USGS WATER RESOURCES
National Water-Quality Assessment (NAWQA) Program

Design of the National Water-Quality
Assessment Program:

Occurrence and Distribution of Water-Quality Conditions

United States Geological Survey Circular 1112
By Robert J. Gilliom, William M. Alley, and Martin E. Gurtz

Bed-Sediment and Tissue Studies

Bed-Sediment and Tissue Studies assess trace elements and hydrophobic organic contaminants in two phases. The Occurrence Survey is designed to provide an initial identification of important constituents in each Study Unit based on data from few sites. The Spatial Distribution Survey improves geographic coverage for priority constituents through broader areal sampling and improved resolution in priority areas. The design of the Spatial Distribution Survey is determined by results of the Occurrence Survey. Data from both phases are combined for assessing distribution.

Occurrence Survey

The primary objective of the Occurrence Survey is to determine which target constituents are important to water-quality conditions in each Study Unit. Importance is determined by the magnitude of constituent levels and the extent of their occurrence. The highest level of importance is assigned to constituents found at elevated levels over a wide geographic area or within many small areas, such that they are viewed as significant water-quality issues for a substantial part of the Study Unit. Site selection and sampling strategy are designed to maximize the probability of detecting important constituents in the Study Unit.

Site Selection

The site-selection strategy for the 15-20 sites sampled for the Occurrence Survey builds on the selection of Basic Fixed Sites (typically 7-13) for water-column sampling. The choice of additional Indicator Sites is a balance between locating sites where contamination is known to be probable and dispersing sites so that streams that drain each major Environmental Setting in the Study Unit are sampled. Integrator Sites are chosen to provide a coarse downstream network of sites where large-scale contaminant occurrences not detected at the Indicator Sites have a reasonable chance of being detected.

The sampling design in each Study Unit thus includes all Basic and Intensive Fixed Sites and additional sites selected specifically to meet objectives for bed sediments and tissues. Usually one or two Indicator Sites are selected to represent the broadest possible range of background trace-element levels expected in the Study Unit, if such sites are not already included as Intensive or Basic Fixed Sites. These reference Indicator Sites also serve to assess the background occurrence of hydrophobic organic contaminants.

Sampling Strategy

Sampling for bed sediment and tissues is done during summer or autumn low flows to minimize seasonal variability. The basic sampling strategy is the same at all sites. Each "site" refers to a reach of stream at that location. Sampling strategies for bed sediment and tissues ideally involve targeted sampling within a reach of stream near the location of water-column sampling or streamflow measurement. The general approach is to composite multiple samples in a manner that averages out anticipated spatial variability within the reach.

Bed Sediment

The strategy for sampling bed sediment is designed to exploit the sorptive properties of trace elements and hydrophobic organic chemicals by collecting fine-grained particles, which are natural accumulators of these chemicals, and to exploit the properties of stream environments by targeting low-flow depositional zones as natural integrators of fine-grained sediment. The general sampling strategy is to collect samples of fine-grained surficial sediments from natural depositional zones during low-flow conditions and to composite samples from several depositional zones in a stream reach, which yields a reach average of fine-grained surficial bed sediment.

The sampling procedures are described by Shelton and Capel (1994). The first step at a site is to identify the sampling reach. The standard sampling reach is the 100-m reach of stream upstream from the location for water-column sampling or streamflow measurement. However, the diverse nature of site locations, some of which are selected primarily for purposes other than bed-sediment sampling, make it necessary to go variable distances upstream or downstream from the water-column sampling or streamflow measurement location to find suitable depositional zones. Care is taken, however, to avoid including or excluding significant point sources or tributaries that may affect the suitability of the reach in representing the sub-basin. The sampling reach is colocated with the reach where tissue samples are collected and within the sampling reach for Ecological Studies.

The ideal sample-collection procedure within each sampling reach is to identify 5-10 wadeable depositional zones that contain fine-grained particulate matter. The depositional zones within the sampling reach are broad areas at some sites and small pockets at other sites. Left- and right-bank and center-channel depositional zones with different depths of water are sampled to ensure that sediment that represents a range of histories and sources important for the reach is sampled. Samples from the surficial 2-3 cm of bed sediment in each depositional zone are collected at several locations, in approximate proportion to its size, and composited with samples from other depositional zones sampled at the site. The composited bed-sediment sample is sieved and processed into several subsamples for analyses of trace elements, hydrophobic organic chemicals, total organic carbon, and particle size.

Tissue

The sampling strategy for tissues in the Occurrence Survey is comparable with bed sediment in that it also is designed to minimize local scale spatial variability and to maximize comparability of data within and among Study Units. Generally, one taxon is collected at each site in the Occurrence Survey; the same taxon is collected at as many sites as possible within a Study Unit. National consistency is provided by a National Target Taxa (NATT) List and decision trees that will guide, with local flexibility, selection from that list (Crawford and Luoma, 1993). The NATT List includes mollusks, insect larvae, fish, and vascular plants (table 8). Selection of target taxa for each Study Unit is based on information from the Retrospective Analysis and water-quality reconnaissance.

Table 8. National Target Taxa List for tissue bioassessment in National Water-Quality Assessment [Listed in order of priority within each group]
Group
Taxon
Mollusks Asiatic clam (Corbicula fluminea)
Insect larvae
Trichoptera (caddisflies):
Hydropsyche sp.
Brachycentrus sp.
Limnephilus sp.

Chironomidae (midges)
Chironomus sp.

Plecoptera (stoneflies)
Perlidae
Perlodidae
Pteronarcyidae
Fish Carp (Cyprinus carpio)
White sucker (Catostomus commersoni)
Longnose sucker (Catostomus catostomus)
Largescale sucker (Catostomus macrocheilus)
Channel catfish (Ictalurus punctatus)

Largemouth bass (Micropterus salmoides)
Bluegill (Lepomis macrochirus)
Brook trout (Salvelinus fontinalis)
Brown trout (Salmo trutta)

Vascular plants Pondweed (Potamogeton sp.)
Hydrilla (Hydrilla verticillata sp.)
Waterweed (Elodea sp.)

Decision trees for selecting target taxa are different for hydrophobic organic contaminants and trace elements because organisms concentrate these contaminants differently (Crawford and Luoma, 1993). For hydrophobic organic compounds, the first-priority taxon for collection is the bivalve mollusk, Corbicula fluminea (the Asiatic clam). If this taxon is not present at a site, then whole fish from a single species of fish on the NATT List would be the second-priority taxon to collect. Of the fish species on the NATT List, bottom-feeders (carp, suckers, channel catfish) are higher priority than predators (largemouth bass, bluegill, brook and brown trout). If adequate numbers of these species cannot be collected, then no sample is submitted for organics analysis, except where a nontarget taxon may be of local importance.

For trace elements, Corbicula fluminea is again the first-priority taxon for collection. If a sufficient sample cannot be collected at a site, then the second-priority target organisms are aquatic insects from the NATT List. Stoneflies are lower priority than the caddisflies on the list. If a sufficient sample of any one of these target taxa cannot be found, then the third- and fourth-priority target organisms from the NATT List are fish livers and vascular plants.

Sample-collection procedures vary for different taxa and are described in detail in Crawford and Luoma (1993). Samples for each taxon are composited for a given site to average individual variability and to meet a minimum mass requirement for the intended analyses.

Sample Analyses

The analytical strategy is uniform for all Occurrence Survey sites except that chlorinated dioxins and furans are analyzed only at selected sites (for example, near potential sources, such as pulp and paper mills, for which existing data are not available) and that polynuclear aromatic hydrocarbons (PAH's) are analyzed only in bed sediment. The analytical strategy for bed sediments and tissues is listed in table 9. The list for tissues is a subset of the list for bed sediments because compounds known to be metabolized by target taxa have been eliminated from the target analyte list for tissues.


Table 9. Analytical strategy for bed-sediment and tissue Occurrence Survey.

[Bed sediments analyzed for all constituents; tissues analyzed only for those indicated by *; some of the analytes may be deleted or qualified depending on method performance for ambient samples.]


Trace elements and major metals
Aluminum*
Antimony*
space(Stibum)
Arsenic*
Barium*
Beryllium*
Bismuth
Boron (tissue only)
Cadmium*
Calcium
Cerium
Chromium*
Cobalt*
Copper*
Europium
Gallium
Gold
Iron*
Holmium
Lanthanum
Lead*
Lithium
Magnesium
Manganese*
Mercury*
Molybdenum*
Neodymium
Nickel*
Niobium
Phosphorus
Potassium
Scandium
Selenium*
Silver*
Sodium
Strontium*
Sulfur
Tantalum
Thorium*
Tin
Titanium
Uranium*
Vanadium*
Yttrium
Ytterblum
Zinc*
Organic contaminants
Organochlorine insecticides and polychloringated biphenyls
Aldrin*
cis-chlordane*
trans-chlordane*
Chloroneb
Dacthal*
o,p'-DDD*
p,p'-DDD*
o,p'-DDE*
p,p'-DDE*
o,p'-DDT*
p,p'-DDT*
Dieldrin*
Endosulfan
Endrin*
Heptachlor*
Heptachlor epoxide*
alpha-HCH*
beta-HCH*
delta-HCH
space(in tissues only)
gamma-HCH
space(Lindane)*
Isodrin
Methoxychlor, o,p'*
Methoxychlor, p,p'*
Mirex*
cis-Nonachlor*
trans-Nonachlor
Oxychlordane*
Polychlorinated
space biphenyls
space(PCBs-total)*
cis-Permethrin
trans-Permethrin
Pentachloroanisole
Toxaphene*
Other semivolatile organic contaminants
Acenaphthene
Acenaphthylene
Acridine
C8-Alkylphenols
Anthracene
Anthraquinone
Azobenzene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(c)quinoline
2,2'-Biquinoline
4-Bromophenylphenylether
Butylbenzyl Phthalate
9H-Carbazole
bis(2-Chloroethoxy) methane
bis(2-Chloroethyl) ether
bis(2-Chloroisopropyl) ether
4-Chloro-3-methylphenol
2-Chlorophenol
2-Chloronaphthalene
4-Chlorophenylphenylether
p-Cresol
Chrysene
Dibenzo(a,h)anthracene
Dibenzothiophene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dichlorophenol
Diethyl Phthalate
3,5-Dimethylphenol
1,2-Dimethylnaphthalene
1,6-Dimethylnaphthalene
2,6-Dimethylnaphthalene
Dimethyl Phthalate
Di-n-butyl Phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl Phthalate
bis(2-Ethylhexyl) Phthalate
2-Ethylnaphthalene
Fluoranthene
9H-Fluorene
Hexachlorobenzene*
Hexachloroethane
Indeno(1,2,3-cd) pyrene
Isophorone
Isoquinoline
2-Methylanthracene
2-Methyl-4,6-Dinitrophenol
4,5-Methylenephenanthrene
1-Methyl-9H-Fluorene
1-Methylphenanthrene
1-Methylpyrene
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitroso-Diphenylamine
N-Nitroso-Di-n-Propyl Amine
Phenanthrene
Pyrene
Pentachloronitrobenzene
Pentachlorophenol
Phenanthridine
Phenol
Quinoline
2,3,5,6-Tetramethylphenol
1,2,4-Trichlorobenzene
2,4,6-Trichlorophenol
2,4,6-Trimethylphenol
2,3,6-Trimethylnaphthalene
Carbon
Carbonate Organic carbon Total carbon

Spatial Distribution Survey

The Spatial Distribution Survey adds improved geographic coverage with particular emphasis on the assessment of priority constituents identified in the Occurrence Survey. Occurrence-Survey results affect the analytical strategy and the geographic distribution of sampling sites. The combined data from the two phases of sampling provide a basic description of spatial distribution for each Study Unit, with emphasis on priority constituents, and support initial evaluation of sources and biological availability for priority constituents.

Site Selection

Typically, 20-30 sites are sampled and include selected sites also sampled during the Occurrence Survey. The general goals in site selection for the Spatial Distribution Survey are to attain improved representation of the most important Environmental Settings in the Study Unit by appropriate addition of Indicator Sites and to attain adequate spatial resolution in priority main-stem channels and major tributaries by addition of Integrator Sites. Large areas with low contaminant levels and low variance require few sites. Compared to the Occurrence Survey, some parts of a Study Unit may require a significant increase in site density to assess priority contaminants.

Sampling Strategy

The sampling strategy for bed sediment in the Spatial Distribution Survey is the same as that for the Occurrence Survey. For tissue studies, samples of more than one species (preferably a fish and an invertebrate species) are collected at as many as 50 percent of the Spatial Distribution Survey sites. This collection ensures that some fish data are obtained for comparison with data from other programs and maximizes the comparability of data among sites within a Study Unit (where a single taxon may not be present at all sites).

Sample Analyses

Sample analyses are the same as those for the Occurrence Survey (table 9) except that the scope is reduced on the basis of results of the Occurrence Survey. To the extent that analytical methods allow, costly analyses are limited to contaminants that are most significant in the Study Unit or for National Synthesis.


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