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USGS2023

Guide for benthic invertebrate studies in support of Natural Resource Damage Assessment and Restoration

This guide is intended to assist with characterizing injury to freshwater benthic macroinvertebrates (BMIs) in Natural Resource Damage Assessment and Restoration (NRDAR) cases. The contents are narrowly focused on insects, crustaceans, snails, and other invertebrate fauna that are typically considered part of BMI communities and are not intended to address studies of injury to larger benthic taxa such as freshwater mussels, crayfish, or benthic fishes or amphibians. Although some percentage of the community functions as predators, BMIs are predominantly primary consumers (for example, scrapers, shredders, and filterer/gatherer feeding groups) that play an essential role in converting carbon and nitrogen from plant tissues into animal biomass for higher-order consumers, especially in flowing waters. Aquatic contaminants can disrupt the quantity and quality of energy transferred (ecosystem function) by reducing invertebrate biomass and diversity. Additionally, the accumulation of toxic residues in invertebrate tissues may be a source of exposure leading to adverse effects in higher trophic levels. The goal of NRDAR BMI assessments is to establish direct linkages of contaminant exposure to injuries reflected by changes in community structure (for example, reduced density and taxa richness) or by effects at the individual population level (for example, survival, growth, and reproduction). BMIs are infrequently the U.S. Department of Interior (DOI)-managed resource in a NRDAR case, with managed resources more frequently including migratory birds, fish, or other insectivorous vertebrates. Therefore, it is critical to have clearly defined objectives for evaluating BMIs and an understanding of how invertebrate data relate to the quantification of injuries to the DOI-managed resource. This guide is intended to assist decisions on whether or not to proceed with BMI studies, use of existing information and data for screening purposes, and what types of studies can support a BMI-injury determination. This document is intended to provide general considerations and best practices for assessing BMIs. Relevant guidance and references are listed throughout the report as sources for specific methods and analysis.

Open-File Report↗
USGS1996

Instream investigations in the Beaver Creek Watershed in West Tennessee, 1991-95

The U.S. Geological Survey (USGS), in cooperation with the Tennessee Department of Agriculture, began a long-term scientific investigation in 1989 to evaluate the effect of agricultural activities on water quality and the effectiveness of agricultural best management practices in the Beaver Creek watershed, West Tennessee. In 1993 as a part of this study, the USGS, in cooperation with the Natural Resources Conservation Service, Shelby County Soil Conservation District, and the Tennessee Soybean Promotion Board, began an evaluation of the physical, chemical, biological and hydrological factors that affect water quality in streams and wetlands, and instream resource-management systems to treat agricultural nonpoint-source runoff and improve water quality. The purpose of this report is to present the results of three studies of stream and wetland investigations and a study on the transport of aldicarb from an agricultural field in the Beaver Creek watershed. A natural bottomland hardwood wetland and an artificially constructed wetland were evaluated as instream resource-management systems. These two studies showed that wetlands are an effective way to improve the quality of agricultural nonpoint-source runoff. The wetlands reduced concentrations and loads of suspended sediments, nutrients, and pesticides in the streams. A third paper documents the influence of riparian vegetation on the biological structure and water quality of a small stream draining an agricultural field. A comparison of the upper reach lined with herbaceous plants and the lower reach with mature woody vegetation showed a more stable biological community structure and Water- quality characteristics in the woody reach than in the herbaceous reach. The water-quality characteristics monitored were pH, temperature, dissolved oxygen, and specific conductance. The herbaceous reach had a greater diversity and abundance of organisms during spring and early summer, but the abundance dropped by approximately 85 percent during late summer. A fourth study describes the transport of aldicarb and its metabolites--aldicarb sulfoxide and aldicarb sulfone-in runoff at a small stream draining a cotton field. During 1991 to 1995, aldicarb and its metabolites were detected in runoff events. The highest concentrations occurred when aldicarb was applied to the field just hours before a rain storm. Aldicarb was not detectable in runoff a few weeks after application. The metabolites of aldicarb were detectable for 76 days after application. These studies demonstrate streambank vegetation and wetlands have a significant influence on stream water quality. The importance of weather conditions to herbicide application and runoff also is evident. This information can be used by resource managers to sustain and improve our Nation's streams for future generations.

Water-Resources Investigations Report↗
USGS2010

Groundwater transport of strontium 90 in a glacial outwash environment

As part of the investigation of groundwater contamination at a uranium-scrap recovery plant at Wood River Junction, Rhode Island, laboratory experiments led to the development of a model for predicting the transport of strontium 90 in glacial outwash sediments based on an approximate mechanism for ion exchange. The multicomponent system was simplified to two components by regarding all exchangeable cations other than strontium 90 as a single component. The binary ion-exchange parameter was a function of the variable, total ion concentration. A one-dimensional solute transport model was formulated to evaluate the time necessary for natural groundwater flow to remove the strontium 90 contamination plume from the groundwater system to the Pawcatuck River. The finite difference transport equations were solved sequentially for total ion concentrations, then strontium 90 concentrations. Clay-free quartz and feldspar sands at the study site have little potential for strontium 90 sorption, and high calcium, magnesium, and sodium concentrations compete for the few ion exchange sites. As the total ion concentration plume moves out of the system, ion exchange of strontium 90 increases, reducing the strontium 90 concentration in the groundwater. Cleanout times predicted using the binary ion exchange mechanism were about two thirds of those predicted using a constant distribution coefficient. It is suggested that this type of model can simulate solute transport more realistically in many groundwater systems where the total ion concentration is not constant.

Rhode Island↗
USGS2009

Organic geochemistry and sources of natural aquatic foams

Aquatic foams and stream-water samples were collected from two pristine sites for humic substances isolation and characterization. Biomarker compounds identified in foam and stream humic substances included phospholipid fatty acids, steroids, and lignin. Results showed that foams had a 10 to 20 fold greater DOC concentration and were enriched in humic substances (90% by weight of DOC) that showed increased hydrophobicity, aliphatic character, and compositional complexity compared to host stream humic substances (55 to 81% by weight of DOC). Foam humic substances also were enriched in humic acid (36 to 83% by weight) compared to host stream humic substances (10 to 14% by weight). Biomarkers, which contributed less than 5% by weight to the DOC pool, indicated higher plants, bacteria, algae, fungi, and diatoms as DOC sources. It is proposed that aquatic foams may be important media for the concentration and transport of organic substances in the aquatic environment.

ACS Symposium Series↗
USGS2007

Dietary and spatial overlap between sympatric ursids relative to salmon use

We hypothesized that there would be minimal dietary overlap between sympatric brown bears ( Ursus arctos ) and American black bears ( U. americanus ) relative to salmon ( Oncorhynchus spp.) utilization when alternative foods (e.g., fruits) are abundant. To maximize the chance that we would reject this hypothesis, we examined the diets of brown and black bears known to have visited salmon streams. Species, sex, and individual identification of bears visiting salmon streams were determined by DNA analysis of hair and feces collected in 2002-2004 along those streams. Diets were estimated from fecal residues and stable isotope analyses of hair. Assimilated diets of brown bears were 66.0% (SD = 16.7%) salmon , 13.9% (SD = 7.5%) terrestrial animal matter, and 20.1% (SD = 17.2%) plant matter. Assimilated diets of black bears were 8.0% (SD = 5.4%) salmon , 8.4% (SD = 9.7%) terrestrial animal matter, and 83.6% (SD = 7.7%) plant matter. Male and female brown bears did not differ in either the proportion of dietary salmon, terrestrial animal matter, or plant matter. The relative amounts of fruit residues in the feces of brown bears (87.0%, SD = 15.2%) and black bears (91.8%, SD = 7.2%) did not differ. Both sexes of brown bears visited salmon streams and consumed significant amounts of salmon, but only male American black bears visited streams and then consumed minimal amounts of salmon. Thus, brown bears were largely carnivorous and black bears were largely herbivorous and frugivorous. This reduced dietary overlap relative to salmon and fruit use is understandable in light of the concentrated, defendable nature of salmon in small streams, the widely dispersed, non-defendable nature of abundant fruits, the dominance of brown over black bears, the higher energy requirement of the larger brown bear, and, therefore, the differing ability of the species to efficiently exploit different food resources.

Ursus↗
USGS2003

Assessment of selected inorganic constituents in streams in the Central Arizona Basins study area, Arizona and northern Mexico, through 1998

Stream properties and water-chemistry constituent concentrations from data collected by the National Water-Quality Assessment and other U.S. Geological Survey water-quality programs were analyzed to (1) assess water quality, (2) determine natural and human factors affecting water quality, and (3) compute stream loads for the surface-water resources in the Central Arizona Basins study area. Stream temperature, pH, dissolved-oxygen concentration and percent saturation, and dissolved-solids, suspended-sediment, and nutrient concentration data collected at 41 stream-water quality monitoring stations through water year 1998 were used in this assessment. Water-quality standards applicable to the stream properties and water-chemistry constituent concentration data for the stations investigated in this study generally were met, although there were some exceedences. In a few samples from the White River, the Black River, and the Salt River below Stewart Mountain Dam, the pH in reaches designated as a domestic drinking water source was higher than the State of Arizona standard. More than half of the samples from the Salt River below Stewart Mountain Dam and almost all of the samples from the stations on the Central Arizona Project Canal—two of the three most important surface-water sources used for drinking water in the Central Arizona Basins study area—exceeded the U.S. Environmental Protection Agency drinking water Secondary Maximum Contaminant Level for dissolved solids. Two reach-specific standards for nutrients established by the State of Arizona were exceeded many times: (1) the annual mean concentration of total phosphorus was exceeded during several years at stations on the main stems of the Salt and Verde Rivers, and (2) the annual mean concentration of total nitrogen was exceeded during several years at the Salt River near Roosevelt and at the Salt River below Stewart Mountain Dam. Stream properties and water-chemistry constituent concentrations were related to streamflow, season, water management, stream permanence, and land and water use. Dissolved-oxygen percent saturation, pH, and nutrient concentrations were dependent on stream regulation, stream permanence, and upstream disposal of wastewater. Seasonality and correlation with streamflow were dependant on stream regulation, stream permanence, and upstream disposal of wastewater. Temporal trends in streamflow, stream properties, and water-chemistry constituent concentrations were common in streams in the Central Arizona Basins study area. Temporal trends in the streamflow of unregulated perennial reaches in the Central Highlands tended to be higher from 1900 through the 1930s, lower from the 1940s through the 1970s, and high again after the 1970s. This is similar to the pattern observed for the mean annual precipitation for the Southwestern United States and indicates long-term trends in flow of streams draining the Central Highlands were driven by long-term trends in climate. Streamflow increased over the period of record at stations on effluent-dependent reaches as a result of the increase in the urban population and associated wastewater returns to the Salt and Gila Rivers in the Phoenix metropolitan area and the Santa Cruz River in the Tucson metropolitan area. Concentrations of dissolved solids decreased in the Salt River below Stewart Mountain Dam and in the Verde River below Bartlett Dam. This decrease represents an improvement in the water quality and resulted from a concurrent increase in the amount of runoff entering the reservoirs. Stream loads of water-chemistry constituents were compared at different locations along the streams with one another, and stream loads were compared to upstream inputs of the constituent from natural and anthropogenic sources to determine the relative importance of different sources and to determine the fate of the water-chemistry constituent. Of the dissolved solids transported into the Basin and Range Lowlands each year from the Central Arizona Project Canal and from streams draining the Central Highlands, about 1.2 billion kilograms accumulated in the soil, unsaturated zone, and aquifers in agricultural and urban areas as a result of irrigating crops and urban vegetation. Stream loads of phosphorus decreased from the 91st Avenue Wastewater-Treatment Plant downstream to the Gila River at Gillespie Dam, probably as a result of adsorption of phosphorus to the streambed sediments. In this same reach, stream loads of nitrogen increased, most likely because of inputs from fertilizers. The annual mass of nitrogen and phosphorus input to developed basins from quantifiable sources was much larger than the mass input to basins that had little or no municipal or agricul-tural development. These computed inputs exclude the mass of nitrogen and phosphorus from sources such as geologic formations and soils that could not be quantified. The quantifiable annual inputs of nitrogen and phosphorus for the upper Salt River Basin and the upper Verde River Basin were similar to those for the West Clear Creek Basin. This similarity suggests that the small amount of municipal and agricultural development in the upper Salt River and the upper Verde River Basins did not greatly change the basin input flux. For basins with minimal urban and agricultural development, the largest quantifiable source of nitrogen was precipitation, and the largest source of phosphorus was human bodily waste treated by sewer and septic systems. This was in contrast to developed basins, for which fertilizer was the largest quantifiable source of both nutrients. For most basins examined, quantifiable inputs of nitrogen and phosphorus from nonpoint sources were greater than inputs from point sources. This relation emphasizes the importance of land- and water-management policies that protect surface-water resources from nonpoint sources of nutrients as well as from point sources. The amount of nitrogen and phosphorus transpor-ted out of basins was a small fraction of the total for the quantifiable inputs. This result indicated that most of the nutrients input to basins were not transported out of the basins in surface water, but rather were transported to the subsurface (the soil, unsaturated zone, or aquifer), released to the atmosphere (such as volatilized ammonia), or incorporated into the biomass.

Central Arizona Basins study area↗
USGS2014

Winter browse selection by white-tailed deer and implications for bottomland forest restoration in the Upper Mississippi River Valley, USA

White-tailed deer ( Odocoileus virginianus ) forage selectively, modifying upland forest species composition and in some cases shifting ecosystems to alternative stable states. Few studies, however, have investigated plant selection by deer in bottomland forests. Herbaceous invasive species are common in wetlands and their expansion could be promoted if deer avoid them and preferentially feed on native woody species. We surveyed plant species composition and winter deer browsing in 14 floodplain forest restoration sites along the Upper Mississippi River and tributaries. Tree seedling density declined rapidly with increasing cover of invasive Phalaris arundinacea , averaging less than 1 per m 2 in all sites in which the grass was present. Deer browsed ∼46% of available tree seedling stems (branches) at mainland restorations, compared to ∼3% at island sites. Across all tree species, the number of browsed stems increased linearly with the number available and responded unimodally to tree height. Maximum browsing rates were observed on trees with high stem abundances (>10 per plant) and of heights between 50 and 150 cm. Deer preferred Ulmus americana and Acer saccharinum , and avoided Fraxinus pennsylvanica , Acer negundo , and Quercus spp. at mainland sites, and did not browse Phalaris arundinacea if present. Depending on plant growth responses to herbivory and the competitive effects of unbrowsed species, our results suggest that selective foraging could promote the expansion of invasive species and/or alter tree species composition in bottomland forest restorations. Islands may, however, serve as refuges from browsing on a regional scale.

Upper Mississippi River↗
USGS2009

Natural offshore oil seepage and related tarball accumulation on the California coastline — Santa Barbara Channel and the southern Santa Maria Basin; source identification and inventory

Oil spillage from natural sources is very common in the waters of southern California. Active oil extraction and shipping is occurring concurrently within the region and it is of great interest to resource managers to be able to distinguish between natural seepage and anthropogenic oil spillage. The major goal of this study was to establish the geologic setting, sources, and ultimate dispersal of natural oil seeps in the offshore southern Santa Maria Basin and Santa Barbara Basins. Our surveys focused on likely areas of hydrocarbon seepage that are known to occur between Point Arguello and Ventura, California. Our approach was to 1) document the locations and geochemically fingerprint natural seep oils or tar; 2) geochemically fingerprint coastal tar residues and potential tar sources in this region, both onshore and offshore; 3) establish chemical correlations between offshore active seeps and coastal residues thus linking seep sources to oil residues; 4) measure the rate of natural seepage of individual seeps and attempt to assess regional natural oil and gas seepage rates; and 5) interpret the petroleum system history for the natural seeps. To document the location of sub-sea oil seeps, we first looked into previous studies within and near our survey area. We measured the concentration of methane gas in the water column in areas of reported seepage and found numerous gas plumes and measured high concentrations of methane in the water column. The result of this work showed that the seeps were widely distributed between Point Conception east to the vicinity of Coal Oil Point, and that they by in large occur within the 3-mile limit of California State waters. Subsequent cruises used sidescan and high resolution seismic to map the seafloor, from just south of Point Arguello, east to near Gaviota, California. The results of the methane survey guided the exploration of the area west of Point Conception east to Gaviota using a combination of seismic instruments. The seafloor was mapped by sidescan sonar, and numerous lines of high -resolution seismic surveys were conducted over areas of interest. Biomarker and stable carbon isotope ratios were used to infer the age, lithology, organic matter input, and depositional environment of the source rocks for 388 samples of produced crude oil, seep oil, and tarballs mainly from coastal California. These samples were used to construct a chemometric fingerprint (multivariate statistics) decision tree to classify 288 additional samples, including tarballs of unknown origin collected from Monterey and San Mateo County beaches after a storm in early 2007. A subset of 9 of 23 active offshore platform oils and one inactive platform oil representing a few oil reservoirs from the western Santa Barbara Channel were used in this analysis, and thus this model is not comprehensive and the findings are not conclusive. The platform oils included in this study are from west to east: Irene, Hildago, Harvest, Hermosa, Heritage, Harmony, Hondo, Holly, Platform A, and Hilda (now removed). The results identify three “tribes” of 13 C-rich oil samples inferred to originate from thermally mature equivalents of the clayey-siliceous, carbonaceous marl, and lower calcareous-siliceous members of the Monterey Formation. Tribe 1 contains four oil families having geochemical traits of clay-rich marine shale source rock deposited under suboxic conditions with substantial higher-plant input. Tribe 2 contains four oil families with intermediate traits, except for abundant 28,30-bisnorhopane, indicating suboxic to anoxic marine marl source rock with hemipelagic input. Tribe 3 contains five oil families with traits of distal marine carbonate source rock deposited under anoxic conditions with pelagic but little or no higher-plant input. Tribes 1 and 2 occur mainly south of Point Conception in paleogeographic settings where deep burial of the Monterey Formation source rock favored generation from all three members or their equivalents. In this area, oil from the clayey-siliceous and carbonaceous marl members (Tribes 1 and 2) may overwhelm that from the lower calcareous-siliceous member (Tribe 3) because the latter is thinner and less oil-prone than the overlying members. Tribe 3 occurs mainly north of Point Conception, where shallow burial caused preferential generation from the underlying lower calcareous-siliceous member or another unit with similar characteristics. It is very desirable to be able to clearly distinguish the naturally occurring seep oils from the anthropogenically derived platform oils. Within the “training set” of oils and tars (388 samples), the biomarker parameters are sometimes sufficient to allow unique discrimination of individual platform oils. More often however, platform samples and seep samples with sources geographically close to each other are too similar to each other, with respect to the biomarker parameters, to definitively differentiate them on that basis alone. In some cases other parameters can be helpful. These other parameters are related to the degree of biogeochemical degradation or weathering that the oils or tars have experienced. These components include the typical oil distribution of n-alkane hydrocarbons and isoprenoids pristane and phytane. All of the platform oils in our sample set contain these components. On the other hand, the seep oils or tars have been exposed to significant biodegradation while in the near subsurface. The majority, but not all of seep oils or tars have been biodegraded up to or beyond the loss of n-alkanes and isoprenoids. Seep oils found in the vicinity of Coal Oil Point or Arroyo Burro are apparently the least weathered and are particularly likely to retain significant n-alkanes and isoprenoids. Therefore the combination of chemometric fingerprinting and the presence or absence of n-alkanes and isoprenoids help to differentiate anthropogenic production oils versus natural seeps oils and tars. The differentiation is not always definitive because of the close chemical similarity of some samples and the variability in the biodegradation progression. This is the case near Coal Oil Point, and near Platform A (Dos Cuadros Field) where seep oils and Platform Holly and Platform A oils are genetically very similar and cannot be definitively distinguished after a period of a few days of weathering. In contrast, oils from the Point Conception platforms can be distinguished on the basis of chemometric fingerprinting alone. In the middle of this spectrum are oils from Platforms Harmony, Heritage, and Hondo, where it is expected that oil weathering would take on the order of two weeks to a month to produce tarballs similar to those seen near Point Conception. In this case there is a much greater degree of weathering needed to proceed from produced oil to the biodegraded tar characteristic of tarball stranded on the beach. Tar deposition on beaches was monitored as part of cooperative with the County of Santa Barbara Energy Division and the U.S. Geological Survey during 2001-2003. We found tar deposition varies on a seasonal basis. In general, tarballs accumulate at a faster rate or remain longer on all beaches during the summer and fall months. The reasons for this are unclear based on our limited observations, however we speculate that factors such as prevailing winds and currents combined with more quiescent wave conditions favors the accumulation and preservation of tarballs on the beach during the summer and fall months. In contrast, winter storms, with much greater wave action remove beach sand and other materials, and stormy seas tend to break up oil that might weather into tarballs. Natural seepage is affected by the spring/neap tidal cycle; however, the link to tar deposition is unclear. Longer periods of monitoring are needed to address the variability in the data and provide a more robust statistical analysis.

California↗
USGS2017

Are exposure predictions, used for the prioritization of pharmaceuticals in the environment, fit for purpose?

Prioritization methodologies are often used for identifying those pharmaceuticals that pose the greatest risk to the natural environment and to focus laboratory testing or environmental monitoring toward pharmaceuticals of greatest concern. Risk-based prioritization approaches, employing models to derive exposure concentrations, are commonly used, but the reliability of these models is unclear. The present study evaluated the accuracy of exposure models commonly used for pharmaceutical prioritization. Targeted monitoring was conducted for 95 pharmaceuticals in the Rivers Foss and Ouse in the City of York (UK). Predicted environmental concentration (PEC) ranges were estimated based on localized prescription, hydrological data, reported metabolism, and wastewater treatment plant (WWTP) removal rates, and were compared with measured environmental concentrations (MECs). For the River Foss, PECs, obtained using highest metabolism and lowest WWTP removal, were similar to MECs. In contrast, this trend was not observed for the River Ouse, possibly because of pharmaceutical inputs unaccounted for by our modeling. Pharmaceuticals were ranked by risk based on either MECs or PECs. With 2 exceptions (dextromethorphan and diphenhydramine), risk ranking based on both MECs and PECs produced similar results in the River Foss. Overall, these findings indicate that PECs may well be appropriate for prioritization of pharmaceuticals in the environment when robust and local data on the system of interest are available and reflective of most source inputs.

City of York↗
USGS2019

Mississippi river sediment diversions and coastal wetland sustainability: Synthesis of responses to freshwater, sediment, and nutrient inputs

Management and restoration of coastal wetlands require insight into how inundation, salinity, and the availability of mineral sediment and nutrients interact to influence ecosystem functions that control sustainability. The Mississippi River Delta, which ranks among the world's largest and most productive coastal wetland complexes, has experienced extensive deterioration over the last century due, in large part, to enhanced vulnerability to relative sea-level rise and lateral erosion caused by a combination of natural processes and anthropogenic modifications of hydrology. This land loss crisis has prompted the State of Louisiana to develop a comprehensive restoration plan that includes constructing and implementing a series of large-scale sediment diversions that will reconnect sediment- and nutrient-rich Mississippi River water to adjacent bays, estuaries, and wetlands. Sediment loading through diversions is predicted to enhance the long-term sustainability of coastal wetlands; however, the additive effects of increased inundation, abrubt changes in the salinity regime, and high nutrient loads on wetland plant growth and organic matter (SOM) decomposition rates, which help regulate accretion and elevation change, is uncertain. Therefore, this review attempts to synthesize existing information to inform predictions of the interactive effects of diversions on these drivers of coastal wetland sustainability. The data suggest that sediment deposition within an optimal elevation range will increase the overall productivity of existing wetlands where prolonged flooding does not counter this effect by limiting plant growth. A reduction in salinity may increase plant productivity and cause vegetation shifts to less salt tolerant species, but seasonal swings in salinity may have unforeseen consequences. Nutrient-loading is predicted to lead to greater aboveground productivity, which, in turn, can facilitate additional sediment trapping; however, belowground productivity may decline, particularly in areas where sediment deposition is limited. In areas experiencing net deposition, nutrient-enrichment is predicted to enhance belowground growth into new sediment and contribute to positive effects on soil organic matter accumulation, accretion, and elevation change. Thus, we contend that sediment input is essential for limiting the negative effects of flooding and nutrient-enrichment on wetland processes. These conclusions are generally supported by the biophysical feedbacks occurring in existing prograding deltas of the Mississippi River Delta complex.

Louisiana↗
USGS2008

Alkylphenols, other endocrine-active chemicals, and fish responses in three streams in Minnesota — Study design and data, February-September 2007

This report presents the study design and environmental data for an integrated chemical and biological study of three streams (South Fork Crow River, Redwood River, and Grindstone River) that receive wastewater in Minnesota. The objective of the study was to identify distribution patterns of endocrine-active chemicals and other organic chemicals indicative of wastewater, and to identify fish responses in the same streams. Endocrine-active chemicals are a class of chemicals that interfere with the natural regulation of endocrine systems, and an understanding of their distribution in aquatic systems is important so that aquatic organism exposure can be evaluated. This study was a cooperative effort of the U.S. Geological Survey (USGS), the Minnesota Pollution Control Agency, and St. Cloud State University (St. Cloud, Minn.). The USGS collected and analyzed water and quality-assurance samples and measured streamflow during six sampling events in each of three streams. Water samples were collected upstream from and at two successive points downstream from wastewater-treatment plant (WWTP) effluent discharge and from treated effluent from February through September 2007. Bed-sediment samples were collected during one sampling period at each of the stream locations. Water and bed-sediment samples were analyzed for endocrine-active chemicals including alkylphenols, alkylphenol polyethoxylates, and nonylphenol ethoxycarboxlylates (NPECs). Water samples also were analyzed for major ions, nutrients, and organic carbon. In addition, as part of an intensive time-series investigation, the USGS staff collected daily water samples for 8 weeks from the Redwood River near Marshall, Minn., for analyses of total alkylphenols and atrazine. St. Cloud State University staff collected and analyzed fish to determine male fish responses at all water sampling sites and at an additional site near the discharge of wastewater-treatment plant effluent to these streams. Male fish responses included the presence and concentration of vitellogenin in plasma, gonadosomatic indices, and histological characterizations of liver and testes tissue. Hydrologic, chemical and biological characteristics were different among sites. The percentage of streamflow contributed by WWTP effluent (ranging from less than 1 to 79 percent) was greatest at the South Fork Crow River and least at the Grindstone River. WWTP effluent generally contributed the greatest percentage of streamflow during winter and late summer when streamflows were low. A wide variety of chemicals were detected. More chemicals were detected in WWTP effluent samples than in stream samples during most time periods. The most commonly detected chemicals in samples collected monthly and analyzed at the USGS National Research Program Laboratory were 2,6-di- tert -butyl-1,4-benzoquinone, 2,6-di- tert -butyl-4-methylphenol, 3- beta -coprostanol, 4-methylphenol, 4-nonylphenol (NP), 4- tert -octylphenol, bisphenol A, cholesterol, ethylenediaminetetraacetic acid, and triclosan. The chemicals 4-nonylphenolmonoethoxycarboxylate (NP1EC), 4-nonylphenoldiethoxycarboxylate (NP2EC), and 4-nonylphenoltriethoxycarboxylate (NP3EC) also were detected. Excluding nondetections, the sum of NP1EC through NP3EC concentrations ranged from 5.1 to 260 µg/L among all samples. NP was detected in upstream, effluent, and downstream samples in each stream during at least one time period. NP was detected in 49 percent of environmental samples. Excluding nondetections, concentrations of NP ranged from 100 to 880 nanograms per liter among all samples. NP was also detected in more than one-half of the bed-sediment samples. The most commonly detected wastewater indicator chemicals in samples analyzed by schedule 4433 at the USGS National Water Quality Laboratory were 3,4-dichlorophenyl isocyanate, acetyl-hexamethyl-tetrahydronaphthalene, benzophenone, cholesterol, hexahydrohexamethyl-cyclopenta-benzopyran, N,N-diethyl- meta -toluamide, and tri(dichloroisopropyl) phosphate. Male fish responses were the focus of the fish analyses, and 508 male fish were collected among all sampling sites. Vitellogenin was detected in 57 percent of the 415 male fish analyzed; concentrations ranged from an estimated value of 0.1 to 330 micrograms per milliliter (µg/mL) (average of 17.1 µg/mL). Intersex (the presence of oocytes in testes tissue) was observed in only one fathead minnow from an upstream site on the Grindstone River.

Minnesota↗
USGS2008

Analytical Results for Municipal Biosolids Samples from a Monitoring Program near Deer Trail, Colorado (U.S.A.), 2007

Since late 1993, the Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado (U.S.A.). In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring ground water at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program recently has been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock ground water, and streambed sediment. Streams at the site are dry most of the year, so samples of streambed sediment deposited after rain were used to indicate surface-water effects. This report will present only analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed during 2007. We have presented earlier a compilation of analytical results for the biosolids samples collected and analyzed for 1999 through 2006. More information about the other monitoring components is presented elsewhere in the literature. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity. Nitrogen and chromium also were priority parameters for ground water and sediment components. In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Previous analytical results indicate that the elemental composition of the biosolids from the Denver plant was consistent during 1999-2006 and this consistency continues with the samples for 2007; total concentrations of regulated trace elements remained consistently lower than the regulatory limits for the entire monitoring period. Our previously reported data (1999-2006) and data presented in this report were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature include bismuth, copper, silver, mercury, phosphorus, and silver. An alternative method of digestion of biosolids was also recently investigated, and the results are presented in this report. A microwave digestion using only nitric acid at controlled elevated temperature and pressure was tested to replace the much more time-consuming and labor-intensive, traditional four-acid, hotplate method for the preparation of solutions to be analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). Elements of concern determined by ICP-MS following digestion include cadmium, copper, lead, molybdenum, nickel, and zinc. The microwave 'digestion' proved to be a strong acid leach, and it was less efficient at digesting the biosolids samples with consistently lower recoveries (compared to the four-acid digestion value) for most elements, but especially for the elements of concern - copper, nickel, and zinc. Other elements traditionally associated with the silicate or oxide minerals demonstrated low recoveries, especially titaniu

Open-File Report↗
USGS2010

Endocrine active chemicals and endocrine disruption in Minnesota streams and lakes: Implications for aquatic resources, 1994-2008

The U.S. Geological Survey, in cooperation with St. Cloud State University, Minnesota Department of Health, Minnesota Pollution Control Agency, Minnesota Department of Natural Resources, Metropolitan Council Environmental Services, and the University of Minnesota, has conducted field monitoring studies and laboratory research to determine the presence of endocrine active chemicals and the incidence of endocrine disruption in Minnesota streams and lakes during 1994–2008. Endocrine active chemicals are chemicals that interfere with the natural regulation of endocrine systems, and may mimic or block the function of natural hormones in fish or other organisms. This interference commonly is referred to as endocrine disruption. Indicators of endocrine disruption in fish include vitellogenin (female egg yolk protein normally expressed in female fish) in male fish, oocytes present in male fish testes, reduced reproductive success, and changes in reproductive behavior. The results from a series of studies during 1994–2008 demonstrate that endocrine active chemicals are present in Minnesota surface waters, indicating that aquatic organism exposure is likely. Endocrine active chemicals have been identified in wastewater-treatment plant effluent and surface waters downstream from discharge of wastewater-treatment plant effluent throughout Minnesota at low concentrations. Biological indicators of endocrine disruption have been detected in wild fish throughout Minnesota at sites directly downstream from wastewater-treatment plant effluent, indicating that endocrine active chemicals in effluent contribute to endocrine disruption in fish. This finding was confirmed in a controlled study exposing fathead minnows to wastewater-treatment plant effluent at an onsite fish exposure laboratory. During this controlled study, changes in biological responses coincided with changes in wastewater-treatment plant effluent composition demonstrating that effluent effects on fish endocrine systems are temporally variable. Although chemicals contributing to endocrine disruption in fish are complex, several laboratory studies have further confirmed that certain classes of chemicals, such as hormones and alkylphenols, which are components of wastewater-treatment plant effluent, affect the endocrine systems of fish through biochemical, structural, and behavioral disruption. Although these studies indicate that wastewater-treatment plant effluent is a conduit for endocrine active chemicals to surface waters, endocrine active chemicals also were present in surface waters with no obvious wastewater-treatment plant effluent sources. Endocrine active chemicals were detected and indicators of endocrine disruption in fish were measured at numerous sites upstream from discharge of wastewater-treatment plant effluent. These observations indicate that other unidentified sources of endocrine active chemicals exist, such as runoff from land surfaces, atmospheric deposition, inputs from onsite septic systems, or other groundwater sources. Alternatively, some endocrine active chemicals may not yet have been identified or measured. The presence of biological indicators of endocrine disruption in male fish indicates that the fish are exposed to endocrine active chemicals. However indicators of endocrine disruption in male fish does not indicate an effect on fish reproduction or changes in fish populations.

Minnesota↗
USGS2006

Comprehensive water quality of the Boulder Creek Watershed, Colorado, during high-flow and low-flow conditions, 2000

Executive Summary The Boulder Creek Watershed, Colorado, is 1160 square kilometers in area and ranges in elevation from 1480 to 4120 meters above sea level. Streamflow originates primarily as snowmelt near the Continental Divide, and thus discharge varies seasonally and annually (Chapter 1). Most of the water in Boulder Creek is diverted for domestic, agricultural, and industrial use. Some diverted water is returned to the creek as wastewater effluent and by ditch returns, and additional water enters as groundwater and by transbasin diversions. These diversions and returns lead to complex temporal and spatial variations in discharge. The variations in discharge, along with natural factors such as geology and climate, and anthropogenic factors such as wastewater treatment, agriculture, mining, and urbanization, can affect water chemistry. As with many watersheds in the American West, dependable water quality and sufficient water supply are issues facing local water managers and users. Detailed water-quality and sediment sampling allows the identification of sources and sinks of chemical constituents and an understanding of the processes at work in a river system. This study, the most comprehensive water-quality analysis performed for Boulder Creek to date, was a cooperative effort of the U.S. Geological Survey (USGS) and the city of Boulder. Geographic information systems and modeling programs were used to delineate watershed boundaries, land cover, and geology (Chapter 2). During high-flow (June 2000) and low-flow (October 2000) conditions, researchers evaluated 226 water-quality variables, including basic water-quality indicators (Chapter 3), major ions and trace elements (Chapter 4), wastewater-derived organic compounds (Chapter 5), and pesticides (Chapter 6). Discharge (Chapter 1) and bed-sediment particle size and mineralogy (Chapter 7) were also evaluated. This cooperative study was facilitated by the Boulder Area Sustainability Information Network (BASIN), which provides public access to environmental information about the Boulder Creek Watershed on a website, www.basin.org. In addition to the USGS and city of Boulder data, researchers at the Institute of Arctic and Alpine Research at the University of Colorado provided water chemistry data for the headwaters of North Boulder Creek, upstream of the reach of the USGS/city of Boulder sampling sites (Chapter 8). Snowmelt produces high flows in Boulder Creek in late spring to early summer (Chapter 1). Because precipitation falling in the headwaters is very dilute (specific conductance about 5 microsiemens per centimeter), most chemical constituents are present in lower concentrations during high flows (Chapters 3, 4, 5, 6, and 8). However, concentrations of some constituents, such as total suspended solids (Chapter 3) and organic carbon (Chapter 5), increase during the spring snowmelt flush. The upper basin, which consists of alpine, subalpine, montane, and foothills regions west of the mouth of Boulder Canyon, is underlain by Precambrian igneous and metamorphic rocks (Chapter 1). Major dissolved inorganic constituents in headwater sites were found to be enriched by factors of 10 to 20 relative to precipitation; this is consistent with minor weathering of the local crystalline bedrock (Chapter 4). Some anthropogenic input is observed in the headwaters; precipitation introduces nitrogen derived from fossil fuel combustion and agricultural activities (Chapter 8). The lower basin, which consists of the plains region east of the mouth of Boulder Canyon, is underlain by Mesozoic sedimentary rock and Quaternary alluvium, and has substantially more anthropogenic sources. Concentrations of most dissolved inorganic constituents increased in the lower basin. Differentiation between natural and anthropogenic sources of some dissolved constituents is difficult because both sources contribute to the water composition in this region. The increase of most major constituents (bicarbonate, calcium, chloride, magnesium, sodium, and sulfate) is consistent with weathering of the underlying sedimentary bedrock (Chapter 4). It is likely that anthropogenic loading of constituents in this reach occurs during storm events. Fecal coliform concentrations were variable and in some cases exceeded state standards, primarily during low-flow conditions (Chapter 3). Effluent from Boulder’s 75th Street Wastewater Treatment Plant (WWTP) has a substantial impact on the water chemistry of lower Boulder Creek. The WWTP increases the concentrations of nutrients such as nitrogen and phosphorus (Chapter 3), major ions and trace metals (Chapter 4), and organic carbon (Chapter 5) in Boulder Creek. The effluent contained a spike in gadolinium, a rare earth element that is ingested for magnetic resonance imaging as a contrasting agent and then excreted to the urban wastewater system. The effluent also contained trace organic compounds such as surfactants, pharmaceuticals, hormones (Chapter 5), and pesticides (Chapter 6), which also were detected at downstream Boulder Creek sites. Water chemistry of Boulder Creek downstream of the WWTP is largely controlled by the degree of dilution of the wastewater effluent, which varies depending on the baseflow of Boulder Creek, the volume of wastewater effluent, and depletion by agricultural diversions. Coal Creek, a tributary of Boulder Creek, contains wastewater effluent from four additional WWTPs, and increases the load of many constituents in Boulder Creek. In addition to the impact from wastewater effluent, lower Boulder Creek is affected by agricultural land use. Eleven of 84 analyzed pesticides were detected in Boulder Creek or its inflows, primarily in the eastern section of the watershed (Chapter 6). This collaborative study provides an in-depth evaluation of the hydrology, water chemistry, and sediment mineralogy of North Boulder Creek, Middle Boulder Creek, Boulder Creek, and major inflows. The detailed sampling and analysis in this report provide a baseline for future reference, as well as information on the effect of land use and geology on water chemistry.

Colorado↗
USGS1997

Effects of produced waters at oilfield production sites on the Osage Indian Reservation, northeastern Oklahoma

The authors conducted limited site surveys in the Wildhorse and Burbank oilfields on the Osage Indian Reservation, northeastern Oklahoma. The purpose was to document salt scarring, erosion, and soil and water salinization, to survey for radioactivity in oilfield equipment, and to determine if trace elements and naturally occurring radioactive materials (NORM) were present in soils affected by oilfield solid waste and produced waters. These surveys were also designed to see if field gamma spectrometry and field soil conductivity measurements were useful in screening for NORM contamination and soil salinity at these sites. Visits to oilfield production sites in the Wildhorse field in June of 1995 and 1996 confirmed the presence of substantial salt scarring, soil salinization, and slight to locally severe erosion. Levels of radioactivity on some oil field equipment, soils, and road surfaces exceed proposed state standards. Radium activities in soils affected by tank sludge and produced waters also locally exceed proposed state standards. Laboratory analyses of samples from two sites show moderate levels of copper, lead, and zinc in brine-affected soils and pipe scale. Several sites showed detectable levels of bromine and iodine, suggesting that these trace elements may be present in sufficient quantity to inhibit plant growth. Surface waters in streams at two sampled sites exceed total dissolved solid limits for drinking waters. At one site in the Wildhorse field, an EM survey showed that saline soils in the upper 6m extend from a surface salt scar downvalley about 150 m. (Photo [95k]: Dead oak trees and partly revegetated salt scar at Site OS95-2 in the Wildhorse field, Osage County, Oklahoma.) In the Burbank field, limited salt scarring and slight erosion occurs in soils at some sites and low to moderate levels of radioactivity were observed in oil field equipment at some sites. The levels of radioactivity and radium observed in some soils and equipment at these sites are above levels of concern as defined in regulations proposed by the Conference of Radiation Control Program Directors. The volumes of material involved appear to be relatively small for most sites. The lead levels observed in soils affected by tank sludge wastes are about one half of the US Environmental Protection Agency (USEPA) interim remedial action levels used for Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) and Resource Conservation and Recovery Act (RCRA) sites (400 ppm). Field gamma spectrometry proved useful in delineating areas where radium has been added to the natural soil by oilfield solid waste and produced water, although the technique does not meet standards of assessment used in the state of Louisiana which require core sampling of 15 cm intervals and radiochemical analysis in the laboratory. Further work is needed to develop field gamma spectrometry as a substitute for the more expensive coring and laboratory analysis. The ratio of radium-228 to radium-226 may hold promise in evaluating the relative ages of NORM contamination at a site.

Oklahoma↗
USGS2011

Isotopic tracing of perchlorate in the environment

Isotopic measurements can be used for tracing the sources and behavior of environmental contaminants. Perchlorate (ClO 4 − ) has been detected widely in groundwater, soils, fertilizers, plants, milk, and human urine since 1997, when improved analytical methods for analyzing ClO 4 − concentration became available for routine use. Perchlorate ingestion poses a risk to human health because of its interference with thyroidal hormone production. Consequently, methods for isotopic analysis of ClO 4 − have been developed and applied to assist evaluation of the origin and migration of this common contaminant. Isotopic data are now available for stable isotopes of oxygen and chlorine, as well as 36 Cl isotopic abundances, in ClO 4 − samples from a variety of natural and synthetic sources. These isotopic data provide a basis for distinguishing sources of ClO 4 − found in the environment, and for understanding the origin of natural ClO 4 − . In addition, the isotope effects of microbial ClO 4 − reduction have been measured in laboratory and field experiments, providing a tool for assessing ClO 4 − attenuation in the environment. Isotopic data have been used successfully in some areas for identifying major sources of ClO 4 − contamination in drinking water supplies. Questions about the origin and global biogeochemical cycle of natural ClO 4 − remain to be addressed; such work would benefit from the development of methods for preparation and isotopic analysis of ClO 4 − in samples with low concentrations and complex matrices.

Book chapter↗
USGS1979

Tolerance of developing salmonid eggs and fry to nitrate exposure

This paper reports on tests which show significant effects on early salmonid life stages of nitrates at levels commonly found in groundwaters in geographical areas that are influenced by fertilizer application. It has long been known, from fish cultural experience, that in certain site specific locations, chronic problems can be expected with salmonid egg development and early fry mortality. However, fingerlings which survive usually grow normally. A complete explanation is lacking although several environmental factors have been proposed to account for this phenomenon. One, which has so far received little attention, is that nitrate levels in the ground and surface waters of many areas have been increasing significantly over historical background levels. Ammonia, urea, and other potential sources of nitrate can enter natural waters from a variety of sources, such as domestic or industrial sewage, animal feedlots, or seepage and return flows from agricultural lands. The latter may be the largest contributor, since billions of tons of nitrate fertilizers are applied to agricultural crops on a worldwide basis each year. In addition, intensive forest management techniques include the aerial application of nitrate fertilizer to increase the yield of wood products, while range management practices call for use of nitrates to increase forage production. The nitrate that is not taken up by plants ultimately appears in ground or surface waters.

Bulletin of Environmental Contamination and Toxico↗
USGS2021

The influence of floral resources and microclimate on pollinator visitation in an agro-ecosystem

As agriculture expands to meet the needs of a growing global population, natural ecosystems are threatened by deforestation and habitat fragmentation. Tropical agroforestry systems offer a sustainable alternative to traditional agriculture by providing food for production while also supporting biodiversity and ecosystem services. Previous studies have shown that these systems may even improve crop pollination, but the mechanisms of how these improvements occur are still poorly understood. Using coffee as a focal crop, we explored how microclimatic conditions affected nectar traits (sugar and caffeine concentration) important for pollinator visitation. We also studied how microclimate, floral traits, floral availability at the coffee plant level, availability of floral resources provided by other plant species in the agroecosystem (neighborhood floral availability), and the presence of other bees affected the amount of time bees spent foraging on coffee flowers and the proportion of coffee pollen carried on their bodies. We explored these factors using the two dominant coffee species farmed on Puerto Rico, Coffea canephora and C. arabica , under sun and shade management. We found that high nectar sugar concentration and temperature were important predictors of short floral visits (<15 seconds), while increased number of bees and open coffee flowers were important predictors of longer floral visits (16-180 seconds). High nectar caffeine concentration was an important predictor of longer visits on C. arabica flowers while the opposite was observed for C. canephora flowers. For both species, high coffee floral availability was the main predicting factor for the proportion of coffee pollen on the bees bodies. Surprisingly, neither neighborhood floral availability nor the type of coffee plantation (agroforest/shade or sun) were important predictors of bee visitation. These results suggest non-coffee flowering plants in coffee plantations were neither competitors nor facilitators of coffee plantes for pollinators. Additionally, most of the bees surveyed were carrying 80% pollen from one species ( C. arabica or C. canephora ), likely resulting in little heterospecific pollen deposition between Coffea and non-Coffea flowers. Shade trees in coffee plantations do not detract from pollinator visitation to coffee flowers, suggesting that the provision of multiple ecological and wildlife conservation benefits by shade trees is not in conflict with a growers ability to maximize the benefits of insect pollination on fruit production.

Adjuntas Lares,Las Marias, Maricao, Puerto Rico Ut↗