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Coal-tar-based pavement sealcoat and PAHs: implications for the environment, human health, and stormwater management

Coal-tar-based sealcoat products, widely used in the central and eastern U.S. on parking lots, driveways, and even playgrounds, are typically 20−35% coal-tar pitch, a known human carcinogen that contains about 200 polycyclic aromatic hydrocarbon (PAH) compounds. Research continues to identify environmental compartments—including stormwater runoff, lake sediment, soil, house dust, and most recently, air—contaminated by PAHs from coal-tar-based sealcoat and to demonstrate potential risks to biological communities and human health. In many cases, the levels of contamination associated with sealed pavement are striking relative to levels near unsealed pavement: PAH concentrations in air over pavement with freshly applied coal-tar-based sealcoat, for example, were hundreds to thousands of times higher than those in air over unsealed pavement. Even a small amount of sealcoated pavement can be the dominant source of PAHs to sediment in stormwater-retention ponds; proper disposal of such PAH-contaminated sediment can be extremely costly. Several local governments, the District of Columbia, and the State of Washington have banned use of these products, and several national and regional hardware and home-improvement retailers have voluntarily ceased selling them.

Environmental Science & Technology

Concentrations of polycyclic aromatic hydrocarbons and inorganic constituents in ambient surface soils, Chicago, Illinois: 2001-2002

Samples of ambient surface soils were collected from 56 locations in Chicago, Illinois, using stratified random sampling techniques and analyzed for polycyclic aromatic hydrocarbon (PAH) compounds and inorganic constituents. PAHs appear to be derived primarily from combustion of fossil fuels and may be affected by proximity to industrial operations, but do not appear to be substantially affected by the organic carbon content of the soil, proximity to nonindustrial land uses, or proximity to a roadway. Atmospheric settling of particulate matter appears to be an important mechanism for the placement of PAH compounds into soils. Concentrations of most inorganic constituents are affected primarily by soil-forming processes. Concentrations of lead, arsenic, mercury, calcium, magnesium, phosphorus, copper, molybdenum, zinc, and selenium are elevated in ambient surface soils in Chicago in comparison to the surrounding area, indicating anthropogenic sources for these elements in Chicago soils. Concentrations of calcium and magnesium in Chicago soils appear to reflect the influence of the carbonate bedrock parent material on the chemical composition of the soil, although the effects of concrete and road fill cannot be discounted. Concentrations of inorganic constituents appear to be largely unaffected by the type of nearby land use. Copyright ?? Taylor & Francis Group, LLC.

Soil and Sediment Contamination

Exposure and effects of bioaccumulative contaminants of emerging concern in tree swallows nesting across the Laurentian Great Lakes

Contaminants of emerging concern (CECs) are a loosely defined group of chemicals whose wide-spread usage or presence in the environment has occurred more recently or for which there has been relatively little research done until recently. Many of these CECs are not currently regulated. The National Toxicology Program within the U.S. Department of Health and Human Services estimates that about 2000 CECs are introduced each year (https://ntp.niehs.nih.gov/about/). An unknown number may pose a risk to human or animal health. The Phase 1 (2010 – 2014) CEC work in birds, which is the subject of this report, assessed exposure across the Great Lakes to polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFASs), and polycyclic aromatic hydrocarbons (PAHs), and put those exposures into context with data from biologically relevant endpoints such as reproductive success, as well as, physiological response indicators (bioindicators) to assess possible effects. The group of chemicals included in Phase 1 were mainly those chemicals that bioaccumulate in tissues. Phase 2 (2015 – 2019) CEC work with tree swallows was expanded to include CECs whose occurrence in the environment is more temporary or seasonal, and that do not necessarily bioaccumulate. These are often called pseudo-persistent, because, while they are not long-lived in the environment, there are often daily inputs via waste water treatment plants, and run-off from farm fields and storm drainages, thereby making them available to biota year-round. These include pharmaceuticals, personal care products, and newer pesticides including herbicides. Tree swallow work on these less persistent CECs will be reported in the future, however see other Appendices in this report for information on some of these types of CECs (Appendices A, B, D).

Laurentian Great Lakes

Assessing biological effects from highway-runoff constituents

Increased emphasis on evaluation of nonpoint-source pollution has intensified the need for techniques that can be used to discern the toxicological effects of complex chemical mixtures. In response, the use of biological assessment techniques is receiving increased regulatory emphasis. When applied with documented habitat assessment and chemical analysis, these techniques can increase our understanding of the influence of environmental contaminants on the biological integrity and ecological function of aquatic communities. The contaminants of greatest potential concern in highway runoff are those that arise from highway construction, maintenance, and use. The major contaminants of interest are deicers; nutrients; metals; petroleum-related organic compounds, such as polycyclic aromatic hydrocarbons (PAHs), benzene, toluene, ethylbenzene, and xylene (BTEX), and methyl tert -butyl ether (MTBE); sediment washed off the road surface; and agricultural chemicals used in highway maintenance. Hundreds, if not thousands, of biological endpoints (measurable responses of living organisms) may be either directly or associatively affected by contaminant exposure. Measurable effects can occur throughout ecosystem processes across the wide range of biological complexity, ranging from responses at the biochemical level to the community level. The challenge to the environmental scientist is to develop an understanding of the relationship of effects at various levels of biological organization in order to determine whether a causal relationship exists between chemical exposure and substantial ecological impairment. This report provides a brief history of the evolution of biological assessment techniques, a description of the major classes of contaminants that are of particular interest in highway runoff, an overview of representative biological assessment techniques, and a discussion of data-quality considerations. Published reports with a focus on the effects of highway runoff on the local ecosystem were reviewed to provide information on (1) the suitability of the existing data for a quantitative national synthesis, (2) the methods available to study the effects of highway runoff on local ecosystems, and (3) the potential for adverse effects on the roadside environment and receiving waters. Although many biological studies have been done, the use of different methods and a general lack of sufficient documentation precludes a quantitative national synthesis on the basis of the existing data. The Federal Highway Administration, the U.S. Environmental Protection Agency, the U.S. Geological Survey, the Intergovernmental Task Force on Monitoring Water Quality, and the National Resources Conservation Service all have developed and documented methods for assessing the effects of contaminants on ecosystems in receiving waters. These published methods can be used to formulate a set of protocols to provide consistent information from highway-runoff studies. Review of the literature indicates (qualitatively) that highway runoff (even from highways with high traffic volume) may not usually be acutely toxic. Tissue analysis and community assessments, however, indicate effects from highway- runoff sediments near discharge points (even from sites near highways with relatively low traffic volumes). At many sites, elevated concentrations of highway-runoff constituents were measured in tissues of species associated with aquatic sediments. Community assessments also indicate decreases in the diversity and productivity of aquatic ecosystems at some sites receiving highway runoff. These results are not definitive, however, and depend on many site-specific criteria that were not sufficiently documented in most of the studies reviewed.

Open-File Report

Characterization of stormwater at selected South Carolina Department of Transportation maintenance yard and section shed facilities in Ballentine, Conway, and North Charleston, South Carolina, 2010-2012

The South Carolina Department of Transportation operates section shed and maintenance yard facilities throughout the State. The U.S. Geological Survey conducted a cooperative investigation with the South Carolina Department of Transportation to characterize water-quality constituents that are transported in stormwater from representative maintenance yard and section shed facilities in South Carolina. At a section shed in Ballentine, S.C., stormwater discharges to a retention pond outfall (Ballentine). At the Conway maintenance yard, stormwater in the southernmost section discharges to a pipe outfall (Conway1), and stormwater in the remaining area discharges to a grass-lined ditch (Conway2). At the North Charleston maintenance yard, stormwater discharges from the yard to Turkey Creek through a combination of pipes, ditches, and overland flow; therefore, samples were collected from the main channel of Turkey Creek at the upstream (North Charleston1) and downstream (North Charleston2) limits of the North Charleston maintenance yard facility. The storms sampled during this study had a wide range of rainfall amounts, durations, and intensities at each of the facilities and, therefore, were considered to be reasonably representative of the potential for contaminant transport. At all facilities, stormwater discharge was significantly correlated to rainfall amount and intensity. Event-mean unit-area stormwater discharge increased with increasing impervious surface at the Conway and North Charleston maintenance yards. The Ballentine facility with 79 percent impervious surface had a mean unit-area discharge similar to that of the North Charleston maintenance yard (62 percent impervious surface). That similarity may be attributed, in part, to the effects of the retention pond on the stormwater runoff at the Ballentine facility and to the greater rainfall intensities and amounts at the North Charleston facility. Stormwater samples from the facilities were analyzed for multiple constituents and characteristics. Concentrations of sediment and concentrations of nutrients and fecal indicator bacteria, which are commonly transported with the sediment in stormwater, were measured. Total and dissolved concentrations of six trace metals were determined in the samples. Stormwater samples also were analyzed for organic compounds including 10 herbicides, 18 organochlorine pesticides, 7 Aroclor or polychlorinated biphenyl congeners, 44 volatile organic compounds, and 16 polycyclic aromatic hydrocarbons. Stormwater often transports large quantities of sediment and sediment-bound contaminants, including nutrients and fecal indicator bacteria. Median event-mean concentrations of suspended sediment in stormwater at these facilities ranged from 54 milligrams per liter in Turkey Creek at North Charleston2 to 147 milligrams per liter in stormwater discharging from the Ballentine retention pond outfall. In general, event-mean concentrations of total nitrogen consisted mainly of total Kjeldahl nitrogen (organic nitrogen plus ammonia) rather than nitrate plus nitrite in stormwater, and the median event-mean concentrations of total nitrogen ranged from 1.59 milligrams per liter at the Conway1 pipe outfall to 2.00 milligrams per liter at the Ballentine retention pond outfall. Median event-mean concentrations of total phosphorus in stormwater ranged from 0.15 milligram per liter at the Conway1 outfall to 0.42 milligram per liter in Turkey Creek at North Charleston1. Escherichia coli and enterococcus concentrations often varied by 3 to 4 orders of magnitude in grab samples collected during the “first flush” of stormwater discharging to the sampled outfalls of Turkey Creek. Additionally, enterococcus concentrations consistently were greater than the corresponding Escherichia coli concentrations in stormwater. Specifically, median "first-flush" Escherichia coli concentrations ranged from 30 colonies per 100 milliliters at the Conway1 outfall to 4,359 colonies per 100 milliliters in Turkey Creek at North Charleston2, whereas enterococcus concentrations ranged from 512 colonies per 100 milliliters at the Conway1 outfall to 6,329 colonies per 100 milliliters in Turkey Creek at North Charleston2. In comparison to the proposed South Carolina Department of Health and Environmental Control primary and secondary body contact criterion of 349 colonies per 100 milliliter, stormwater had Escherichia coli concentrations that were greater than the criterion in 4 of the 9 storms at Ballentine retention pond outfall, 1 of the 8 storms at the Conway1 pipe outfall, 5 of the 7 storms at the Conway2 grass-lined ditch outfall, 2 of the 8 storms at North Charleston1 on Turkey Creek, and 8 of the 8 storms at North Charleston2 on Turkey Creek. Of the six trace metals measured in stormwater, only copper and zinc had event-mean concentrations greater than the hardness-dependent South Carolina Department of Health and Environmental Control aquatic life criteria maximum concentrations. Measured dissolved copper event-mean concentrations in stormwater were greater than the criterion in 5 of the samples at the Ballentine facility, 1 of the samples at Conway1, 2 of the samples at Conway2, and 1 of the samples at North Charleston2. Measured dissolved zinc event-mean concentrations in stormwater were greater than the criterion in 3 of the samples at the Ballentine facility, 1 of the samples at Conway1, 2 of the samples at Conway2, and 0 of the samples at North Charleston2. At North Charleston1 upstream from the North Charleston maintenance yard, the measured dissolved trace-metal concentrations were all less than the criterion maximum concentrations. Among the three facilities, Conway1 outfall had the greatest range in event-mean yields in stormwater for total phosphorus, total nitrogen, total suspended solids, and suspended sediment, and both Conway outfalls tended to have median event-mean yields greater than those of the Ballentine and North Charleston yard facilities. "First-flush” yields of Escherichia coli in stormwater were not statistically different among the three facilities. Median event-mean yields of suspended sediment, total nitrogen, total phosphorus, total copper, and total zinc in stormwater demonstrated a strong linear relation to impervious surface at the three facilities. However, median "first-flush" fecal indicator bacterial yields did not have a linear relation to impervious surface.

South Carolina

Sources of contamination in an urban basin in Marquette, Michigan and an analysis of concentrations, loads, and data quality

The concentrations of contaminants generated from discrete source areas are critical to urban nonpoint Source Load and Management Model (SLAMM) loading calculations to Lake Superior. This study summarizes data-collection efforts during 12 storms in October 1993 and from May through August 1994, in which stormwater data were collected concurrently at 33 sites representing the eight major source areas in a 117-hectare urban basin in Marquette, Mich. For the 12 storms, commercial rooftops produced the highest geometric mean concentrations of dissolved metals such as lead (20 mg/L), zinc (263 mg/L), cadmium (0.71 mg/L), and copper (17.8 mg/L). Parking lots produced the highest concentration for all of the individual polycyclic aromatic hydrocarbon (PAH) compounds (summation equal to 64 mg/L). Residential lawns generated the highest concentrations of total kjeldahl nitrogen (9.3 mg/L) and total phosphorus (2.3 mg/L). A mass-budget approach, in which summed source area loads are compared to those measured at the basin outlet for individual storms, provided the basis for an error analysis to identify unreliable concentration data. Of the 611 concentration samples used in the mass budgets, 59 were identified as unreliable. Seventy-six percent of the unreliable samples came from collection bottles that were filled prior to the end of runoff. These full bottles may have captured a first-flush effect or acted as a sediment trap. The relative importance of an individual source-area load to the overall basin-outlet load varied according to the individual constituent. Parking lots were a major contributor of total zinc (30 percent), total cadmium (25 percent), total copper (22 percent), and all the PAH compounds (=64 percent); whereas low-traffic streets were a major producer of total suspended solids (27 percent), nitrate plus nitrite (21 percent), and total cadmium (25 percent). Grass areas were a major producer of total kjeldahl nitrogen (31 percent) and total phosphorus (26 percent), even though the water volume generated from grass areas was low (5.8 percent of the total water volume generated).

Michigan

Detailed study of selenium and selected constituents in water, bottom sediment, soil, and biota associated with irrigation drainage in the San Juan River area, New Mexico, 1991-95

In response to increasing concern about the quality of irrigation drainage and its potential effects on fish, wildlife, and human health, the U.S. Department of the Interior began the National Irrigation Water Quality Program (NIWQP) to investigate these concerns at irrigation projects sponsored by the Department. The San Juan River area in northwestern New Mexico was one of the areas designated for study. Study teams composed of scientists from the U.S. Geological Survey, the U.S. Fish and Wildlife Service, the Bureau of Reclamation, and the Bureau of Indian Affairs collected water, bottom-sediment, soil, and biological samples at 61 sites in the San Juan River area during 1993-94. Supplemental data collection conducted during 1991-95 by the Bureau of Indian Affairs and its contractor extended the time period and sampling sites available for analysis. Analytical chemistry performed on samples indicated that most potentially toxic elements other than selenium generally were not high enough to be of concern to fish, wildlife, and human health. Element concentrations in some water, bottom-sediment, soil, and biological samples exceeded applicable standards and criteria suggested by researchers in current literature. Selenium concentrations in water samples from 28 sites in the study area exceeded the 2-microgramper-liter (lg/L) wildlife-habitat standard. Vanadium concentrations in water exceeded the 100-Kg/L standard for livestock-drinking water at one site. In biota, selenium and aluminum concentrations regularly equaled or exceeded avian dietary threshold concentrations. In bottom sediment and soil, element concentrations above the upper limit of the baseline range for western soils were: selenium, 24 exceedances; lead, 2 exceedances; molybdenum, 2 exceedances;strontium, 4 exceedances; and zinc, 4 exceedances. Concentrations of total selenium in bottom-sediment and soil samples were significantly greater for Cretaceous than for non-Cretaceous soil types in the study area and were generally similar for habitats within and outside irrigation-affected areas. Mean and median total-selenium concentrations in samples from areas with Cretaceous soil types were 4.6 and 2.2 micrograms per gram (ps/g), respectively. Mean and median total-selenium concentrations in samples from areas with non-Cretaceous soil types were 0.6 and 0.15 pg/g, respectively. Samples from the study area had low concentrations of organic constituents. Organochlorine pesticides and polychlorinated biphenyls were detected in a few biological samples at low concentrations. Polycyclic aromatic hydrocarbon (PAH) compounds were not detected in whole-water samples collected using conventional water-sampling techniques. In tests involving the use of semipermeable-membrane devices to supplement conventional water assays for PAH's, low concentrations of PAH's were found at several locations in the Hammond Irrigation Supply Canal, but were not detected in the Hammond ponds at the downstream reach of the Hammond irrigation service area. PAH compounds do not appear to reach the San Juan River through the Hammond Canal. Data indicate that water samples from irrigation-drainage-affected habitats had increased mean selenium concentrations compared with samples from irrigation-delivery habitat. The mean selenium concentration in water was greatest at seeps and tributaries draining irrigated land (17 μg/L); less in irrigation drains and in ponds on irrigated land (61.tg/L); and least in backwater, the San Juan River, and irrigation-supply water (0.5 - 0.6 μg/L). Statistical tests imply that irrigation significantly increases selenium concentrations in water samples when a Department of the Interior irrigation project is developed on selenium-rich sediments. Water samples from sites with Cretaceous soils had significantly greater selenium concentrations than water samples from sites with non-Cretaceous soils. Water samples from Department of the Interior project irrigation-drainage sites developed on Cretaceous soils contained a mean selenium concentration about 10 times greater than those in samples from Department of the Interior project sites developed on non-Cretaceous soils. Selenium was much less concentrated in water than in bottom sediment, soil, or biota in the study area. The range in concentrations of dissolved selenium in water was less than 1 ptg/L to 37 1.1g/L (less than 1 to 37 parts per billion). The range in concentrations of total selenium in bottom sediment and soil was less than 0.1 to 23lig/g (less than 100 to 23,000 parts per billion). The range in concentration of selenium in biota was less than 0.1 to 24.0 fig/g (less than 100 to 24,000 parts per billion). Data indicated that bioaccumulation and leaching from soil were the important processes at the study area that lead to elevated levels of selenium. Other processes examined included: (1) evapoconcentration of selenium; (2) atmospheric deposition of aerosols containing selenium; and (3) contamination of surface water by point-source or non-point-source discharges. Selenium concentrations in biological samples were evaluated by a number of variables including: (1) media sampled (emergent and submergent plants, nektonic and benthic invertebrates, omnivore/herbivore and carnivore fish, and terrestrial and aquatic amphibians); (2) habitat (San Juan River main-stem reaches, backwaters, tributary reaches, irrigation delivery or drainage canals, and ponds); (3) irrigation project area and reference sites; and (4) soil type (non-Cretaceous or Cretaceous soils). Graphical techniques and nonparametric statistical tests were applied to determine the influence of selected physiographic variables on selenium concentrations in biological samples collected in the San Juan River area. Species of sucker and of smaller fish contained significantly higher selenium concentrations in the upstream portion of the river where a productive community of plants and animals is found that is associated with warming, nutrient-rich waters discharged from an upstream reservoir. Selenium concentrations in algae, odonates, and mosquitofish collected from both irrigation-drain and pond habitats underlain by Cretaceous soils were significantly greater than in those collected from similar habitats underlain by non-Cretaceous soils. Investigators conclude that the major factor affecting the variability of selenium accumulation in biota at aquatic habitats was the presence of underlying Cretaceous soils. Median selenium concentrations were less than 2 lAg/g for plant samples, less than 7 μg/g for invertebrate samples, and less than 6 lAg/g for whole-fish samples collected from aquatic habitats underlain by non-Cretaceous soils. Similar samples collected from aquatic habitats underlain by Cretaceous soils contained median selenium concentrations two to five times greater. Leaching of selenium from Cretaceous soils in the San Juan River area increases the accumulation of selenium concentrations in the biota and thereby increases the exposure and potential health risks associated with selenium to migratory birds, fish, and other wildlife that use these aquatic habitats extensively. Aquatic habitats presenting the greatest average exposure to excess selenium concentrations in the diets of resident wildlife are from consumption of plants, invertebrates, and fish at irrigation-drain habitats underlain by Cretaceous soils. Of the irrigation projects evaluated in the San Juan River area, the highest median selenium concentrations in algae, cattail leaves, odonate nymphs, mosquitofish, and leopard frog samples from the study area were collected from the east hogback irrigation drain.

New Mexico

Use of chemical analysis and assays of semipermeable membrane devices extracts to assess the response of bioavailable organic pollutants in streams to urbanization in six metropolitan areas of the United States

Studies to assess the effects of urbanization on stream ecosystems are being conducted as part of the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program. The overall objectives of these studies are to (1) determine how hydrologic, geomorphic, water quality, habitat, and biological characteristics respond to land-use changes associated with urbanization in specific environmental settings, and (2) compare these responses across environmental settings. As part of an integrated assessment, semipermeable membrane devices (SPMDs) were deployed in streams along a gradient of urban land-use intensity in and around Atlanta, Georgia; Raleigh-Durham, North Carolina; and Denver-Fort Collins, Colorado, in 2003; and Dallas-Fort Worth, Texas; Milwaukee-Green Bay, Wisconsin; and Portland, Oregon, in 2004. Sites were selected to avoid point-source discharge and to minimize natural variability within each of the six metropolitan areas. In addition to standard chemical analysis for hydrophobic organic contaminants, three assays were used to address mixtures and potential toxicity: (1) Fluoroscan provides an estimate of the total concentration of polycyclic aromatic hydrocarbons (PAHs); (2) the P450RGS assay indicates the presence and levels of aryl hydrocarbon receptor agonists; and (3) Microtox® measures toxicological effects on photo-luminescent bacteria. Of the 140 compounds targeted or identified by gas chromatography/mass spectrometry analysis in this study, 67 were not detected. In terms of numbers and types of compounds, the following were detected: 2 wood preservatives, 6 insecticides (parent compounds), 5 herbicides, 22 polycyclic aromatic hydrocarbons, 2 dibenzofurans, 4 polychlorinated biphenyls, 7 compounds associated with fragrances or personal care products, 4 steroids associated with wastewater, 5 polydibromated diphenyl ethers (flame retardants), 3 plasticizers, 3 antimicrobials/disinfectants, and 3 detergent metabolites. Of the 73 compounds detected and three assays utilized, 29 were detected in 25 percent or more of the streams and were strongly related to increases in urban intensity (defined as having a Spearman’s rho > 0.5 with percent urban land cover) in at least one of the six metropolitan areas investigated. These 29 endpoints included 16 PAHs, a wood preservative (pentachloroanisole), 2 insecticides (chlorpyrifos and chlordane), 3 herbicides (benfluralin, trifluralin, and dacthal), a synthetic musk (hexahydrohexamethylcyclopentabenzopyran, HHCB), 2 furans (methyldibenzofuran and benzo[b]naphtho[2,3-d]furan), and a flame retardant (BDE 47). In addition, the number of compounds detected and results of the Fluoroscan and P450RGS assays were strongly related to urban intensity. Average water concentrations estimated from SPMDs were compared to screening benchmarks for the protection of human health and aquatic life; of the 14 compounds with available benchmarks, 3 compounds (anthracene, dieldrin, and diazinon) exceeded those levels in one or more streams. Both dieldrin and anthracene exceeded their respective benchmarks in seven streams, and diazinon in only one stream. There were more exceedances in Milwaukee-Green Bay and Raleigh-Durham than in the other metropolitan areas, and there were no exceedances in Dallas-Fort Worth. The six metropolitan areas studied differed in the number and types of endpoints related to urban intensity, probably from a combination of factors governing source strength, transport, and fate of hydrophobic compounds. The number of endpoints strongly related to urban intensity ranged from 3 in Dallas-Fort Worth and Portland to 21 in Raleigh-Durham. High frequencies of detection and strong correlations with urban land cover for pyrogenic PAHs (such as unsubstituted 4-ringed PAHs) in all six metropolitan areas indicate that these compounds are an important component of urbanization, regardless of location. Pentachloroanisole, dibenzofurans, and petrogenic PAHs (alkylated PAHs and heterocyclic dibenzothiophenes) were frequently detected and strongly related to urban intensity in Atlanta, Raleigh-Durham, Milwaukee-Green Bay, and Denver-Fort Collins. Two insecticides were related to urban intensity: chlorpyrifos in Atlanta, Raleigh-Durham, and Dallas-Fort Worth; and chlordane in Raleigh-Durham. Three herbicides were strongly related to urban intensity: trifluralin in Atlanta and Raleigh-Durham; benfluralin in Atlanta, and dacthal in Denver-Fort Collins. The detection frequencies for most wastewater indicator compounds were too low to establish relations with urban intensity. Of the wastewater compounds analyzed, HHCB in Raleigh-Durham and Denver-Fort Collins, and BDE 47 in Denver-Fort Collins and Dallas-Forth Worth, had the strongest relations with urban intensity. In addition to pyrogenic PAHs, levels of aryl hydrocarbon receptor agonists (as measured by the P450RGS assay) were strongly related to increasing urban intensity in all six metropolitan areas. PAHs were the only group of aryl hydrocarbon agonists consistently detected and related with urban intensity in all six metropolitan areas. It is unknown which compounds in the SPMDs caused the increased response in the P450RGS assay because the SPMDs likely contained many aryl hydrocarbon receptor agonists not quantified by chemical analysis. It is clear that bioavailable, aryl hydrocarbon receptor agonists increase in streams with increasing urban intensity in the basin. Potential toxicity mediated by this metabolic pathway should be considered in integrated assessments of the response of aquatic biota to urbanization.

Scientific Investigations Report

Water- and air-quality and surficial bed-sediment monitoring of the Sweetwater Reservoir watershed, San Diego County, California, 2003-09

In 1998, the U.S. Geological Survey, in cooperation with the Sweetwater Authority, began a study to assess the overall health of the Sweetwater watershed in San Diego County, California. This study was designed to provide a data set that could be used to evaluate potential effects from the construction and operation of State Route 125 within the broader context of the water quality and air quality in the watershed. The study included regular sampling of water, air, and surficial bed sediment at Sweetwater Reservoir (SWR) for chemical constituents, including volatile organic compounds (VOCs), base-neutral and acid- extractable organic compounds (BNAs) that include polycyclic aromatic hydrocarbons (PAHs), pesticides, and metals. Additionally, water samples were collected for anthropogenic organic indicator compounds in and around SWR. Background water samples were collected at Loveland Reservoir for VOCs, BNAs, pesticides, and metals. Surficial bed-sediment samples were collected for PAHs, organochlorine pesticides, and metals at Sweetwater and Loveland Reservoirs. To monitor changes in contaminant concentration in water and air at SWR during the construction and operation of State Route 125, this study was divided into three phases. Phase One sampling (September 1998 to September 2004) was designed to establish baseline conditions for target compounds in terms of detection frequency and concentration in air and water. Phase Two (October 2004 to September 2007) continued sampling at selected monitoring sites during construction of State Route 125 to assess any effect from the construction process and the use of heavy equipment to build the roadway. Phase Three (October 2007 to August 2009) continued sampling for 2 years after the opening of State Route 125 to assess the potential changes in water quality related to vehicle emissions from the roadway alignment. Surficial bed-sediment samples were collected three times during the study—at the beginning of the study, at the start of Phase Two, and at the end of the study. This report describes the study design and the sampling and analytical methods and presents data from water, air, and surficial bed-sediment samples collected from the sixth to eleventh years of the study (October 2003–August 2009), spanning the last year of Phase one and all of Phases Two and Three. Data collected during the first 5 years of sampling have been previously published. Three types of quality-control samples were used in this study—matrix spikes, blanks, and replicates. Matrix-spike data are considered to be adequate if the recovery concentration is within 30 percent of the matrix concentration. Replicate data are considered to be adequate if the replicate sample concentration is within 30 percent of the environmental sample concentration. Additionally, surrogate compounds were added to most samples to monitor sample-specific performance of the analytical method. Most VOC matrix-spike recovery data associated with water samples are within acceptable criteria, but three VOCs had recoveries below the acceptable criteria; these compounds may not have been detected in water samples if they were present at low concentrations. Data for blanks associated with water samples for VOCs and metals showed no detections above their laboratory reporting levels. Most replicate data are within acceptable criteria. Quality-control data for VOC air samples resulted in flagging several reported concentrations for acetone, benzene, ethenylbenzene, and naphthalene because they may be biased high. Acetone, benzene, and toluene were detected at low concentrations in almost every VOC air blank. Some PAH and pesticide concentrations in air samples were designated as estimated because of method performance limitations. PAHs in surficial bed sediment had 83 percent of surrogates below the acceptable criteria. No matrix-spike data for metals in surficial bed sediment were outside the acceptable criteria; only beryllium had a replicate comparison outside the acceptable criteria. Sampling results show concentrations of the gasoline oxygenate methyl tert -butyl ether in water and air samples declined after it was phased out by the State of California in January 2004. The largest concentrations of gasoline hydrocarbons benzene and toluene in water were detected at or near the surface of the SWR. Isophorone and phenol were the two most frequently detected BNA compounds in water. Diuron, prometon, and simazine were the most frequently detected pesticide compounds in water. Concentrations of benzene and toluene in air samples were highest during the cooler months and had a consistent seasonal pattern over time. Ten PAH compounds were detected frequently in air samples. Twelve pesticide compounds were also detected in air samples. Surficial bed-sediment samples were analyzed for 53 PAHs; 22 of the compounds had one or more detections. Surficial bed-sediment samples were analyzed for 22 organic compounds; only 6 compounds had one or more detections. Surficial bed-sediment samples were analyzed for 37 metals.

California

Organic compounds in produced waters from the Bakken Formation and Three Forks Formation in the Williston Basin, North Dakota

The organic composition of produced waters (flowback and formation waters) from the middle member of the Bakken Formation and the Three Forks Formation in the Williston Basin, North Dakota were examined to aid in the remediation of surface contamination and help develop treatment methods for produced-water recycling. Twelve produced water samples were collected from the Bakken and Three Forks Formations and analyzed for non-purgeable dissolved organic carbon (NPDOC), acetate, and extractable hydrocarbons. NPDOC and acetate concentrations from sampled wells from ranged from 33-190 milligrams per liter (mg/L) and 16-40 mg/L, respectively. Concentrations of individual extractable hydrocarbon compounds ranged from less than 1 to greater than 400 micrograms per liter (µg/L), and included polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, glycol ethers, and cyclic ketones. While the limited number of samples, varying well production age, and lack of knowledge of on-going well treatments complicate conclusions, this report aids adds to the limited knowledge of organics in produced waters from the Bakken and Three Forks Formations.

North Dakota

Manmade organic compounds in the surface waters of the United States: a review of current understanding

This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves between water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be absorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rate commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence that the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison to concentrations determined during ongoing research. Finally, where sufficient data exist, regional and temporal contamination trends in the United States are discussed.

Open-File Report

Evaluation of persistent hydrophobic organic compounds in the Columbia River Basin using semipermeable-membrane devices

Persistent hydrophobic organic compounds are of concern in the Columbia River because they have been correlated with adverse effects on wildlife. We analysed samples from nine main-stem and six tributary sites throughout the Columbia River Basin (Washington and Oregon) for polychlorinated dibenzo-p-dioxins, dibenzofurans, polychlorinated biphenyls, organochlorine pesticides, and priority-pollutant polycyclic aromatic hydrocarbons. Because these compounds may have important biological consequences at aqueous concentrations well below the detection limits associated with conventional sampling methods, we used semipermeable-membrane devices to sample water and achieved parts-per-quintillion detection limits. All of these compound classes were prevalent within the basin, but concentrations of many analytes were highest in the vicinity of Portland-Vancouver, indicating that the Willamette subbasin-and perhaps the urban area in particular-is an important source of these compounds. Data collected during basin low-flow conditions in 1997 and again during basin high-flow conditions in 1998 indicate that in-stream processes such as dilution by relatively clean inflow, and flow through island hyporheic zones may be important mechanisms for attenuating dissolved concentrations of hydrophobic compounds.

Hydrological Processes

Water quality, sediment quality, and stream-channel classification of Rock Creek, Washington, D.C., 1999-2000

Rock Creek Park is within the National Capital Region in Washington, D.C., and is maintained by the National Park Service. Part of Montgomery County, Maryland, and part of the District of Columbia drain into Rock Creek, which is a tributary of the Potomac River. Water quality in Rock Creek is important to biotic life in and near the creek, and in the Potomac River Basin and the Chesapeake Bay. The water quality of the Rock Creek Basin has been affected by continued urban and agricultural growth and development. The U.S. Geological Survey, in cooperation with the National Park Service, investigated water quality and sediment quality in Rock Creek over a 2-year period (1998?2000), and performed a stream-channel classification to determine the distribution of bottom sediment in Rock Creek. This report presents and evaluates water quality and bottom sediment in Rock Creek for water years 1999 (October 1, 1998 to September 30, 1999) and 2000 (October 1, 1999 to September 30, 2000). A synoptic surface-water assessment was conducted at five stations from June 23 to June 25, 1999, a temporal surface-water assessment was conducted at one station from February 18, 1999 to September 26, 2000, and bed-sediment samples were collected and assessed from three stations from August 17 to August 19, 1999. The synoptic surface-water assessment included pesticides (parent compounds and selected transformation products), field parameters, nutrients, and major ions. The temporal surface-water assessment included pesticides (parent compounds and selected transformation products) and field parameters. The bed-sediment assessment included trace elements and organic compounds (including low- and high-molecular weight polycyclic aromatic hydrocarbons, poly-chlorinated biphenyls, pesticides, and phthalates). Some, but not all, of the pesticides known to be used in the area were included in the synoptic water-quality assessment, the temporal water-quality assessment, and the bed-sediment assessment. In addition to the water-quality and sediment-quality assessments, a Rosgen stream-channel classification was performed on a 900-foot-long segment of Rock Creek. In the synoptic water-quality assessment, two pesticides were found to be above published criteria for the protection of aquatic life. In the temporal water-quality assessment, four pesticides were found to be above published criteria for the protection of aquatic life. In the bed-sediment assessment, 8 trace elements, 14 polycyclic aromatic hydrocarbons, 6 pesticides, and 1 phthalate compound were found to be above published criteria for the protection of aquatic life. In the Rosgen classification, a comparison to a previous classification for this segment showed an increase in sands and other fine-grained sediments in the creek bed.

Water-Resources Investigations Report

Occurrence and Distribution of Organic Wastewater Compounds in Rock Creek Park, Washington, D.C., 2007-08

The U.S. Geological Survey, and the National Park Service Police Aviation Group, conducted a high-resolution, low-altitude aerial thermal infrared survey of the Washington, D.C. section of Rock Creek Basin within the Park boundaries to identify specific locations where warm water was discharging from seeps or pipes to the creek. Twenty-three stream sites in Rock Creek Park were selected based on the thermal infrared images. Sites were sampled during the summers of 2007 and 2008 for the analysis of organic wastewater compounds to verify potential sources of sewage and other anthropogenic wastewater. Two sets of stormwater samples were collected, on June 27-28 and September 6, 2008, at the Rock Creek at Joyce Road water-quality station using an automated sampler that began sampling when a specified stage threshold value was exceeded. Passive-sampler devices that accumulate organic chemicals over the duration of deployment were placed in July 2008 at the five locations that had the greatest number of detections of organic wastewater compounds from the June 2007 base-flow sampling. During the 2007 base-flow synoptic sampling, there were ubiquitous low-level detections of dissolved organic wastewater indicator compounds such as DEET, caffeine, HHCB, and organophosphate flame retardants at more than half of the 23 sites sampled in Rock Creek Park. Concentrations of DEET and caffeine in the tributaries to Rock Creek were variable, but in the main stem of Rock Creek, the concentrations were constant throughout the length of the creek, which likely reflects a distributed source. Organophosphate flame retardants in the main stem of Rock Creek were detected at estimated concentrations of 0.2 micrograms per liter or less, and generally did not increase with distance downstream. Overall, concentrations of most wastewater indicators in whole-water samples in the Park were similar to the concentrations found at the upstream sampling station at the Maryland/District of Columbia boundary. Polycyclic aromatic hydrocarbons were the dominant organic compounds found in the stormwater samples at the Joyce Road station. Polycyclic aromatic hydrocarbons were consistently found in higher concentrations either in sediment or in whole-water samples than in the dissolved samples collected during base-flow conditions at the 23 synoptic sites, or in the Joyce Road station stormwater samples.

Scientific Investigations Report

Effects of urban stormwater and iron‐enhanced sand filtration on Daphnia magna and Pimephales promelas

Urban stormwater is an important but incompletely characterized contributor to surface‐water toxicity. The present study used 5 bioassays of 2 model organisms ( Daphnia magna and fathead minnow, Pimephales promelas ) to investigate stormwater toxicity and mitigation by full‐scale iron‐enhanced sand filters (IESFs). Stormwater samples were collected from major stormwater conveyances and full‐scale IESFs during 4 seasonal events (winter snowmelt and spring, early summer, and late summer rainfalls) and analyzed for a diverse range of contaminants of emerging concern including pharmaceuticals, personal care products, industrial chemicals, and pesticides. Concurrently, stormwater samples were collected for toxicity testing. Seasonality appeared more influential and consistent than site type for most bioassays. Typically, biological consequences were least in early summer and greatest in late summer and winter. In contrast with the unimproved and occasionally reduced biological outcomes in IESF‐treated and late summer samples, water chemistry indicated that numbers and total concentrations of detected organic chemicals, metals, and nutrients were reduced in late summer and in IESF‐treated stormwater samples. Some potent toxicants showed more specific seasonality (e.g., high concentrations of polycyclic aromatic hydrocarbons and industrial compounds in winter, pesticides in early summer and spring, flame retardants in late summer), which may have influenced outcomes. Potential explanations for insignificant or unexpected stormwater treatment outcomes include confounding effects of complex stormwater matrices, IESF nutrient removal, and, less likely, unmonitored toxicants.

Environmental Toxicology and Chemistry

Effects of hurricanes Katrina and Rita on the chemistry of bottom sediments in Lake Pontchartrain, Louisiana, USA

The effects of Hurricanes Katrina and Rita and the subsequent unwatering of New Orleans, Louisiana, on the sediment chemistry of Lake Pontchartrain were evaluated by chemical analysis of samples of street mud and suspended and bottom sediments. The highest concentrations of urban-related elements and compounds (e.g., Pb, Zn, polycyclic aromatic hydrocarbons, and chlordane) in bottom sediments exceeded median concentrations in U.S. urban lakes and sediment-quality guidelines. The extent of the elevated concentrations was limited, however, to within a few hundred meters of the mouth of the 17th Street Canal, similar to results of historical assessments. Chemical and radionuclide analysis of pre- and post-Hurricane Rita samples indicates that remobilization of near-shore sediment by lake currents and storms is an ongoing process. The effects of Hurricanes Katrina and Rita on the sediment chemistry of Lake Pontchartrain are limited spatially and are most likely transitory.

Environmental Science & Technology

Hydrologic setting and geochemical characterization of free-phase hydrocarbons in the alluvial aquifer at Mandan, North Dakota, November 2000

Free-phase hydrocarbons are present in the alluvial aquifer at Mandan, North Dakota. A large contaminant body of the hydrocarbons [light nonaqueous phase liquid (LNAPL)] floats on the water table about 20 feet below land surface. The main LNAPL body is about 6 feet thick, and the areal extent is about 657,000 square feet. A study was conducted to describe the hydrologic setting and characterize the geochemical composition of the free-phase hydrocarbons in the alluvial aquifer. Most of the study area is underlain by alluvium of the Heart River Valley that ranges in thickness from about 25 to 109 feet. The alluvium can be divided into three stratigraphic units silty clay, silty sand, and sand and is underlain by shales and sandstones. Monitoring wells were installed prior to this study, to an average depth of about 29 feet. Regional ground-water flow in the Heart River aquifer generally may be from west-northwest to eastsoutheast and is influenced by hydraulic connections to the river. Hydraulic connections also are probable between the aquifer and the Missouri River. Ground-water flow across the north boundary of the aquifer is minimal because of adjacent shales and sandstones of relatively low permeability. Recharge occurs from infiltration of precipitation and is spatially variable depending on the thickness of overlying clays and silts. Although the general water-table gradient may be from west-northwest to east-southeast, the flow directions can vary depending on the river stage and recharge events. Any movement of the LNAPL is influenced by the gradients created by changes in water-level altitudes. LNAPL samples were collected from monitoring wells using dedicated bailers. The samples were transferred to glass containers, stored in the dark, and refrigerated before shipment for analysis by a variety of analytical techniques. For comparison purposes, reference-fuel samples provided by the refinery in Mandan also were analyzed. These reference-fuel samples included a current diesel fuel, a closely related but slightly broader refinery-cut fuel, a crude-oil composite, unleaded regular gasoline, and additives. Four principal analytical techniques were used for geochemical characterization: Purge-and-trap gas chromatography/mass spectrometry (volatile components); capillary gas chromatography/mass spectrometry (semivolatile components); isotope ratio mass spectrometry (carbon isotopes; whole oils); and liquid chromatography/mass spectrometry with electrospray ionization (additives and other organic components). Volatile analytes included solvents, disinfection byproducts, halogenated hydrocarbons, and alkylbenzenes, including benzene, toluene, ethylbenzene, and meta-, para-, and orf/zo-xylenes. Semivolatile analytes included rt-alkanes, isoprenoid alkanes, cycloalkanes, and polycyclic aromatic hydrocarbons and related compounds (naphthalenes, phenanthrenes, and dibenzothiophenes and their alkylated derivatives). Of the additives, only the diesel-fuel additive with the red dye marker was amenable to electrospray ionization. Results indicate the LNAPL consists of closely correlatable diesel fuel at various stages of degradation. All LNAPL samples contained the red dye marker for diesel fuel. None of the samples contained chlorinated solvents associated with industries such as drycleaning or automotive maintenance. Solvents such as acetone, dimethyl ether, and methylene chloride and the gasoline additives methyl-t-butyl ether (MTBE), ethyl-t-butyl ether (ETBE), and t-amyl-methyl ether (TAME) were not found. With one possible exception, no evidence of a different diesel or other hydrocarbon fuel contribution was identified. At one site near the north edge of the main LNAPL body, evidence exists for traces of possible gasoline components in addition to the diesel fuel. The geochemical analysis of the LNAPL and correlations with other fuel products and additives strongly suggest episodic releases of a single, local-source, diesel fuel into the aquifer over an extended period of time.

North Dakota

Benzo[ b ]naphthothiophenes and alkyl dibenzothiophenes: molecular tracers for oil migration distances

The secondary migration of petroleum is one of the most critical geological processes responsible for the accumulation of hydrocarbons in a sedimentary basin. Pyrrolic nitrogen compounds such as carbazoles and benzocarbazoles are thought to be practical molecular indicators for estimating relative migration distances of oil. In light oils or condensates, however, considerable analytical errors are usually caused by low concentrations of NSO-compounds. Here we show that polycyclic sulfur aromatic hydrocarbons such as dibenzothiophene, C 1 ∼C 3 alkylated dibenzothiophenes and benzo[ b ]naphthothiophenes, which are present in relatively higher concentrations than the pyrrolic nitrogen compounds, exhibit changes in both absolute and relative concentrations that correlate with migration distances. The polycyclic sulfur aromatic hydrocarbons related parameters — benzo[ b ]naphtho[2,1- d ]thiophene/{benzo[ b ]naphtho[2,1- d ]thiophene + benzo[ b ]naphtho[1,2- d ]thiophene} (abbreviated as [2,1]BNT/([2,1]BNT+[1,2]BNT) and the concentration of total dibenzothiophenes plus benzo[ b ]naphthothiophenes — are proposed by this paper to trace the oil migration distances.

Tarim Basin;Tahe Oil Field