Quality-Control Design for Surface-Water

Sampling in the National Water-Quality

Assessment Program

U.S. GEOLOGICAL SURVEY

Open-File Report 97–223

Quality-Control Design for Surface-Water
Sampling in the National Water-Quality
Assessment Program

By David K. Mueller, Jeffrey D. Martin, and Thomas J. Lopes

U.S. GEOLOGICAL SURVEY

Open-File Report 97–223

Denver, Colorado
1997
U.S. DEPARTMENT OF THE INTERIOR
BRUCE BABBITT, Secretary

U.S. GEOLOGICAL SURVEY

Gordon P. Eaton, Director

The use of firm, trade, and brand names in this report is for identification purposes only and does
not constitute endorsement by the U.S. Geological Survey.

For additional information write to: Copies of this report can be purchased
from:

Chief, NAWQA Program U.S. Geological Survey

U.S. Geological Survey Information Services
12201 Sunrise Valley Drive Box 25286
Mail Stop 413 Federal Center
Reston, VA 20192 Denver, CO 80225

Information regarding the National Water-Quality Assessment (NAWQA) Program is available on the
Internet via the World Wide Web. You may connect to the NAWQA Home Page using the Universal
Resources Locator (URL) at http://wwwrvares.er.usgs.gov/nawqa/nawqa_home.html>
FOREWORD

The mission of the U.S. Geological Survey • Describe how water quality is changing over
(USGS) is to assess the quantity and quality of the time.
earth resources of the Nation and to provide informa- • Improve understanding of the primary natural
tion that will assist resource managers and policy- and human factors that affect water-quality
makers at Federal, State, and local levels in making conditions.
sound decisions. Assessment of water-quality condi- This information will help support the development
tions and trends is an important part of this overall and evaluation of management, regulatory, and moni-
mission. toring decisions by other Federal, State, and local
One of the greatest challenges faced by water- agencies to protect, use, and enhance water resources.
resources scientists is acquiring reliable information The goals of the NAWQA Program are being
that will guide the use and protection of the Nation’s achieved through ongoing and proposed investigations
water resources. That challenge is being addressed by of 59 of the Nation’s most important river basins and
Federal, State, interstate, and local water-resource aquifer systems, which are referred to as study units.
agencies and by many academic institutions. These These study units are distributed throughout the
organizations are collecting water-quality data for a Nation and cover a diversity of hydrogeologic settings.
host of purposes that include: compliance with permits More than two-thirds of the Nation’s freshwater use
and water-supply standards; development of remedia- occurs within the 59 study units and more than two-
tion plans for specific contamination problems; opera- thirds of the people served by public water-supply
tional decisions on industrial, wastewater, or water- systems live within their boundaries.
supply facilities; and research on factors that affect National synthesis of data analysis, based on
water quality. An additional need for water-quality aggregation of comparable information obtained from
information is to provide a basis on which regional- the study units, is a major component of the program.
and national-level policy decisions can be based. Wise This effort focuses on selected water-quality topics
decisions must be based on sound information. As a using nationally consistent information. Comparative
society we need to know whether certain types of studies will explain differences and similarities in
water-quality problems are isolated or ubiquitous, observed water-quality conditions among study areas
whether there are significant differences in conditions and will identify changes and trends and their causes.
among regions, whether the conditions are changing The first topics addressed by the national synthesis are
pesticides, nutrients, volatile organic compounds, and
over time, and why these conditions change from place
aquatic biology. Discussions on these and other water-
to place and over time. The information can be used to
quality topics will be published in periodic summaries
help determine the efficacy of existing water-quality
of the quality of the Nation’s ground and surface water
policies and to help analysts determine the need for
as the information becomes available.
and likely consequences of new policies.
This report is an element of the comprehensive
To address these needs, the U.S. Congress appropri- body of information developed as part of the NAWQA
ated funds in 1986 for the USGS to begin a pilot pro- Program. The program depends heavily on the advice,
gram in seven project areas to develop and refine the cooperation, and information from many Federal,
National Water-Quality Assessment (NAWQA) State, interstate, Tribal, and local agencies and the
Program. In 1991, the USGS began full implementation public. The assistance and suggestions of all are
of the program. The NAWQA Program builds upon an greatly appreciated.
existing base of water-quality studies of the USGS, as
well as those of other Federal, State, and local agencies.
The objectives of the NAWQA Program are to:
(signed)
• Describe current water-quality conditions for a
large part of the Nation’s freshwater streams, Robert M. Hirsch
rivers, and aquifers. Chief Hydrologist

FOREWORD iii
CONTENTS
Foreword................................................................................................................................................................................ iii
Abstract.................................................................................................................................................................................. 1
Introduction ........................................................................................................................................................................... 1
Purpose and Scope....................................................................................................................................................... 1
Acknowledgments ....................................................................................................................................................... 1
Types of Quality-Control Samples ........................................................................................................................................ 2
Collection and Processing of Quality-Control Samples ........................................................................................................ 3
Field Blanks................................................................................................................................................................. 3
Inorganic Constituents and Pesticides ............................................................................................................... 3
Dissolved and Suspended Organic Carbon........................................................................................................ 3
Volatile Organic Compounds............................................................................................................................. 4
Trip Blanks .................................................................................................................................................................. 4
Field Matrix Spikes ..................................................................................................................................................... 4
Pesticides ........................................................................................................................................................... 4
Volatile Organic Compounds............................................................................................................................. 5
Spike Recovery Calculations............................................................................................................................. 5
Replicates..................................................................................................................................................................... 6
Inorganic Constituents, Pesticides, and Suspended Sediment........................................................................... 6
Dissolved and Suspended Organic Carbon........................................................................................................ 6
Volatile Organic Compounds............................................................................................................................. 6
Frequency, Timing, and Location of Quality-Control Sample Collection ............................................................................ 7
Data Management.................................................................................................................................................................. 8
References ............................................................................................................................................................................. 8
Appendix A—Constituents Included in National Water Quality Laboratory Schedules and Codes
Referred to in this Report ........................................................................................................................................ 11
Appendix B—Analytical Services Request and National Water Information System Data-Base
Coding Required for Quality-Control Samples and Associated Environmental Samples
Collected as Part of the National Water-Quality Assessment Program................................................................... 15
Blanks .......................................................................................................................................................................... 15
Environmental Sample Associated with the Blank ........................................................................................... 15
Field Blank ........................................................................................................................................................ 15
Canister Blank ................................................................................................................................................... 15
Trip Blank.......................................................................................................................................................... 15
Spikes........................................................................................................................................................................... 16
Primary Environmental Sample Associated with the Spikes............................................................................. 16
Duplicate Environmental Sample Associated with the Spikes.......................................................................... 16
Field Matrix Spike ............................................................................................................................................. 16
Field Matrix Spike Duplicate ............................................................................................................................ 16
Replicates..................................................................................................................................................................... 17
Primary Environmental Sample......................................................................................................................... 17
Duplicate Environmental Sample ...................................................................................................................... 17

TABLES
1. Collection frequencies for routine quality-control samples .................................................................................... 7
A1. Pesticides analyzed in National Water Quality Laboratory schedules 2001 and 2010 ........................................... 11
A2. Pesticides analyzed in National Water Quality Laboratory schedules 2050 and 2051 ........................................... 12
A3. Volatile organic compounds analyzed in National Water Quality Laboratory schedule 2020................................ 13

CONTENTS v
CONVERSION FACTORS AND ABBREVIATIONS

Multiply By To obtain

liter (L) 1.057 quart

liter (L) 0.2642 gallon
gram (g) 0.03527 ounce, avoirdupois

Additional Abbreviations

milliliter (mL)
microliter (µL)
milligram per liter (mg/L)
microgram per liter (µg/L)
microgram per milliliter (µg/mL)

vi CONTENTS
Quality-Control Design for Surface-Water Sampling
in the National Water-Quality Assessment Program
By David K. Mueller, Jeffrey D. Martin, and Thomas J. Lopes

Abstract 2. Sample-matrix interference or analyte degradation

affect the recovery (bias and variability) of
The data-quality objectives of the National organic compounds.
Water-Quality Assessment Program include 3. Sample collection, processing, and analysis
estimating the extent to which contamination, affect the variability of measured constituent
matrix effects, and measurement variability affect concentrations.
interpretation of chemical analyses of surface- Data obtained from routine quality-control (QC)
water samples. The quality-control samples used samples are used by NAWQA study-unit and
to make these estimates include field blanks, field national-synthesis teams to meet these objectives
matrix spikes, and replicates. This report and to evaluate potential effects on the interpretation
describes the design for collection of these of environmental data.
quality-control samples in National Water-Quality
Assessment Program studies and the data
Purpose and Scope
management needed to properly identify these
samples in the U.S. Geological Survey’s national This report describes:
data base.
1. Procedures used to collect QC samples at surface-
water sites in the NAWQA Program.
2. Sampling design, including frequency, timing, and
INTRODUCTION location of sample collection.
A primary goal of the National Water-Quality 3. Data management, including coding used to submit
Assessment (NAWQA) Program is to describe the samples for laboratory analysis and to store
occurrence, distribution, and trends of selected results in electronic data bases.
chemical constituents in the Nation’s surface and The scope is limited to NAWQA study units that began
ground water. To interpret water-quality data properly, operation in 1994 or that are to begin later.
information is needed to estimate the bias and The first surface-water samples in these study units
variability that result from sample collection, sample were collected during 1995–96.
processing, and chemical analysis. Bias is the system-
atic error inherent in a method and may be either
positive or negative. Variability is the degree of Acknowledgments
random error in repeated measurements of the same
quantity. The procedures and sampling design described
in this report were developed in extensive discussions
The objectives in evaluating sampling bias and
by the NAWQA QC Workgroup. The authors acknowl-
variability for surface-water chemical analyses are to
edge the substantial contributions of other members of
determine the extent to which: the Workgroup: Michael Koterba
1. Sampling methods and equipment introduce (Project Chief), Greg Delzer, Kimberly Pirkey,
contaminants (positive bias) into water samples. Barbara Ruddy, Terry Schertz, and Jonathan Scott.

Abstract 1
TYPES OF QUALITY-CONTROL SAMPLES matrix interference or analyte degradation. Matrix
interference is the effect that the sample matrix has on
Three types of QC samples are routinely measurement of individual analytes within the sample.
collected in NAWQA studies. Blanks and spikes are A field matrix spike is a specific type of spiked sample
used to estimate bias. Replicates are used to estimate that is fortified in the field prior to shipping. These
variability. samples are used to assess the potential bias for
A blank is a water sample that is intended to analytes in a particular sample matrix. This bias also
be free of the analytes of interest. Blank samples are might include analyte degradation during shipping and
analyzed to test for bias that could result from contam- handling. Bias is estimated from spiked samples by
ination of environmental samples by the analytes calculating the percentage of the added analyte that is
of interest during any stage of sample collection, measured (recovered) in the sample. Recovery can be
processing, and analysis. A field blank is prepared in either greater than or less than 100 percent, so the bias
the field and used to demonstrate that: (1) Equipment can be either positive or negative; however, matrix
has been adequately cleaned to remove contamination interference and analyte degradation generally result
introduced by samples obtained at previous sites, in a negative bias.
(2) sample collection and processing have not resulted
Replicates are two or more samples collected
in contamination, and (3) sample handling and
or processed so that the samples are considered to be
transport have not introduced contamination. In
essentially identical in composition. Split replicates
addition, because the field blank is treated like an
environmental sample at the laboratory, it includes are prepared by dividing a single volume of water into
potential contamination introduced during laboratory multiple samples. These replicates provide a measure
handling and analysis. of the variability introduced during sample processing
An equipment blank is used to demonstrate and analysis. Concurrent replicates are multiple
that the sample-collection and sample-processing samples collected from an environmental matrix as
equipment is not introducing contamination. closely as possible to the same location and time.
Equipment blanks can be prepared using individual These replicates account for the variability measured
pieces of the collection and processing equipment. by split replicates and the additional variability
For example, a sample prepared by exposing the blank introduced by sample collection. Depending on
solution just to the filter apparatus would be a filter sampling procedures, concurrent replicates also might
blank. In the NAWQA Program, the only type of include an unknown amount of short-term environ-
equipment blank that is routinely prepared is a canister mental variability. Sequential replicates are multiple
blank, which is collected from the canister used to samples collected at the same location, but at slightly
prepare volatile organic compound (VOC) blanks. It is different times, generally one right after the other.
used to determine whether the canister is introducing These replicates provide a measure of the same
contamination into the VOC field blank in excess of sources of variability as concurrent replicates and
that which might be introduced by the VOC sampler the additional variability associated with short-term
itself. A canister blank is prepared only in association environmental fluctuation.
with a VOC field blank. For the purposes of this report, the term
A trip blank is a sample of analyte-free water “replicates” is used to refer to all similarly collected or
that is prepared in the laboratory or in the office. It is processed samples. The terms “primary environmental
transported, unopened, to the field with other sample sample” and “duplicate environmental sample” are
bottles and is shipped to the laboratory for analysis used to identify particular samples in a replicate pair.
with the collected samples. Trip blanks are used to Likewise, the term “field matrix spike replicates” is
identify contamination that might occur during sample used to refer to all similarly collected, processed, and
transport and analysis rather than as a result of sample spiked samples, and the terms “field matrix spike” or
collection and processing in the field. Because the “field matrix spike duplicate” are used to identify
primary source of this contamination is airborne, trip particular spiked samples. The term “subsample”
blanks are normally prepared only for VOC’s. refers to that portion of any individual sample (or
A spike is an environmental sample that is duplicate) that is processed for analysis of a particular
fortified with a known mass of the analyte of interest. group of analytes (such as anions, cations, dissolved
Spiked samples are used to test for bias resulting from nutrients, or pesticides).

2 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
COLLECTION AND PROCESSING Inorganic Constituents and Pesticides
OF QUALITY-CONTROL SAMPLES 1. Rinse all equipment with the appropriate type of
blank water (IG or PG). Follow the procedures
normally used for field rinsing.
Field Blanks
2. Obtain a field-blank sample by pouring the blank
Field blanks should be prepared immediately water into the bottle used with a US DH–81
before collecting and processing an environ- or US D–77 sampler (Edwards and Glysson,
mental sample at a selected site. All equipment 1988). Cap and shake. If environmental samples
should have been cleaned, either in the field or normally are composited, pour about 0.5 L of
in the laboratory, following use at the previous blank water from the sampler bottle through
the sampler cap and nozzle into the compositing
site. Shelton (1994, p. 13) describes the cleaning
container. Pouring through the sampler cap
procedure.
and nozzle simulates water contact with these
The water used for NAWQA field blanks components during sample collection. Then pour
must be either Ocala inorganic-grade (IG) deionized additional blank water directly from the sampler
water, National Water Quality Laboratory (NWQL) bottle into the compositing container until there
pesticide-grade (PG) water, or NWQL volatile-grade is sufficient volume to prepare all the necessary
(VG) water. Pesticide blanks must be prepared from subsamples. If environmental samples normally
PG water. Dissolved organic carbon (DOC) and are poured directly into a U.S. Geological Survey
suspended organic carbon (SOC) blanks can be (USGS) Teflon cone splitter (Capel and Larson,
prepared using either PG water or VG water. The VOC 1996), pour about 0.5 L of blank water through
blanks must be prepared from VG water. The DOC, the sampler cap and nozzle into the splitter. Then
SOC, and VOC blanks must be prepared using pour additional blank water directly from the
water from a previously unopened (fresh) bottle. sampler bottle into the cone splitter to fill the
Opened bottles might no longer be free of organic- subsample containers. If multiple sampler bottles
carbon species. are used to collect samples, pour some blank
To avoid the necessity of rinsing equipment with water from each bottle into the compositing
container or cone splitter.
both IG water and PG water, field blanks for inorganic
constituents should not be prepared during the same 3. Process the subsamples according to normal
site visit as field blanks for pesticides. In addition, procedures for a surface-water site (Shelton,
preparing the first blank could remove 1994, p. 20 and p. 23–26). Rinse sample bottles
most of the residual contamination, so the second and filters following normal procedures, using
blank might not be representative. To avoid blank water instead of native water.
data-base conflicts in specifying the type of blank 4. Record the lot number of the blank water in
water, field blanks prepared for different organic field notes and on the Comments line of the
constituents using different grades of water at the same ASR form. Also, record the last site and date
site visit must be assigned different times and at which the sampling equipment was used so
submitted with separate Analytical Services Request this possible source of contamination can be
(ASR) forms. identified.
Equipment need not be cleaned nor filters
changed between processing the field blank and the Dissolved and Suspended Organic Carbon
environmental sample. Simply field rinse with native Rinse a new, laboratory-baked sampler bottle,
water as would normally be done. However, certain such as normally used to collect the single-vertical
pieces of equipment should be cleaned if they have organic-carbon sample, with blank water. Fill the
obviously been contaminated or if there is a significant sampler bottle with fresh PG or VG water. Process
potential for contamination, such as a sample splitter the blank according to the DOC/SOC procedure for
sitting exposed to the environment for a long period samples containing less than 30 mg/L suspended
of time. sediment (Shelton, 1994, p. 21).

COLLECTION AND PROCESSING OF QUALITY-CONTROL SAMPLES 3

Volatile Organic Compounds (Compounds included in these pesticide schedules
1. Rinse the VOC hand-sampler and the steel transport and VOC schedule 2020 are listed in appendix A.)
canister (supplied by VOC National Synthesis) Spikes are always prepared in duplicate and
three times with fresh VG water. require at least one environmental sample to estimate
background concentrations of the spiked analytes. If
2. While wearing vinyl gloves, uncap six 40-mL vials.
Set two vials aside for the canister blank; place detectable background concentrations of the spiked
the remaining four vials into the sampler. Do not analytes are expected, replicate environmental samples
label the vials until sample processing has been should be collected to provide more precise estimates
completed. of background concentrations.
3. Fill the transport canister with fresh VG water. Pesticide spikes are split replicates from an
environmental sample. The VOC spikes are sequential
4. Submerge and fill the two canister-blank vials in the
replicates of an environmental sample. For all routine
canister.
spiked samples, the spiking solution should be
5. Submerge the sampler in the canister and fill the added in the field, even if extraction is done at the
remaining four vials. Select three of these vials NWQL. Spike kits and solutions must be obtained
to use for the field blank.
from the NWQL and should be used within 2 months.
6. Preserve, cap, and process both blanks according Always store spike solutions in a refrigerator or on
to the procedure used for environmental samples ice to minimize degradation, and discard unused
(L.R. Shelton, U.S. Geological Survey, written solution after opening.
commun., 1996).
Pesticides
Trip Blanks 1. Collect a sample using normal procedures (Shelton,
1994, p. 14). Obtain enough water for the extra
Trip blanks are used only for VOC’s. Pre-filled
vials of VG water, prepared at the NWQL, can be pesticide subsamples. The necessary volume
special ordered from the laboratory. Also, trip blanks depends on the number of environmental samples
can be included with regular orders for 40-mL sample that will be used to estimate background concen-
vials, if requested. trations (one or two) and on the pesticides
Trip blanks can become contaminated when that will be spiked (schedules 2001/2010 or
stored for long periods. To avoid this problem, 2050/2051, or both). At least an additional 6 L
pre-filled blanks should be stored in sealed containers, of water are required if spikes are prepared for
such as clean mason jars, and should be used within both pesticide schedules and if replicate environ-
1 week. Thus, blanks should not be ordered until just mental samples are collected.
before they are intended to be used. 2. Split the sample using a USGS Teflon cone splitter.
Select three pre-filled vials to be the trip blank Obtain three subsamples for pesticide analysis
and transport them to the field with the other VOC
(or four subsamples if replicate environmental
vials. Label the trip-blank vials with the same site
samples are needed). Use one of these subsam-
number and date as used for a field blank prepared
ples to prepare the environmental sample, use
during the sampling trip. Ship the trip blank to the
laboratory with the field blank and the environmental another to prepare the duplicate environmental
samples from that site. Do not open the trip-blank vial sample (if needed), and use the remaining two
at any time. subsamples to prepare replicate field matrix
spikes.
3. Filter the environmental sample following normal
Field Matrix Spikes procedures (Shelton, 1994, p. 23).
Field matrix spikes are required for 4. If replicate environmental samples are needed, load
pesticides (NWQL schedules 2001, 2010, 2050, and rinse a new filter, and filter the duplicate
and 2051) and for VOC’s (NWQL schedule 2020). environmental sample.

4 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
5. Filter the subsample replicates that are to be spiked uncapped, exposing the sample to volatilization
following the same procedures used for the loss.
environmental sample. Use a new filter for each 5. Process both spiked replicates following the same
replicate to minimize the variability associated procedures used for the environmental sample.
with filter loading. Filter approximately the same Label the first two spiked vials with FS (field
volume of water for each replicate. After filtering spike) and the second two spiked vials with FSD
and before extraction, add 0.1 mL (100 µL) (field spike duplicate).
of the appropriate spike solution to each replicate
using a micropipette (ignore instructions 6. On the ASR forms for each spiked replicate, record
in the spike kit about NWQL spiking one that only two vials have been submitted. Record
of the replicates in the laboratory). Use a new the lot number of the spike solution and the
micropipette for each spike. Allow the spike volume of spike solution in field notes and on the
solution to warm to room temperature before Comments line of the ASR forms. (This informa-
spiking. tion is necessary for computing spike recovery.)
6. Finish processing the environmental sample (and
Spike Recovery Calculations
duplicate) and spiked replicates. For each spiked
replicate, record the lot number of the spike Spike recovery (percent) for pesticides and
solution, the volume (milliliters) of spike solution VOC’s is calculated as follows:
used, and the volume (milliliters)
of the spiked subsample in field notes and on the
Comments line of the ASR form. (This informa- C Spiked – C Environ
Recovery = 100 ⋅ ------------------------------------------- (1)
tion is necessary for computing spike recovery.) C Expect

Volatile Organic Compounds

where
1. Load four 40-mL vials into the VOC hand-sampler CSpiked = the measured concentration in the spiked
and collect a sample. Three of these vials consti- sample, in micrograms per liter;
tute the environmental sample, and one vial is CEnviron = the measured concentration in the
used for backup if bubbles are present in one of associated environmental sample, in
the other vials after processing. If replicate micrograms per liter, or the mean
environmental samples are needed to estimate concentration in the associated replicate
background concentrations, two of the vials will environmental samples, in micrograms per
constitute the primary environmental sample and liter; and
the other two will constitute the duplicate CExpect = the expected concentration of the spike in
environmental sample. the spiked sample, in micrograms per liter.
2. Process and cap the environmental samples
The expected concentration is calculated as follows:
following normal procedures (L.R. Shelton,
U.S. Geological Survey, written commun., 1996).
If replicate environmental samples are needed, C Soln × V Soln
note on each ASR form that only two vials have C Expect = 1,000 ⋅ ------------------------------- (2)
V Samp
been submitted (instead of the usual three).
3. Immediately load four additional vials and collect
another sample. These vials will constitute the
spiked replicates (two vials each). where
4. Following the instructions provided with the CSoln = the concentration of the spike solution, in
spiking kit, use a syringe to inject the spike micrograms per milliliter;
solution into the four spike-replicate vials. Do VSoln = the volume of spike solution added to the
not inject the spike solution through the septum sample, in milliliters; and
in the cap. Minimize the time that the vial is VSamp = the volume of the sample, in milliliters.

COLLECTION AND PROCESSING OF QUALITY-CONTROL SAMPLES 5

Replicates 3. Rinse the cone splitter and additional split
containers with native water. Split
Replicates for analysis of inorganic constituents, the primary sample as is normally done
pesticides, and suspended sediment are produced by to obtain the necessary whole-water subsamples
splitting a single, large volume of water, collected and additional subsamples to be filtered later.
from the stream, into two samples (one primary Place these subsamples in a second cooler.
and one duplicate). Replicates for DOC, SOC, and 4. Repeat step 3 for the duplicate sample. Place the
VOC’s are collected from concurrent grab samples resultant subsamples in the first cooler.
(a sample splitter is not used for these analytes). The 5. Filter the subsamples in the normal order used
reason for selecting split replicates for most analytes for the different analyte groups (major ions,
is to exclude variability caused by short-term environ- nutrients, trace elements, or pesticides). For each
mental fluctuations, which might affect sequential group, filter the primary sample first, then the
replicates and, to some degree, concurrent replicates. duplicate sample. Filter the primary sample for
Split replicates allow assessment of sources of all analyte groups that normally use the same
variability (sample processing, handling, and analysis) filter (for example, nutrients and major ions)
before proceeding to the duplicate sample. Load
that can be controlled by field and laboratory
and rinse new filters prior to filtering the
procedures. Topical (nonroutine) QC samples are
duplicate sample. Do not clean the equipment
collected at selected sites to assess the variability
between samples.
caused by sample collection (Timothy L. Miller,
6. Sometimes only selected analyte groups are
U.S. Geological Survey, written commun., 1996).
obtained from the duplicate sample (for
These samples require the collection of concurrent example, pesticides, but not inorganic constitu-
replicates by different field crews during targeted ents). A suspended-sediment analysis should
conditions. be obtained from every duplicate sample.
Study units need to procure additional 3-L 7. Make separate field measurements of pH, specific
Teflon sampler bottles and 2-L glass split containers conductance, and alkalinity in the primary and
to collect and process sufficient volumes of water for duplicate samples.
split-replicate samples.
The split replicates (primary and duplicate Dissolved and Suspended Organic Carbon
samples) are processed sequentially by analyte group
1. Collect grab samples in two glass bottles following
(major ions, nutrients, trace elements, or pesticides).
normal procedures for organic-carbon sampling
Sequential processing minimizes the variability caused
(Shelton, 1994). Minimize the time interval
by differences in holding times of the primary and
between the two grabs. These samples are
duplicate samples.
considered concurrent for the purposes of data
management.
Inorganic Constituents, Pesticides, 2. Store the duplicate sample in a cooler. Process the
and Suspended Sediment primary sample according to normal procedures.
1. Collect a volume of stream water large enough for Rinse the filter holder with PG or VG water
all subsamples that are obtained for the primary between samples to remove any sediment. Then,
process the duplicate sample.
and duplicate samples. Often, this volume is
double the amount normally collected.
Volatile Organic Compounds
2. Rinse a USGS Teflon cone splitter and large split
containers with native water. Pour the water 1. Load four 40-mL vials into the VOC hand-sampler
collected from the stream through the cone and collect a sample.
splitter into two sets of containers. One set is 2. Process two vials as the primary sample and the
used for the primary sample, and the other is other two as the duplicate sample. Process the
used for the duplicate sample. Do not mix water primary sample first, then the duplicate sample,
between the two sets of containers. Place the following normal procedures. On each ASR
containers for the duplicate sample on ice in a form, record that only two vials have been
cooler. submitted (instead of the usual three).

6 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
FREQUENCY, TIMING, AND LOCATION OF of blanks throughout the year in proportion to the
QUALITY-CONTROL SAMPLE COLLEC- number of surface-water samples the team collects.
TION The goal is to evaluate each sampling team and each
equipment set often enough to ensure that procedures
The minimum number of each type of QC are adequate or that corrective actions are taken.
sample required to meet the stated QC objectives is Trip blanks for VOC’s should be shipped for
listed in table 1. The criteria used in determining this analysis with selected field blanks. Because field
sampling distribution are based on characteristics of vehicles contain various sources of VOC’s (such as
the constituents, expected constituent concentrations adhesives and gasoline) that might contaminate
in surface waters of the study unit, and results of samples, trip blanks should be distributed among all
previous QC analyses. The minimum numbers can vehicles used in VOC sampling. Trip blanks do not
be increased if necessary to meet individual study-unit need to be distributed among different field crews and
objectives. sites; however, they should be collected throughout the
The first field blank should be collected time period of VOC sampling.
as soon as a sampling routine has been established. Field matrix spikes should be prepared when
Subsequent field blanks should be collected environmental concentrations of the spiked analyte
throughout the sampling period in proportion to the are expected to be low (no more than 10 percent
number of environmental samples. Field blanks can of the expected concentration in the spiked sample).
be prepared at any surface-water site; however, certain Ideally, other chemical characteristics, particularly
sites should be targeted to test the greatest potential the concentration of organic carbon, should be similar
risk of contamination (for example, sites sampled to characteristics present when environmental concen-
following use of the equipment in water with high trations of the spiked analyte are high. If pesticide
analyte concentrations). Field blanks do not need to or VOC samples are collected for more than 1 year,
be prepared at every surface-water site. If surface- spike results should be evaluated after the first year
water samples are collected by more than one to determine if a different (generally higher) spike
sampling team, each team should prepare a number concentration needs to be used during the second year.

Table 1. Collection frequencies for routine quality-control samples

[--, no samples required]

Number of quality-control samples per total number of environmental samples

Constituent (at all surface-water sites, each year)
or group Field Trip Replicate field
Replicates
blanks blanks matrix spikes
Major ions 1 per 30a -- -- 1 per 20a
Nutrients 1 per 20a -- -- 1 per 20a
Suspended sediment 1 per 30a -- -- With each inorganic or
pesticide replicate
Dissolved and suspended 1 per 15–20a, b -- -- 1 per 15–20a, b
organic carbon
Pesticides 1 per 20a, c -- 1 set per site 1 per 10d
Volatile organic compounds 1 per 10–20b, c, e 1 per 20f 1 set per site 1 per 10–20b, c, d
Trace elements 1 per 10–20a, b, c -- -- 1 per 10–20a, b, c, d
a
If a large number of environmental samples are collected in a short period of time, reduce the quality-control sampling frequency to
one per month during that period.
b
If concentrations of interest are low (less than 10 times the detection limit), collect more blanks; if expected concentrations are high,
collect more replicates.
c
Minimum three per year.
d
If concentrations of all target analytes are expected to be less than detection, collection of replicates should be deferred until
conditions are more favorable for detection.
e
Prepare a canister blank with each field blank.
f
Minimum two per year. Send with a volatile-organic-compound field blank.

FREQUENCY, TIMING, AND LOCATION OF QUALITY-CONTROL SAMPLE COLLECTION 7

 Replicates should be targeted at sites and times blank, pesticide spike and spike duplicate, or
where concentrations of at least some target analytes VOC spike and spike duplicate) that is coded for
are expected to exceed detection limits. If concentra- a particular site and date must have a unique time.
tions of all target analytes are expected to be less than All routine QC samples should be associated
detection, collection of replicates should be deferred with an environmental sample. Do not use fictitious
until conditions are more favorable for detection. station ID numbers for routine QC samples.
Attempt to collect replicates over the range of detect- The NWIS data base cannot store lot numbers
able concentrations expected within the study unit, exactly as assigned for blank water or spike solutions.
but give greater emphasis to collecting replicates at For consistency within the NAWQA Program, use
high concentrations. Replicate samples need not be parameter code 99104 (reference material or spike
collected uniformly throughout the sampling period source code number) to store the first five numeric
or at all surface-water sites; however, they should digits of the lot number associated with blanks or
be scheduled to cover a broad range of hydrologic spikes. For example, PG water lot H16251, used
conditions. If surface-water samples are collected for a pesticide blank, should be stored as 16251;
by more than one sampling team, each team should VG lot 34116, used for a VOC blank, should be
collect at least one replicate during the sampling entered as 34116; IG water lot 94314 (#18),
period. bottle #20, used for an inorganic blank, should be
entered as 94314; and pesticide spike solution
lot LA38492 should be entered as 38492.
DATA MANAGEMENT The ASR and NWIS data base (QWDATA
or QADATA) coding required for QC samples and
Consistent coding of routine QC samples associated environmental samples collected as part
among study units is essential. For this reason, data- of the NAWQA Program are listed in appendix B.
management protocols have been developed for the
NAWQA Program. Use the following instructions
for coding information on ASR forms and into the REFERENCES
National Water Information System (NWIS) data base.
The most critical codes for proper sample identifi- Capel, P.D., and Larson, S.J., 1996, Evaluation of selected
cation are the station ID, sample medium, sample information on splitting devices for water samples:
type, and the QADATA parameter codes. U.S. Geological Survey Water-Resources Investiga-
tions Report 95–4141, 103 p.
Time coding of the sample is specified to distin-
Edwards, T.K., and Glysson, G.D., 1988, Field methods
guish among multiple samples at the same site visit, for measurement of fluvial sediment: U.S. Geological
particularly field matrix spikes for which different lot Survey Open-File Report 86–531, 118 p.
numbers of spike solutions are used and field blanks Shelton, L.R., 1994, Field guide for collecting and
for which different water types are used. Each type of processing stream-water samples for the National
sample (environmental, duplicate, inorganic field Water-Quality Assessment Program: U.S. Geological
blank, organic field blank, canister blank, trip Survey Open-File Report 94–455, 42 p.

8 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
APPENDIXES
APPENDIX A. CONSTITUENTS INCLUDED IN NATIONAL WATER QUALITY
LABORATORY SCHEDULES AND CODES REFERRED TO IN THIS REPORT

Table A1. Pesticides analyzed in National Water Quality Laboratory schedules 2001
and 2010

Watstore code CAS number Constituent

82660 579–66–8 2,6-Diethylaniline
49260 34256–82–1 Acetochlor
46342 15972–60–8 Alachlor
39632 1912–24–9 Atrazine
82686 86–50–0 Azinphos-methyl
82673 1861–40–1 Benfluralin
04028 2008–41–5 Butylate
82680 63–25–2 Carbaryl
82674 1563–66–2 Carbofuran
38933 2921–88–2 Chlorpyrifos
04041 21725–46–2 Cyanazine
82682 1861–32–1 Dacthal
04040 6190–65–4 Deethylatrazine
39572 333–41–5 Diazinon
39381 60–57–1 Dieldrin
82677 298–04–4 Disulfoton
82668 759–94–4 EPTC
82663 55283–68–6 Ethalfluralin
82672 13194–48–4 Ethoprophos
04095 944–22–9 Fonofos
39341 58–89–9 Lindane
82666 330–55–2 Linuron
39532 121–75–5 Malathion
39415 51218–45–2 Metolachlor
82630 21087–64–9 Metribuzin
82671 2212–67–1 Molinate
82684 15299–99–7 Napropamide
39542 56–38–2 Parathion
82667 298–00–0 Parathion-methyl
82669 1114–71–2 Pebulate
82683 40487–42–1 Pendimethalin
82664 298–02–2 Phorate
04037 1610–18–0 Prometon
04024 1918–16–7 Propachlor
82679 709–98–8 Propanil
82685 2312–35–8 Propargite
82676 23950–58–5 Propyzamide
04035 122–34–9 Simazine
82670 34014–18–1 Tebuthiuron
82665 5902–51–2 Terbacil
82675 13071–79–9 Terbufos
82681 28249–77–6 Thiobencarb
82678 2303–17–5 Tri-allate
82661 1582–09–8 Trifluralin
34253 319–84–6 alpha-HCH
34653 72–55–9 p,p’-DDE
82687 5264–55–3 Permethrin

APPENDIXES 11
 Table A2. Pesticides analyzed in National Water Quality Laboratory schedules 2050
and 2051

Watstore code CAS number Constituent

49295 90–15–3 1-Naphthol
39742 93–76–5 2,4,5-T
39732 94–75–7 2,4-D
38746 94–82–6 2,4-DB
39762 93–72–1 2-(2,4,5-Trichlorophenoxy) propanoic acid
49308 16655–82–6 3-Hydroxycarbofuran
49299 534–52–1 4, 6-Dinitro-2-methylphenol
49315 50594–66–6 Acifluorfen
49312 116–06–3 Aldicarb
49313 1646–88–4 Aldicarb sulfone
49314 1646–87–3 Aldicarb sulfoxide
38711 25057–89–0 Bentazon
04029 314–40–9 Bromacil
49311 1689–99–2 Bromoxynil
49310 63–25–2 Carbaryl
49309 1563–66–2 Carbofuran
49307 133–90–4 Chloramben
49306 1897–45–6 Chlorothalonil
49305 1702–17–6 Clopyralid
49304 887–54–7 Dacthal monoacid
38442 1918–00–9 Dicamba
49303 1194–65–6 Dichlobenil
49302 120–36–5 Dichlorprop
49301 88–85–7 Dinoseb
49300 330–54–1 Diuron
49298 66230–04–4 Esfenvalerate
49297 101–42–8 Fenuron
38811 2164–17–2 Fluometuron
38478 330–55–2 Linuron
38482 94–74–6 MCPA
38487 94–81–5 MCPB
38501 2032–65–7 Methiocarb
49296 16752–77–5 Methomyl
49294 555–37–3 Neburon
49293 27314–13–2 Norflurazon
49292 19044–88–3 Oryzalin
38866 23135–22–0 Oxamyl
49291 1918–02–1 Picloram
49236 122–42–9 Propham
38538 114–26–1 Propoxur
49235 55335–06–3 Triclopyr

12 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
Table A3. Volatile organic compounds analyzed in National Water Quality Laboratory
schedule 2020

Watstore code CAS number Constituent

Primary target analytes
32101 75–27–4 Bromodichloromethane
32102 56–23–5 Tetrachloromethane
32103 107–06–2 1,2-Dichloroethane
32104 75–25–2 Tribromomethane
32105 124–48–1 Dibromochloromethane
32106 67–66–3 Trichloromethane
34010 108–88–3 Methylbenzene
34030 71–43–2 Benzene
34210 107–02–8 2-Propenal
34215 107–13–1 2-Propenenitrile
34301 108–90–7 Chlorobenzene
34311 75–00–3 Chloroethane
34371 100–41–4 Ethylbenzene
34396 67–72–1 1,1,1,2,2,2-Hexachloroethane
34413 74–83–9 Bromomethane
34418 74–87–3 Chloromethane
34423 75–09–2 Dichloromethane
34475 127–18–4 Tetrachloroethene
34488 75–69–4 Trichlorofluoromethane
34496 75–34–3 1,1-Dichloroethane
34501 75–35–4 1,1-Dichloroethene
34506 71–55–6 1,1,1-Trichloroethane
34511 79–00–5 1,1,2-Trichloroethane
34536 95–50–1 1,2-Dichlorobenzene
34541 78–87–5 1,2-Dichloropropane
34546 156–60–5 trans-1,2-Dichloroethene
34551 120–82–1 1,2,4-Trichlorobenzene
34566 541–73–1 1,3-Dichlorobenzene
34571 106–46–7 1,4-Dichlorobenzene
34668 75–71–8 Dichlorodifluoromethane
34696 91–20–3 Naphthalene
34699 10061–02–6 trans-1,3-Dichloropropene
34704 10061–01–5 cis-1,3-Dichloropropene
39175 75–01–4 Chloroethene
39180 79–01–6 Trichloroethene
39702 87–68–3 Hexachlorobutadiene
50002 593–60–2 Bromoethene
50004 637–92–3 Ethyl tert-butyl ether
50005 994–05–8 tert-Amyl methyl ether
77093 156–59–2 cis-1,2-Dichloroethene
77128 100–42–5 Ethenylbenzene
77135 95–47–6 1,2-Dimethylbenzene
77222 95–63–6 1,2,4-Trimethylbenzene
77223 98–82–8 (1-Methylethyl)benzene
77224 103–65–1 n-Propylbenzene
77342 104–51–8 n-Butylbenzene
77443 96–18–4 1,2,3-Trichloropropane
77613 87–61–6 1,2,3-Trichlorobenzene

APPENDIXES 13
 Table A3. Volatile organic compounds analyzed in National Water Quality Laboratory
schedule 2020—Continued

Watstore code CAS number Constituent

Primary target analytes—Continued
77651 106–93–4 1,2-Dibromoethane
77652 76–13–1 1,1,2-Trichloro-1,2,2-trifluoroethane
78032 1634–04–4 Methyl tert-butyl ether
81577 108–20–3 Diisopropyl ether
82625 96–12–8 1,2-Dibromo-3-chloropropane
106–42–3 1,3-Dimethylbenzene
85795 108–38–3 1,4-Dimethylbenzene
Other analytes
30217 74–95–3 Dibromomethane
34516 79–34–5 1,1,2,2-Tetrachloroethane
49991 96–33–3 Methyl acrylate
49999 488–23–3 1,2,3,4-Tetramethylbenzene
50000 527–53–7 1,2,3,5-Tetramethylbenzene
73547 110–57–6 trans-1,4-Dichloro-2-butene
73570 97–63–2 Ethyl methacrylate
77041 75–15–0 Carbon disulfide
77057 108–05–4 Vinyl acetate
77103 591–78–6 2-Hexanone
77168 563–58–6 1,1-Dichloropropene
77170 594–20–7 2,2-Dichloropropane
77173 142–28–9 1,3-Dichloropropane
77220 611–14–3 2-Ethyltoluene
77221 526–73–8 1,2,3-Trimethylbenzene
77226 108–67–8 1,3,5-Trimethylbenzene
77275 95–49–8 1-Chloro-2-methylbenzene
77277 106–43–4 1-Chloro-4-methylbenzene
77297 74–97–5 Bromochloromethane
77350 135–98–8 (1-Methylpropyl)benzene
77353 98–06–6 (1,1-Dimethylethyl)benzene
77356 99–87–6 1-Isopropyl-4-methylbenzene
77424 74–88–4 Iodomethane
77562 630–20–6 1,1,1,2-Tetrachloroethane
78109 107–05–1 3-Chloro-1-propene
78133 108–10–1 4-Methyl-2-pentanone
81552 67–64–1 Acetone
81555 108–86–1 Bromobenzene
81576 60–29–7 Diethyl ether
81593 126–98–7 Methyl acrylonitrile
81595 78–93–3 2-Butanone
81597 80–62–6 Methyl methacrylate
81607 109–99–9 Tetrahydrofuran

14 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
APPENDIX B. ANALYTICAL SERVICES REQUEST AND NATIONAL WATER
INFORMATION SYSTEM DATA-BASE CODING REQUIRED FOR QUALITY-CONTROL
SAMPLES AND ASSOCIATED ENVIRONMENTAL SAMPLES COLLECTED AS PART
OF THE NATIONAL WATER-QUALITY ASSESSMENT PROGRAM
Blanks Canister Blank

ASR coding
Environmental Sample Associated with the Blank
STATION ID and DATE - Same as environmental
ASR coding sample
TIME - Time of sample collection rounded to nearest TIME - 1 minute earlier than the VOC field blank
10-minute interval (HH:X0)
SAMPLE MEDIUM - Q (QA sample - artificial)
SAMPLE MEDIUM - 9 (surface water)
SAMPLE TYPE - B (other QA)
SAMPLE TYPE - 9 (regular)
QADATA coding
QWDATA coding
Parameter 71999 (sample purpose) - 15 (NAWQA)
Parameter 71999 (sample purpose) - 15 (NAWQA)
Parameter 99100 (type of blank solution) - 50
Parameter 99111 (QA data associated with sample) - 10
(VG water)
(blank)
Parameter 99101 (source of blank solution) - 10
Field Blank (NWQL)
Parameter 99102 (type of blank sample) - 200 (other)
ASR coding
Parameter 99104 (blank lot number) - First five digits
STATION ID and DATE - Same as environmental of lot number
sample
TIME - Time of preparation (different from environmen- Trip Blank
tal sample) (NOTE: Blanks made from different
source solutions must have unique times.) ASR coding
SAMPLE MEDIUM - Q (QA sample - artificial) STATION ID and DATE - Same as environmental
SAMPLE TYPE - 2 (blank) sample
LOGIN COMMENTS - “PREVIOUS SAMPLE AT: TIME - 1 minute later than the VOC field blank
previous station ID, date/time”
SAMPLE MEDIUM - Q (QA sample - artificial)
QADATA coding
SAMPLE TYPE - 2 (blank)
Parameter 71999 (sample purpose) - 15 (NAWQA)
QADATA coding
Inorganic blanks:
Parameter 71999 (sample purpose) - 15 (NAWQA)
Parameter 99100 (type of blank solution) - 10
(IG water) Parameter 99100 (type of blank solution) - 50
Parameter 99101 (source of blank solution) - 80 (VG water)
(Ocala) Parameter 99101 (source of blank solution) - 10
Organic blanks: (NWQL)
Parameter 99100 (type of blank solution) - 40 Parameter 99102 (type of blank sample) - 30 (trip)
(PG water) or 50 (VG water)
Parameter 99109 (start date YMMDD) - Date trip
Parameter 99101 (source of blank solution) - 10 blanks received from NWQL (for example, 60522,
(NWQL) for May 22, 1996)
Parameter 99102 (type of blank sample) - 100 (field) Parameter 99110 (end date YMMDD) - Date trip
Parameter 99104 (blank lot number) - First five digits of blanks shipped to NWQL (for example, 60530, for
lot number May 30, 1996)

APPENDIXES 15
Spikes SAMPLE MEDIUM - R (QA sample - surface water)
SAMPLE TYPE - 1 (spike)
Primary Environmental Sample Associated
with the Spikes LOGIN COMMENTS - “SH____: spike lot number”
(for example - SH2001: LA38492)
ASR coding
QADATA coding
TIME - Time of collection rounded to nearest 10-minute
interval (HH:X0) (NOTE: The VOC samples must Parameter 71999 (sample purpose) - 15 (NAWQA)
have a time different from other samples.)
Parameter 99104 (spike lot number) - Enter first five
SAMPLE MEDIUM - 9 (surface water) numeric digits of lot number
SAMPLE TYPE - 9 (regular), or 7 (replicate) if replicate
Parameter 99105 (replicate type) - 30 (split) for
environmental samples are used to estimate back-
pesticides or 10 (concurrent) for VOC’s
ground concentrations
Parameter 99106 (spike type) - 10 (field)
QWDATA coding
Parameter 99107 (spike source) - 10 (NWQL)
Parameter 71999 (sample purpose) - 15 (NAWQA)
Parameter 99111 (QA data associated with sample) - Parameter 99108 (spike volume) - volume used,
40 (spike) or 100 (more than one type) if replicate in milliliters (100 µL = 0.1 mL)
environmental samples are used to estimate
background concentrations Field Matrix Spike Duplicate

Duplicate Environmental Sample Associated ASR coding

with the Spikes
STATION ID and DATE - Same as primary environmen-
ASR coding tal sample associated with the spikes
STATION ID and DATE - Same as primary environmen- TIME - Schedule 2001/2010: 3 minutes later than envi-
tal sample associated with the spikes ronmental sample (HH:X3)
TIME - 1 minute later than primary environmental sam- Schedule 2050/2051: 5 minutes later than envi-
ple (HH:X1) (NOTE: The VOC samples must have a ronmental sample (HH:X5)
time different from other samples.)
Schedule 2020: 7 minutes later than environ-
SAMPLE MEDIUM - R (QA sample - surface water) mental sample (HH:X7)
SAMPLE TYPE - 7 (replicate) Q SAMPLE MEDIUM - R (QA sample - surface water)
QWDATA coding SAMPLE TYPE - 1 (spike)
Parameter 71999 (sample purpose) - 15 (NAWQA) LOGIN COMMENTS - “SH____: spike lot number”
Parameter 99105 (replicate type) - 30 (split) for (for example - SH2001: LA38492)
pesticides or 10 (concurrent) for VOC’s
QADATA coding
Field Matrix Spike Parameter 71999 (sample purpose) - 15 (NAWQA)
ASR coding Parameter 99104 (spike lot number) - Enter first five
STATION ID and DATE - Same as primary environmen- numeric digits of lot number
tal sample associated with the spikes Parameter 99105 (replicate type) - 30 (split) for
TIME - Schedule 2001/2010: 2 minutes later than pesticides or 10 (concurrent) for VOC’s
environmental sample (HH:X2) Parameter 99106 (spike type) - 10 (field)
Schedule 2050/2051: 4 minutes later than
environmental sample (HH:X4) Parameter 99107 (spike source) - 10 (NWQL)
Schedule 2020: 6 minutes later than environ- Parameter 99108 (spike volume) - volume used,
mental sample (HH:X6) in milliliters (100 µL = 0.1 mL)

16 Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program
Replicates Duplicate Environmental Sample

Primary Environmental Sample ASR coding

ASR coding STATION ID and DATE - Same as primary environmen-

tal sample
TIME - Time of collection rounded to nearest 10-minute
interval (HH:X0) (NOTE: The VOC samples must TIME - 1 minute later than primary environmental
have a time different from other samples.) sample (HH:X1)
SAMPLE MEDIUM - 9 (surface water)
SAMPLE MEDIUM - R (QA sample - surface water)
SAMPLE TYPE - 7 (replicate)
SAMPLE TYPE - 7 (replicate)
QWDATA coding
Parameter 71999 (sample purpose) - 15 (NAWQA) QADATA coding
Parameter 99105 (replicate type) - 30 (split) for inor-
ganic constituents or pesticides or 10 (concurrent) Parameter 71999 (sample purpose) - 15 (NAWQA)
for DOC, SOC, or VOC’s. (If either inorganic con- Parameter 99105 (replicate type) - 30 (split) for inor-
stituents or pesticide replicates are prepared at ganic constituents or pesticides or 10 (concurrent)
the same time as DOC and SOC replicates, code for DOC, SOC, or VOC’s. (If either inorganic con-
this parameter 30.) stituents or pesticide replicates are prepared at
Parameter 99111 (QA data associated with sample) - 30 the same time as DOC and SOC replicates, code
(replicate sample) this parameter 30.)

APPENDIXES 17
Mueller and others—QUALITY-CONTROL DESIGN FOR SURFACE-WATER SAMPLING IN THE NATIONAL WATER-QUALITY ASSESSMENT PROGRAM USGS/OFR 97–223