
COMPREHENSIVE SITES
Core Water Sample Analyses
Fecal Coliform (cfu/100 ml)
Nitrate + Nitrite as N (mg/L)
Total Kjeldahl Nitrogen (mg/L)
Total Phosphorus (mg/L)
Ammonia (mg/L)
5-Day Biochemical Oxygen Demand (mg/L)
Total Suspended Solids (mg/L)
Total Hardness (calculated; mg/L)
Total and Dissolved Copper (ug/L)
Total and Dissolved Zinc (ug/L)
Total Calcium (ug/L)
Total Magnesium (ug/L)
Site -Specific Water Sample Analyses
Total Organic Carbon (mg/L)
Dissolved Organic Carbon (mg/L)

introduce oxygen to the water and result in an artificially high DO reading. All probes should
measure within 0.1 m of the surface while remaining fully submerged. For turbidity, the sample
vial should be rinsed three times with native water. Rinsate should always be discarded
downstream. Care should be taken to avoid collecting a turbidity sample where sediment has
been disturbed. The outside of the turbidity vial should be cleaned and dried with a KimWipe
prior to reading. Users should be familiar with the manufacturer's guidelines and instructions for
calibration, storage, maintenance, and use of any water quality instrumentation used during
ambient water chemistry monitoring.
Grab samples are collected at each ambient monitoring sample location. Direct dip is the
preferred sampling method although; the use of a scoop or peristaltic pump may be necessary
when the stream is inaccessible or hazardous (e.g. elevated water level or high flows). The
sample scoop is properly decontaminated in the Water Quality Laboratory in City Hall prior to
deployment in the field and rinsed at least three times with stream water prior to filling sample
bottles. Decontamination consists of cleaning the scoop with alconox or liquinox and a non -
reactive bristle brush and tap water. The scoop is then rinsed three times with DI water, visually
inspected, and wrapped in a new Ziploc bag for transport in the field. Equipment blanks are
collected prior to sampling if the use of a sample scoop is anticipated. If a pump is used to collect
samples, associated tubing should be new and free from contaminants. Tubing should be
transported in the field in a new Zip-Loc or similar bag to prevent contamination.
Bottleware used for the direct dip method is always faced upstream and samples are collected
just below the surface (0.1 m) and in the thalweg if possible. Dissolved phase samples (dissolved
metals) are field filtered at the site using a peristaltic pump to pump ambient stream water
through virgin tubing and a new 0.45 µm in -line disposable filter capsule. To flush the filter,
water is pumped through the filter for a minimum of 30 seconds before sample collection. These
samples are also collected in the thalweg of the stream and within 0.1 m of water surface. Care
is made not to disturb sediment during all sample collection. Samples are placed on wet ice
immediately after sampling. Nitrile gloves are worn during all monitoring activities.
Monitoring may be scheduled during inclement weather. Under no circumstances will any
personnel work outdoors and/or conduct monitoring during periods of lightning and/or thunder
storms. If during the course of a monitoring event lightning and/or thunder conditions arise,
monitoring staff should seek shelter immediately.
Table 5. Field Parameters Methods Requirements
Sample Holding
Method
Maximum Holding
Parameter
Sampling equipment
Sample
Container
Time
Preservative
YSI Pro Plus w/Quatro
Immediately; in -
Temperature
Cable
None
None
situ reading
YSI Pro Plus w/Quatro
Immediately; in -
Dissolved oxygen
Cable
None
None
situ reading
YSI Pro Plus w/Quatro
Immediately; in -
Conductivity
Cable
None
None
situ reading
YSI Pro Plus w/Quatro
Immediately; in -
pH
Cable
None
None
situ reading
Turbidity
Hach Model 2100P
None
None
Immediately; in -
situ reading
15

Table 6. Laboratory Analysis Methods Requirements
Parameter'
Minimum Required
Container 2
Preservation 3
Maximum Hold Time'
Volume
A. TSS
500 mL
P
cool, <_6°C
7 days
A. 5-Day Biochemical
1,000 mL
P
cool, _<6°C
48 hours
Oxygen Demand
A. Total Alkalinity
500 mL
P
cool, <_6°C
6 months
(mg CaCO3/L)
A. TKN as N s
500 mL
P
cool, <_6°C, 25% H2SO4 to pH<2
28 days
A. NO3+NO2 as N
Combined with TKN
P
cool, 56°C
48 hours
as N
A. TP, total as P s
Combined with TKN
P
cool, <_6°C, 25% H2SO4 to pH<2
28 days
A. NH3 as N 5
Combined with TKN
P
cool, 56°C, 25% H2SO4 to pH<2
28 days
Metals, Total: Ca, Cu,
500 mL
P (Disposable)
1+1 HNO3 to pH<2
6 months
Mg, Zn
Metals, Dissolved
500 mL
P (Disposable)
1+1 HNO3 to pH<2
6 months
(Filtered): Cu, Zn
Fecal Coliform/E. Coli
250 mL
Sterile P
cool, <_4°C, NaS203
6 hours
Organic Carbon,
250 mL
AG
cool, <_4°C, H3PO4to pH<2
28 days
Total
Organic Carbon,
250 mL
AG
cool, <_4°C, H3PO4to pH<2
28 days
Dissolved (Filtered)
1 Determinations preceded by the same letter (i.e., A, B) may be submitted in the same bottle if the bottle contains
enough sample. If no letter precedes a parameter, it must be submitted in a separate bottle.
2 The container types listed are those commonly found used for sample collection. Other container types may be
acceptable. Plastic bottleware should be made of HDPE or PTFE (Teflon). Please consult the laboratory about use of
proper containers before deviating from those listed. P - plastic, G - glass, AG - amber glass, AV — amber VOA vial, P
(Disposable) - plastic disposable "juice" bottle.
3 Sample preservation should be performed immediately upon collection. For composite samples, each aliquot
should be preserved at the time of collection.
4 Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that
samples may be held before analysis or extraction and still be considered valid. Collection times must allow for
sample preparation and analytical set-up. Some samples may not be stable for the maximum time period given in the
table. Collectors are obligated to hold the sample for as short a time as possible especially if knowledge exists
showing that this is necessary to maintain sample stability.
5 If collected in an unpreserved container in the field, sample will be split in the laboratory and preserved with H2SO4
to pH<2 immediately upon sample receipt.
12. Sample Handling and Custody
Sample handling is designed to maintain viability of all water samples. Sample bottles containing
appropriate preservatives are obtained from the SDWRF laboratory. All plastic bottleware are
constructed of high density polyethylene (HDPE). Disposable bottles are properly discarded by SDWRF
laboratory staff following sample analysis. One gallon Nalgene bottleware are thoroughly cleaned by
SDWRF laboratory staff between sampling events. Nalgene bottleware for fecal coliform samples are
thoroughly cleaned and autoclaved between sample events. Sample bottles obtained from the
laboratory have unique numeric identifiers for each set of bottles. Bottleware used for ambient water
chemistry monitoring are included in Figure 3.
16

Figure 4. Bottleware used for ambient water chemistry monitoring.
Each set of bottles are assigned to a monitoring location or as a quality assurance sample by the Project
Manager. Problems with bottles (e.g., broken or missing bottles) are reported to the Laboratory
Manager. During transport of sample bottles from the analytical laboratory to the Water Quality
Laboratory at City Hall, care should be taken to reduce the chance of contamination. Samples should be
transported to the field in a clean vessel in the cab of a truck or trunk of a vehicle and not in the bed of a
truck.
Prior to departing for the field, a sufficient number of coolers should be filled with wet ice to ensure
samples can be properly temperature preserved until delivered to the laboratory. All bottleware should
be pre -labeled prior to departing for the field. Bottleware that will be delivered to the SDWRF
laboratory should be labeled with the numeric identifiers that correspond to the sampling locations that
will be sampled, including field blank bottleware. Bottleware that will be picked up or delivered to the
contract laboratory will be labeled with the site name, date and time, project name, preservatives, and
required analyses. Equipment blanks, if needed, are sampled in the laboratory and immediately placed
on ice prior to departure from City Hall.
After collection, samples are immediately placed in coolers with wet ice and remain there for the
duration of transport to the corresponding analytical laboratory. All samples will be accompanied by a
chain of custody (COC). The COC should be properly and completely filled out with the project name,
sample location, date, time, sample ID, analysis required and collector's name and signature. Samples
received by the laboratory either have a pre -assigned laboratory number or are assigned a laboratory
number and are checked for signs of damage. The temperatures of the samples are verified by checking
the temperature of the temperature blank (a bottle filled with water) that is placed in the sampling
17

coolers before sampling. The temperature blank is important because samples must be stored at less
than 4° C after sample collection until delivered to the laboratory. When relinquishing the samples to
the laboratory or laboratory's courier, the receiver and staff member relinquishing the samples must
sign and date the COC. Each party retains a copy of the COC for record keeping.
13. Analytical Methods
Table 6. Minimum Method Detection Limits, minimum Reporting Limits, and analytical methods for parameters
evaluated for the Citv's ambient water chemistry monitoring program.
Analyte
Method Detection
Limit
Reporting
Limit
Analytical
Method
Total suspended solids (TSS)
1.0 mg/L
2.5 mg/L
SM 2540 D
Nitrate + Nitrite Nitrogen
0.01 mg/L
0.10 mg/L
EPA 300.0
Ammonia-N (NH3-N)
0.01 mg/L
0.05 mg/L
SM 4500 NH3 D
Total Kjeldahl nitrogen (TKN)
0.12 mg/L
0.30 mg/L
EPA 351.2
Total phosphorus (TP)
0.02 mg/L
0.03 mg/L
EPA 365.3
Copper, Total
0.04 µg/L
5.0 µg/L
EPA 200.8
Copper, Dissolved
0.04 µg/L
5.0 µg/L
EPA 200.8
Zinc, Dissolved
0.7 µg/L
10.0 µg/L
EPA 200.8
Calcium, Total
37 µg/L
1000 µg/L
SM 3111B
Magnesium, Total
28 µg/L
1000 µg/L
SM 3111B
Fecal Coliform
1.0 cfu/100ml
1.0 cfu/100ml
SM 9222 D
Organic Carbon, Total (TOC)
0.32 mg/L
1.0 mg/L
SM5310B
Organic Carbon, Dissolved (DOC)
0.32 mg/L
1.0 mg/L
SM5310B
14. Quality Control
Quality control (QC) requirements include field audits, the collection of QC samples, and method quality
control in the analytical laboratory. Field audits are performed at least once per calendar year. Every
member that acts as a team lead during ambient monitoring is included in the audit. The audit
evaluates calibration/post check methods, sampling methods, and proper documentation. QC samples
may consist of field blanks, equipment blanks, field duplicates, and split samples. A contract laboratory
supplies deionized (DI) water in 1L, certified clean, plastic and glass bottles for all blanks.
Field blanks are collected to detect contamination from ambient conditions during sampling and
laboratory sources of contamination. Field blanks are collected by pouring DI water directly into
the bottleware at one of the sampling locations. One set of field blanks is collected each sample
day. The station that the field blanks are sampled from is rotated each month.
Equipment blanks are collected to detect sources of contamination from sampling equipment
(e.g. sample scoop). Equipment blanks are collected in the Water Quality Laboratory in City Hall
prior to use in the field. Separate equipment blanks are collected for each piece of equipment
that is used in the field. Equipment blanks are collected by pouring DI water over the
decontaminated sampling equipment that is used the same sampling day. If no sampling
18

equipment is used on a given sample day, then no equipment blank is required to be submitted
to the laboratory.
Field duplicates are collected to estimate sampling and laboratory analysis precision. Field
duplicates are collected concurrently.
Split samples are collected to evaluate laboratory performance by determining data precision
between laboratories. Split samples are collected and analyzed twice annually. At least one split
sampling event includes the NCDWR laboratory. Other split samples go to contract laboratories.
Reference samples may be submitted to any laboratory performing ambient water chemistry
sample analysis. Reference samples must be from an accredited ISO Guide 34 and ISO 17025
laboratory.
Laboratory QC Checks
Laboratory quality assurance/quality control (QA/QC) is performed as described in the laboratory QA
Plan. Duplicates, matrix spikes, method blanks, and other quality control samples are analyzed for this
project. Any samples analyzed by the contract laboratory for this project will report associated data
qualifiers as described by the NCDWR.
15. Instrument/Equipment Testing, Inspection, and Maintenance
Equipment testing, inspection, and maintenance occur according to the manufacturer's
recommendations. This includes pre and post calibration of field equipment (described below), pre -
washing sampling equipment, and proper maintenance of all field meters used. All maintenance is
recorded in an equipment service log located in the Water Quality Laboratory in City Hall (Appendix D).
This service log includes the date the service or maintenance was performed, the name of the person
performing the service or maintenance, and the service or maintenance performed.
16. Instrument Calibration and Frequency
Field meters are calibrated against known standards in the Stormwater Services laboratory per the
Ambient Water Chemistry Monitoring SOP and manufacturer's guidelines each sampling day prior to use
in the field. Field meters are also post checked against known standards at the end of each sampling
day.
17. Inspection/Acceptance Requirements for Supplies and Consumables
The SDWRF Laboratory performs quality assurance for sample bottles and chemical preservatives that
are provided to Stormwater Services staff. Sample bottles are visibly inspected by field staff prior to use
to ensure bottle integrity and cleanliness. Bottles should be re -inspected for faulty seals or leaks
following sample collection. New or disposable containers purchased as pre -cleaned are certified by the
manufacturer or checked to ensure the parameters tested are below the published reporting limits.
Bottles are capped until use and stored in a manner that does not leave them susceptible to
contamination by dust or other particulates. If any bottle is suspected to be contaminated, that bottle is
discarded or properly decontaminated.
19

The expiration date for standard solutions is checked prior to instrument calibration or post -monitoring
check. Expired standard solutions are never used for calibration or post -check. Any expired solution is
immediately discarded according to the manufacturer's recommendation.
18. Data Acquisition
All data from the ambient water chemistry monitoring program are generated from field observations,
field measurements, and sample analysis at the laboratory. On a monthly basist these data are
uploaded to the City's Water Quality Web Portal located at http://cormp2.das.uncw.edu/durhamwq/.
19. Data Management
Field measurements and site information are recorded on field data sheets (Appendix A). These
measurements and site information are transcribed into a Microsoft Excel file template used to upload
field data to the Water Quality Web Portal. This template is available for download from the web portal
under the "Upload Data File" tab, which is available to Level 2 and Level 3 users. A description of data
management to the web portal is provided in Appendix F.
Laboratory data are delivered via e-mail from the analytical laboratories to the City's Water Quality Unit
in a Microsoft Excel file. These files must be in a format suitable for upload to the City's Water Quality
Web Portal. A flow chart of data collected at ambient water chemistry monitoring sites is included in
Figure 4.

AMBIENT WATER
QUALITY MONITORING
SITE VISIT
FIELD MEASUREMENTS
AND OBSERVATIONS
RECORDED ON FIELD
FORM
FIELD MEASUREMENTS
AND OBSERVATIONS
TRANSCRIBED INTO
EXCEL FIELD FILE
TEMPLATE
ELECTRONIC FIELD FILE
UPLOADED TO WEB
PORTAL
HARD COPY OF FIELD
FORM FILED AT CITY
HALL AND RETAINED
FOR 5+ YEARS.
ELECTRONIC FIELD FILE
STORED ON THE CITY'S
SHARED DRIVE AND
RETAINED INDEFINITELY
SAMPLE INFORMATION
RECORDED ON CHAIN OF
CUSTODY FORM;
SAMPLES SUBMITTED TO
SDWRF LABORATORY
SDWRF FACILITY
PREPARES LAB REPORT
WITH SAMPLE RESULTS
AND E-MAILS REPORT TO
WATER QUALITY GROUP
LAB REPORT FILE
UPLOADED TO WEB
PORTAL
FIELD AND LABORATORY
FILES LINKED BY SITE ID,
DATE, AND TIME
DATA REVIEWED AND
QUALIFIED BY THE
PROJECT MANAGER
DATA PUSHED TO THE
WEB, AVAILABLE FOR
VIEW AND DOWNLOAD
BY REGISTERED USERS
LAB REPORT PRINTED
AND HARD COPY FILED
AT CITY HALL AND
RETAINED FOR 5+
YEARS. ELECTRONIC
LAB FILE ARCHIVED ON
THE CITY'S SHARED
DRIVE AND RETAINED
INDEFINITELY

PART C: ASSESSMENT AND OVERSIGHT
20. Assessments and Response Actions
Field activities are reviewed via field monitoring audits and ancillary reporting by field staff to the
Project Manager. Identified deficiencies result in additional training to staff members. Until the
deficiency has been remedied, the Project Manager will monitor the staff members during monitoring.
In addition, problem areas identified during the field audit are mentioned in the audit memorandum
along with recommended corrective action(s). The audit memorandum is generated after the field audit
and is distributed to all staff that performs ambient water chemistry monitoring. All staff members that
act as a team lead for ambient water chemistry monitoring are audited a minimum of once per calendar
year.
Laboratory personnel are responsible for assessments and response actions related to laboratory
activities. The laboratory is also assessed by the Project Manager through QA sample review and split -
sample studies. During split -sample studies, samples are split between the laboratory performing
ambient water chemistry analysis and the NCDWR laboratory, and/or another contract laboratory. A
minimum of one split -sample study is performed each calendar year. Any laboratory deficiencies
identified by the Project Manager are relayed to laboratory staff upon discovery. Any deficiencies
discovered by laboratory personnel are relayed to the Project Manager upon discovery. An action plan
should be developed by the appropriate laboratory personnel to rectify any deficiencies.
21. Reports
Stormwater Services provides regular updates of water quality to the public and to NCDWR. There are
two primary methods of reporting annual water quality assessments, the annual State of Our Streams
report and the NPDES annual report. The Water Quality Monitoring and Assessment Plan, Water Quality
Recovery Plan, and TMDL implementation reports also contain analyses of water quality data. The State
of Our Streams report summarizes the water quality index, fecal coliform bacteria, and water clarity in a
simplified format. These reports, which are available on the Stormwater Services website, also include
other information regarding water quality protection efforts made by the City of Durham. The State of
Our Streams reports are available beginning in 2004.
Several different matrices are generated for the NPDES annual report with a higher focus on reporting
implementation efforts. However, there is some overlap with the State of Our Streams report in terms
of water quality reporting. A summary table of parameters is provided in each NPDES Annual Report.
Future reports may contain comparisons of monitoring locations for selected parameters, including box
and whiskers plots of DO, conductivity, turbidity, TSS, TN, and TP.
22

PART D: DATA VALIDATION AND USABILITY
22. Data Review, Verification, and Validation
Data received from field measurements and laboratory analysis are compared and reviewed monthly by
the Project Manager and periodically by the QA Officer. Any data that are found to be incorrect or
unusual are reviewed by the Project Manager to determine if the data need to be qualified or rejected.
23. Validation and Verification Methods
Field staff visually checks and verifies for accuracy information included on the following items:
• Calibration/Post Check Form
• Bottle Labels
• Chain of Custody Form
• Field Forms
• Electronic Field Data Spreadsheet Template
SDWRF laboratory personnel are responsible for validating and verifying laboratory -generated data
reported to Stormwater Services. Data are qualified, when applicable, with the flags/qualifier codes
included in Table 8.
Final data validation and verification is performed by the Project Manager and occurs in the Water
Quality Web Portal. This procedure is outlined in the City of Durham Water and Sediment Quality Data
Management SOP (Appendix E). During this process, field and laboratory data are graphed for visual
comparison amongst site data and compared against the mean historical data for each site. Field data
are also compared against the calibration/post check form and qualified or rejected if there is evidence
of the following:
• Calibration error
• Equipment error
• User error
• Drift
• Use of improper or expired calibration standard
Laboratory data are compared against blank data to determine if there is evidence of blank
contamination that may indicate sample contamination. If there is evidence blank and/or sample
contamination, data may be qualified or rejected.
24. Reconciliation with Data Quality Objectives
When data are received from the laboratory, the Project Manager evaluates the data for precision,
completeness, and accuracy. If data quality indicators do not meet ambient water chemistry monitoring
specifications, the data are rejected and the cause for failure is evaluated. If the cause is found to be
equipment failure, calibration and/or maintenance techniques are reassessed and improved. If the
problem is related to sampling techniques, field staff undergoes additional training. Any significant
23

limitations on data use (resulting in >10% rejected data during a single sampling event or over the
course of a sample year) are detailed in a memorandum that is provided to key personnel. If the cause
is found to be unrelated to equipment, methods, or sample error, specifications are revised for the
following sample year.
Table 7. Data qualifier codes (flags) used for ambient water chemistry monitoring data.
Category
Qualifier
Code
Description
B
Results based on colony count outside of the acceptable range and should be used with caution.
131
Countable membranes w/ less than 20 colonies. Reported value is estimated or is a total o fthe
counts on all filters reported per 100mL.
Counts from all filters were zero. The value reported is based on the number of colonies per
B2
100mL that would have been reported if there had been one colony on the filter representing the
largest filtration volume ( reported as "<" value).
B: Microbial tests
membrane filter (MF)
counts
B3
Countable membranes with more than 60 (or 80) colonies. The value reported is calculated using
the count from the smallest volume filtered (reported as a ">" value).
B4
Filters have counts of both >60 (or >80) and <20. Reported value is a total of the counts from all
countable filters reported per 100mL.
Too many colonies were present / too numerous to count (TNTC). The numeric value represents
B5
the max number of counts typically accepted on a filter membrane (60 or 80), multiplied by 100
and then divided by the smallest filtration volume analyzed (reported as a ">" value).
B6
Estimated value. Blank contamination evident.
D: Dilution
D
Sample analyzed at dilution
G: Depletion
-
<1 mg/L DO remained for all dilutions set. The reported value is an estimated > value and is
calculated for the dilution using the least amount of sample
G8
Oxygen Usage <2 mg/L for all dilution sets. The reported value is an estimate < value and is
calculated for dilution using the most amount of sample.
J
The reported value is less than the laboratory Method Reporting Limit (MRL) but greater than or
equal to the Method Detection Limit (MDL)
JS
Surrogate recovery limits have been exceeded
J2
The reported value failed to meet the established QC criteria for either precision or accuracy
J3
The sample matrix interfered with the ability to make any accurate determination.
1: Estimated
J4
The data are questionable because of improper laboratory or field protocols
J5
Temperature limits exceeded (samples frozen or> 4 C) during transport
J6
Laboratory analysis was from an unpreserved or improperly chemically preserved sample.
J7
Blank contamination evident, value may not be accurate
The reported value is determined by a one -point estimation rather than against a regression
J9
equation. The estimated concentration is less than the practical quantitation limit and greater
than the method detection limit.
P: Elevated PQL
P
Elevated PQL due to matrix interference and/or sample dilution
Q
Holding time exceeded
Q1
Holding time exceeded prior to receipt by lab
Q: Holding Time
Q2
Holding time exceeded following receipt by lab
R: Rejected
R
Sample rejected due to blank contamination exceeding value reported
U: Non -detect
U
The contaminant was not detected at a concentration greater than the detection limit
X1
Sample not screened for this constituent
X: Not Analyzed
X2
Sampled, but analysis lost or not performed - field error.
X3
Sampled, but analysis lost or not performed - lab error
Y: Elevated PQL
Y
Elevated PQL due to insufficient sample size
Z: Rejected
Z
Sample results are rejected due to serious deficiencies in the ability to analyze the sample and
meet QC criteria. The presence or absence of the analyte can't be verified.
24

REFERENCES
City of Durham, Annual Report NPDES Municipal Stormwater Permit Number NCS000249
October 1, 2011 - September 30,2012
City of Durham Water and Sediment Quality Data Management Standard Operating Procedures, July
2013
Falls Lake Nutrient Management Strategy: Effective Date July 15, 2011 (NCGS 15A NCAC 02B .0275
through .0282 and amended .0235 and .0315)
http://Porta1.ncdenr.org/web/faIIslake/read-the-rules (Accessed September 2013)
North Carolina Division of Water Resources Ambient Lakes Monitoring Program Quality Assurance
Project Plan: July 2012 http://portal.ncdenr.org/web/wq/ambientlake (Accessed September
2013)
25