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Identifying sources of contaminants in urban stormwater and evaluation of their removal efficacy across a continuum of urban best management practices

Precipitation events in urban areas often result in stormwater runoff containing a diverse array of chemical contaminants. Although many traditional contaminants, such as nutrients, heavy metals, and polycyclic aromatic hydrocarbons have been studied extensively, only recently has evidence emerged showing that trace organic compounds (TrOCs), including pharmaceuticals, personal care products and pesticides are frequently found in stormwater runoff. As there is little existing information about the sources of TrOCs in urban stormwater or their removal efficacy across a range of stormwater treatment options, we conducted a study to address these knowledge gaps and to characterize the potential contribution of TrOCs to groundwater resources from stormwater infiltration practices, based on several synoptic measurements. The current study allowed us to enhance an existing effort to assess TrOC presence and toxicity in stormwater runoff and treatment pond outflow by addressing questions related to TrOC sources to stormwater and TrOC transport to groundwaters. Analysis of eDNA confirms multiple sources of TrOCs to stormwater including human sewage, dog waste, and feces from waterfowl. It is likely that the presence of some TrOCs detected in stormwater are the result of direct, untreated sewage inputs to stormwater from either human (i.e., leaking sewer infrastructure) or pet waste (washed from sidewalks into storm drains). The seasonal detection of avian eDNA is noteworthy as it highlights seasonality and patterns of migration patterns as contributing factors to stormwater contamination. In contrast to human and pet waste, which likely enters stormwater ponds via the stormwater conveyance system, avian feces may enter ponds either through stormwater runoff or through direct inputs by waterfowl stopping-over temporarily at stormwater ponds. Stormwater ponds had little effect in reducing TrOCs as determined by comparative inflow and outflow analysis. Our results also indicate that overall few TrOCs were present in receiving groundwater adjacent to underground infiltration basins, compared to inflow. However, some contaminants were present at relatively high concentrations compared to stormwater flowing into the basins. This is particularly true for pesticides and their degradants. Fewer TrOCs were detected in interstitial water collected near stormwater ponds compared to inflow and outflow. The presence and concentrations of TrOCs in outflow from ponds was generally similar to or higher than what was observed in inflow. The data collected as part of this study can be used to guide future research or monitoring in an effort to better understand TrOC fate and transport in the environment via stormwater BMPs. Specifically, more work is needed to track parcels of water as they flow through BMPs to better quantify transport and degradation of TrOCs, monitor flow into and out of ponds for mass balance calculations, and conduct tracer tests to better quantify the amount of water that monitoring wells are intercepting from underground infiltration basins. These results have been shared in multiple presentations and in meetings with high school teachers to develop age-appropriate curriculum to highlight the role of individuals in reducing and preventing stormwater contamination. The ongoing pandemic hindered some of these efforts (cancelled conferences; suspended MN Water Roundtable meetings; pre-occupation with teachers moving materials online), however, as dissemination activities become more common in the near future, we will continue to educate stakeholders and educators about the root causes and effects of urban stormwater contamination.

Minnesota

The presence and distribution of polycyclic aromatic hydrocarbons and inorganic elements in water and lakebed materials and the potential for bioconcentration in biota at established sampling sites on Lake Powell, Utah and Arizona

The National Park Service is responsible for monitoring the effects of visitor use on the quality of water, lakebed material (bottom sediments), and biota, in Lake Powell, Utah and Arizona. A sampling program was begun in 2010 to assess the presence, distribution, and concentrations of organic and inorganic compounds in the water column and bottom sediment. In response to an Environmental Impact Statement regarding personal watercraft and as a continuation from previous studies by the U.S. Geological Survey and the National Park Service, Glen Canyon National Recreation Area, water samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) using semipermeable membrane devices and inorganic elements using a fixed-bottle sampler deployed at established monitoring sites during 2010 and 2011. Lakebed material samples were also analyzed for polycyclic aromatic hydrocarbons and inorganic elements, some of which could be harmful to aquatic biota if present at concentrations above established aquatic life criteria. Of the 44 PAH compounds analyzed, 26 individual compounds were detected above the censoring limit in the water column by semipermeable membrane devices. The highest number of compounds detected were at Lone Rock Beach, Wahweap Marina, Rainbow Bridge National Monument, and Antelope Marina which are all located in the southern part of Lake Powell where visitation and boat use is high. Because PAHs can remain near their source, the potential for bioconcentration is highest near these sites. The PAH compound found in the highest concentration was phenol (5,902 nanograms per liter), which is included in the U.S. Environmental Protection Agency’s priority pollutants list. The dissolved inorganic chemistry of water samples measured at the sampling sites in Lake Powell defined three different patterns of elements: (1) concentrations were similar between sites in the upper part of the lake near Farley Canyon downstream to Halls Crossing Marina, a distance of about 36 lake miles, (2) concentrations varied depending on the element between Halls Crossing Marina downstream to the mouth of the Escalante River, a distance of about 33 lake miles, and (3) concentrations were similar between sites from below the mouth of the Escalante River to Glen Canyon Dam, a distance of about 68 lake miles. Analysis of lakebed bottom sediment material samples detected PAH compounds at all sampling sites except at Halls Crossing Marina, Stanton Creek, and Forgotten Canyon. Twenty-four of 44 PAHs analyzed in lakebed material were detected above the reporting limit. Perylene was the most prevalent compound detected above the reporting limit in lakebed material and was detected at three sampling sites. Concentrations of perylene ranged from an estimate of 24.0 to 47.9 micrograms per kilogram (μg/kg). Fluoranthene had the highest concentration of any PAH and was detected at the Wahweap Marina with a concentration of 565 μg/kg. The highest sum of concentrations for all compounds found in lakebed material samples at one site was at the Wahweap Marina, which had concentrations five times higher than the next highest site. The three major tributaries to Lake Powell—the Colorado, Escalante, and San Juan Rivers—all showed elevated concentrations of inorganic elements in their delta sediments for most elements relative to the majority of the sediment samples taken from the lake itself. However, there were four lake sites that had concentrations for most inorganic elements that equaled or exceeded those of the tributaries. Two of these sites were at the northeast part of the lake, nearest to the Colorado River as it enters Lake Powell (Farley Canyon and Blue Notch Canyon), one was at the Escalante River below 50-Mile Canyon, and other was at Antelope Marina.

Arizona;Utah

Summary of urban stormwater quality in Albuquerque, New Mexico, 2003-12

Urban stormwater in the Albuquerque metropolitan area was sampled by the U.S. Geological Survey in cooperation with the City of Albuquerque, the Albuquerque Metropolitan Arroyo Flood Control Authority, the New Mexico Department of Transportation, and the University of New Mexico. Stormwater was sampled from a network of monitoring stations from 2003 to 2012 by following regulatory requirements for the National Pollutant Discharge Elimination System stormwater permit. During this period, stormwater was sampled in the Albuquerque metropolitan area at outfalls from nine drainage basins with residential, industrial, commercial, agricultural, and undeveloped land uses. Stormwater samples were analyzed for selected physical and chemical characteristics, nutrients, major ions, metals, organic compounds, and bacteria. General quality of stormwater samples, as measured by dissolved solids, nutrient (with the exception of phosphorus), major ion, and dissolved metal concentrations, was similar to that in samples from the Rio Grande. Of the nearly 200 organic compounds that were analyzed for this study, less than one-third (58 constituents) were positively identified at or above the analytical detection limit in stormwater. Concentrations for volatile organic compounds, semivolatile organic compounds, polychlorinated biphenyls, and pesticides were generally low in the stormwater samples. Fifteen of the 16 polycyclic aromatic hydrocarbons listed on the U.S. Environmental Protection Agency Priority Chemicals list were detected in at least one stormwater sample from each outfall. Maximum concentrations for some polycyclic aromatic hydrocarbons in stormwater did exceed a water-quality criterion. Median concentrations for Escherichia coli ( E. coli ) bacteria in the stormwater samples, including those from the background location (Embudo Arroyo), were above the New Mexico water-quality standard. Concentrations for E. coli in stormwater often exceeded the water-quality criterion. The stormwater quality in Albuquerque was compared with that of six other Western U.S. cities (Phoenix, Arizona; Tucson, Arizona; Las Vegas, Nevada; Denver, Colorado; Salt Lake City, Utah; and Boise, Idaho) for selected constituents. In general, water-quality data for stormwater samples from these six other Western U.S. cities were similar to water-quality data for the stormwater samples from the Albuquerque outfalls. Median concentrations for suspended solids, total phosphorus, and bacteria ( E. coli and fecal coliform) in stormwater samples from the Albuquerque outfalls, as a whole, were higher than those in samples from the other Western U.S. cities except for Las Vegas.

New Mexico

Environmental contaminants

The purpose of this chapter is to provide an overview of the ecotoxicology of major classes of environmental contaminants, with respect to sources, environmental chemistry, most likely routes of exposure, potential bioaccumulation and biomagification, mechanisms of toxicity, and effects on potentially vulnerable species of mammalian wildlife. Major contaminants reviewed were selected on the basis of their use patterns, availability and potential toxicity to wild mammals. These included pesticides used in agroecosystems (organochlorines, organophosphorus and carbamate compounds, anticoagulants, herbicides and fungicides), various organic pollutants (chlorobenzenes, chlorophenols, polychlorinated biphenyls, dibenzodioxins and dibenzofurans, and polycyclic aromatic hydrocarbons), heavy metals (lead, mercury, and cadmium), agricultural drainwater mixtures, leachates and radionuclides. Many of the above aspects of ecotoxicology and contaminants will be expanded upon in subsequent chapters of this book as they relate to distinct mammalian species and potential risk.

Book chapter

Characterization of selected bed-sediment-bound organic and inorganic contaminants and toxicity, Barnegat Bay and major tributaries, New Jersey, 2012

A study of bed-sediment toxicity and organic and inorganic contaminants was conducted by the U.S. Geological Survey (USGS) in cooperation with the New Jersey Department of Environmental Protection (NJDEP). Bed-sediment samples were collected once from 22 sites in Barnegat Bay and selected major tributaries during August–September 2012 and analyzed for toxicity and a suite of organic and inorganic contaminants by the USGS and the U.S. Army Corps of Engineers. Sampling sites were selected to coincide with an existing water-quality monitoring network used by the NJDEP and others in order to evaluate water-quality conditions in Barnegat Bay and the surrounding watershed. Two of the 22 sites are reference sites and are within or adjacent to the study area; bed-sediment samples from reference sites allow for comparisons of results for the Barnegat Bay watershed to results from less affected settings within the region. Toxicity testing was conducted by exposing the estuarine amphipod Leptocheirus plumulosus and the freshwater amphipod Hyalella azteca to sediments for 28 days, and the percent survival, difference in biomass, and individual dry weights were measured. Reproductive effects also were evaluated for estuarine samples. Bed-sediment samples from four sites within Barnegat Bay were subjected to a toxicity identification evaluation to determine probable causes of toxicity. Samples were analyzed for a suite of 94 currently-used pesticides, 21 legacy pesticides, 24 trace elements, 40 polycyclic aromatic hydrocarbons, 7 polychlorinated biphenyls (PCBs) as Arochlor mixtures, and 145 individual PCB congeners. Concentrations of detected compounds were compared to sediment-quality guidelines, where appropriate.

New Jersey

Survey of chemical contaminants in the Hanalei River, Kaua'i, Hawai'i, 2001

The Hanalei River on the island of Kaua'i in Hawai'i was designated an American Heritage River in 1998, providing special attention to natural resource protection, economic revitalization, and historic and cultural preservation. Agricultural, urban, and tourism-related activities are potential sources of contamination within the Hanalei River watershed. The objective of this study was to measure certain persistent organic chemicals and elements in the Hanalei River. During a relatively low-flow period in December of 2001, samples of native Akupa sleeper fish ( Eleotris sandwicensis ), freshwater Asian clam ( Corbicula fluminea ), giant mud crab ( Scylla serrata ), surface water, and stream bed sediment were collected from a lower estuarine reach of the river near its mouth at Hanalei Bay and from an upper reach at the Hanalei National Wildlife Refuge. Samples were analyzed for residues of urban and agricultural chemicals including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, and elements (including mercury, lead, cadmium, arsenic, and selenium). Organic contaminants were extracted from the samples with solvent, enriched, and then analyzed by gas chromatographic analysis with electron capture or mass spectrometric detection. Samples were acid-digested for semi-quantitative analysis for elements by inductively-coupled plasma-mass spectrometry and for quantitative analysis by atomic absorption spectrophotometry. Concentrations of organochlorine pesticides, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls in biota, surface water, and bed sediment sampled from the Hanalei River ranged from nondetectable to very low levels. Polychlorinated biphenyls were below detection in all samples. Dieldrin, the only compound detected in the water samples, was present at very low concentrations of 1-2 nanograms per liter. Akupa sleeper fish and giant mud crabs from the lower reach ranged from 1 to 5 nanograms per gram (wet weight) dieldrin and from less than 0.3 to 2.1 nanograms per gram total chlordane. Concentrations of individual polycyclic aromatic hydrocarbons in the lower reach bed sediments ranged from less than 1 to 190 nanograms per gram (dry weight). Relative concentrations (patterns) of the polycyclic aromatic hydrocarbons in one portion of a sediment sample indicated combustion sources. Concentrations of elements in the surface water, biota, and sediment samples were below toxicity thresholds of ecological concern. In summary, concentrations of the organic contaminants and elements targeted by this study of the Hanalei River in 2001 were below U.S. Environmental Protection Agency probable adverse effects levels for aquatic organisms.

Scientific Investigations Report

Sedimentary organics in Glen Torridon, Gale Crater, Mars: Results from the SAM instrument suite and supporting laboratory analyses

The Sample Analysis at Mars (SAM) suite instrument on board NASA's Curiosity rover has characterized the inorganic and organic chemical composition of seven samples from the Glen Torridon (GT) clay-bearing unit. A variety of organic molecules were detected with SAM using pyrolysis (up to ∼850°C) and wet chemistry experiments coupled with evolved gas analysis (EGA) and gas chromatography-mass spectrometry. SAM EGA and GCMS analyses revealed a greater diversity and abundance of sulfur-bearing aliphatic and aromatic organic compounds in the sediments of this Gale crater unit than earlier in the mission. We also report the detection of nitrogen-containing, oxygen-containing, and chlorine-containing molecules, as well as polycyclic aromatic hydrocarbons found in GT, although the sources of some of these organics may be related to the presence of chemical reagents in the SAM instrument background. However, sulfur-bearing organics released at high temperature (≥600°C) are likely derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources and consistent with the presence of recalcitrant organic materials in the sample. The SAM measurements of the GT clay-bearing unit expand the inventory of organic matter present in Gale crater and is also consistent with the hypothesis that clay minerals played an important role in the preservation of ancient refractory organic matter on Mars. These findings deepen our understanding of the past habitability and biological potential of Gale crater.

JGR Planets

Effects of humic substances on the bioconcentration of polycyclic aromatic hydrocarbons: Correlations with spectroscopic and chemical properties of humic substances

The presence of dissolved humic substances (HS, fulvic and humic acids) generally reduces the up take of hydrophobic organic compounds into aquatic organisms. The extent of this effect depends both on the concentration and on the origin of the HS. The aim of this study was to investigate the role of qualitative differences between HS from different origins. The effects of seven different HS on the bioconcentration of pyrene and benzo[ a ]pyrene (B a P) in the nematode Caenorhabditis elegans were related to the spectroscopic and chemical properties of the HS. The effect of each humic material on the bioconcentration of pyrene or B a P was quantified as a “biologically determined” partition coefficient K DOC . We observed significant linear relationships between K DOC and the atomic H/C ratio, the specific absorptivity at 254 nm, the content of aromatic carbons (as determined by 13 C nuclear magnetic resonance spectroscopy, the copper-complexing capacity, the content of phenolic OH groups, and the molecular weight of the HS. There was no discernible relationship of K DOC with the atomic (N + O)/C ratio, an indicator of the polarity of HS. Taken together, our results show that the variability in the effects of HS from different origins could be related to variations in bulk properties of the HS. Parameters describing the aromaticity of the humic materials seemed to be most useful for estimating effects of HS on the bioconcentration of pyrene and B a P.

Environmental Toxicology and Chemistry

Legacy and current-use toxic contaminants in Pacific sand lance (Ammodytes personatus) from Puget Sound, Washington

Forage fish are primary prey for seabirds, fish and marine mammals. Elevated levels of pollutants in Puget Sound, Washington salmon and killer whale tissues potentially could be sufficiently high to elicit adverse effects and hamper population recovery efforts. Contaminant transfer and biomagnification of the toxic compounds measured in this study likely contribute to those elevated concentrations. Pacific sand lance tissues from nine locations were analyzed for a suite of legacy and emerging contaminants including polychlorinated biphenyls, polybrominated diphenyl ethers, chlorinated pesticides, polycyclic aromatic hydrocarbons, alkylphenols, and chlorinated paraffins. Chemicals were detected at all sites generally below available health effect levels for the host. However, sub-lethal effects are known to occur and additive effects from exposure to multiple compounds, like this study’s mixture, are not well understood. Biomagnification calculations suggest that, in some locations, concentrations of polychlorinated biphenyls in forage fish could result in predator tissue concentrations that exceed effect levels.

Washington

Organic Compounds, Trace Elements, Suspended Sediment, and Field Characteristics at the Heads-of-Tide of the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers, New Jersey, 2000-03

Concentrations of suspended sediment, particulate and dissolved organic carbon, trace elements, and organic compounds were measured in samples from the heads-of-tide of the five tributaries to the Newark and Raritan Bays during June 2000 to June 2003. The samples were collected as part of the New Jersey Department of Environmental Protection Toxics Reduction Workplan/Contaminant Assessment Reduction Program. Samples of streamwater were collected at water-quality sampling stations constructed near U.S. Geological Survey gaging stations on the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers. Sampling was conducted during base-flow conditions and storms. Constituent concentrations were measured to determine the water quality and to calculate the load of sediment and contaminants contributed to the bays from upstream sources. Water samples were analyzed for suspended sediment, dissolved organic carbon, particulate organic carbon, and specific conductance. Samples of suspended sediment and water were analyzed for 98 distinct polychlorinated biphenyl congeners, 7 dioxins, 10 furans, 27 pesticides, 26 polycyclic aromatic hydrocarbons, and the trace elements cadmium, lead, mercury, and methyl-mercury. Measurements of ultra-low concentrations of organic compounds in sediment and water were obtained by collecting 1 to 3 grams of suspended sediment on glass fiber filters and by passing at least 20 liters of filtered water through XAD-2 resin. The extracted sediment and XAD-2 resin were analyzed for organic compounds by high- and low-resolution gas chromatography mass-spectrometry that uses isotope dilution procedures. Trace elements in filtered and unfiltered samples were analyzed for cadmium, lead, mercury, and methyl-mercury by inductively coupled charged plasma and mass-spectrometry. All constituent concentrations are raw data. Interpretation of the data will be completed in the second phase of the study.

Data Series

Ecotoxicological profile of a high prevalence marine disease area in Florida's Gulf coast

Pervasive marine pollution can have devastating effects on ocean health. Polychlorinated Biphenyls (PCB), Polycyclic Aromatic Hydrocarbons (PAH), and Organochlorine Pesticides (OCP) are of particular concern given their high level of toxicity and carcinogenicity. These compounds originate from anthropogenic activity, therefore are often ubiquitous in coastal environments close to human sources. Marine turtles in coastal Florida (USA) are affected by fibropapillomatosis, a tumor-causing panzootic with highly debilitating symptoms. Despite repeated associations between fibropapillomatosis occurrence and carcinogenic pollution, the ecotoxicological status of high disease areas in the Florida Gulf has been unknown. Our study deployed passive sampling devices along a structured inshore-to-offshore coastal grid to generate the first comprehensive dataset on the concentration and diversity of oncogenic pollutants in Crystal River, Florida, where juvenile green turtles exhibit a fibropapillomatosis prevalence of 74%. Multiple OCP, PAH, and PCB compounds were detected for a total chemical concentration of 16,086.98 pg/L (Σ OCP 45.51 pg/L + Σ PAH 16,014.53 pg/L + Σ PCB 26.94 pg/L). Density and composition of carcinogenic pollution was found to be significantly lower in offshore green turtle habitats compared to inshore habitats (p=0.02), suggesting multiple potential contamination sources along the coastline. The carcinogenic compounds detected have been shown to have associations with fibropapillomatosis in other parts of the world, as well as having wider ecosystem implications. Our work contributes to the body of knowledge correlating the emerging threat of harmful ocean pollution and marine wildlife diseases.

Florida

PAH refractory index as a source discriminant of hydrocarbon input from crude oil and coal in Prince William Sound, Alaska

Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty. A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.

Conference Paper

Trace elements and organic compounds in streambed sediment and fish tissue of coastal New England streams, 1998-99

Streambed sediment and fish tissue were collected at 14 river sites in eastern New England during low-flow conditions in 1998 and 1999 as part of the New England Coastal Basins (NECB) study of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program. Sampling sites were selected over a range of urban settings. Population densities at selected sites ranged from 26 to 3,585 people per square mile, and urban land use ranged from 1 to 68 percent. The streambed sediment samples were analyzed for a total of 141 contaminants, including 45 trace elements, 32 organochlorine compounds, and 64 semi-volatile organic compounds. The fish tissue samples were analyzed for 22 trace elements and 28 organochlorine compounds. Concentrations of selected contaminants in both streambed sediment and fish tissue correlated more strongly with population density than with other watershed characteristics. Cadmium, copper, lead, mercury, zinc, total polycyclic aromatic hydrocarbons (PAHs), total polychlorinated biphenyls (PCBs), dichloro diphenyl trichloroethane and metabolites (DDTM), and total chlordane in streambed sediment all showed strong positive correlations with population density (rho = 0.71 to 0.85, p value = 0.005 to <0.001). Correlations between population density and selected contaminants in fish tissue were less significant than with streambed sediment (rho = 0.62 to 0.72, p value = 0.03 to 0.008). Organic carbon concentrations were correlated with concentrations of arsenic, selenium, total PAHs, total PCBs, and DDTM in streambed sediment. The relation between concentrations of contaminants in streambed sediment and fish tissue was stronger for organochlorine compounds (rho = 0.75 to 0.55, p = 0.005 to 0.065) than for trace elements (rho = 0.63 to 0.53, p = 0.029 to 0.069). The NECB study area had the highest median concentrations of lead, mercury, total PAHs, total PCBs, and DDTM in streambed sediment and the highest median concentration of PCBs in fish tissue compared to 45 other NAWQA study units across the Nation. Concentrations of many of these constituents in streambed sediment also were frequently above the consensus-based Sediment-Quality Guidelines for the protection of wildlife, suggesting they are a threat to the health of aquatic biota in New England.

Water-Resources Investigations Report

Organic markers as source discriminants and sediment transport indicators in south San Francisco Bay, California

Sediment samples from nearshore sites in south San Francisco Bay and from streams flowing into that section of the Bay have been characterized in terms of their content of biogenic and anthropogenic molecular marker compounds. The distributions, input sources, and applicability of these compounds in determining sediment movement are discussed. By means of inspection and multivariate analysis, the compounds were grouped according to probable input sources and the sampling stations according to the relative importance of source contributions. A suite of polycyclic aromatic hydrocarbons (PAHs) dominated by pyrene, fluoranthene and phenanthrene, typical of estuarine environments worldwide, and suites of mature sterane and hopane biomarkers were found to be most suitable as background markers for the Bay. A homologous series of long-chain n-aldehydes (C12-C32) with a strong even-over-odd carbon number dominance in the higher molecular weight range and the ubiquitous n-alkanes (n-C24-C34) with a strong odd-over-even carbon number dominance were utilized as terrigenous markers. Several ratios of these terrigenous and Bay markers were calculated for each station. These ratios and the statistical indicators from the multivariate analysis point toward a strong terrigenous signal in the terminus of South Bay and indicate net directional movement of recently introduced sediment where nontidal currents had been considered to be minimal or nonexistent and tidal currents had been assumed to be dominant.

California

Distributions and fate of chlorinated pesticides, biomarkers and polycyclic aromatic hydrocarbons in sediments along a contamination gradient from a point-source in San Francisco Bay, California

The distribution and fate of chlorinated pesticides, biomarkers, and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments along a contamination gradient in the Lauritzen Canal and Richmond Harbor in San Francisco Bay was investigated. Compounds were identified and quantified using gas chromatography-ion trap mass spectrometry. Biomarkers and PAHs were derived primarily from weathered petroleum. DDT was reductively dechlorinated under anoxic conditions to DDD and several minor degradation products, DDMU, DDMS, and DDNU. Under aerobic conditions, DDT was dehydrochlorinated to DDE and DBP. Aerobic degradation of DDT was diminished or inhibited in zones of high concentration, and increased significantly in zones of lower concentration: Other chlorinated pesticides identified in sediment included dieldrin and chlordane isomers. Multivariate analysis of the distributions of the DDTs suggested that there are probably two sources of DDD. In addition, DDE and DDMU are probably formed by similar mechanisms, i.e. dehydrochlorination. A steep concentration gradient existed from the Canal to the Outer Richmond Harbor, but higher levels of DDD than those found in the remainder of the Bay indicated that these contaminants are transported on particulates and colloidal organic matter from this source into San Francisco Bay. Chlorinated pesticides and PAHs may pose a potential problem to biota in San Francisco Bay.

Marine Environmental Research

Trace elements and organic compounds in sediment and fish tissue from the Great Salt Lake basins, Utah, Idaho, and Wyoming, 1998-99

A study to determine the occurrence and distribution of trace elements, organochlorine pesticides, polychlorinated biphenyls (PCBs), and semivolatile organic compounds in sediment and in fish tissue was conducted in the Great Salt Lake Basins study unit of the National Water-Quality Assessment (NAWQA) program during 1998-99. Streambed-sediment and fish-tissue samples were collected concurrently at 11 sites and analyzed for trace-element concentration. An additional four sites were sampled for streambed sediment only and one site for fish tissue only. Organic compounds were analyzed from streambed-sediment and fish-tissue samples at 15 sites concurrently. Bed-sediment cores from lakes, reservoirs, and Farmington Bay collected by the NAWQA program in 1998 and by other researchers in 1982 were used to examine historical trends in trace-element concentration and to determine anthropogenic sources of contaminants. Cores collected in 1982 from Mirror Lake, a high-mountain reference location, showed an enrichment of arsenic, cadmium, copper, lead, tin, and zinc in the surface sediments relative to the deeper sediments, indicating that enrichment likely began after about 1900. This enrichment was attributed to atmospheric deposition during the period of metal-ore mining and smelting. A core from Echo Reservoir, in the Weber River Basin, however, showed a different pattern of trace-element concentration that was attributed to a local source. This site is located downstream from the Park City mining district, which is the most likely historical source of trace elements. Cores collected in 1998 from Farmington Bay show that the concentration of lead began to increase after 1842 and peaked during the mid-1980s and has been in decline since. Recent sediments deposited during 1996-98 indicate a 41- to 62-percent reduction since the peak in the mid-1980s. The concentration of trace elements in streambed sediment was greatest at sites that have been affected by historic mining, including sites on Little Cottonwood Creek in the Jordan River basin, Silver Creek in the Weber River basin, and the Weber River below the confluence with Silver Creek. There was significant correlation of lead concentrations in streambed sediment and fish tissue, but other trace elements did not correlate well. Streambed sediment and fish tissue collected from sites in the Bear River basin, which is predominantly rangeland and agriculture, generally had low concentrations of most elements. Sediment-quality guidelines were used to assess the relative toxicity of streambed-sediment sites to aquatic communities. Sites affected by mining exceeded the Probable Effect Concentration (PEC), the concentration at which it is likely there will be a negative effect on the aquatic community, for arsenic, cadmium, copper, lead, silver, mercury, and zinc. Sites that were not affected by mining did not exceed these criteria. Concentrations of trace elements in samples collected from the Great Salt Lake Basins study unit (GRSL) are high compared to those of samples collected nationally with the NAWQA program. Nine of 15 streambed-sediment samples and 11 of 14 fish-tissue samples had concentrations of at least one trace element greater than the concentration of 90 percent of the samples collected nationally during 1993-2000. Organic compounds that were examined in streambed sediment and fish-tissue samples also were examined in bed-sediment cores. A bed-sediment core from Farmington Bay of Great Salt Lake showed an increase in total polycyclic aromatic hydrocarbon (PAH) concentrations coincident with the increase in population in Salt Lake Valley, which drains into this bay. Analysis of streambed-sediment samples showed that the highest concentrations of PAHs were detected at urban sites, including two sites in the lower Jordan River (the Jordan River flows into Farmington Bay), the Weber River at Ogden Bay, and the Provo River near Provo. Other organic compounds detected in streambed sediment in the lower Jordan River were PCBs, DDT compounds, and chlordane compounds. Organic compounds were detected more frequently in fish tissue than in streambed sediment. Chlordane compounds and PCBs were detected more frequently at urban sites. DDT compounds were detected at 13 of 15 sites including urban and agricultural sites. Concentrations of total DDT in fish tissue exceeded the guideline for protection of fish-eating wildlife at two urban sites. The concentration of organic compounds in the GRSL study unit is low compared with that of samples collected nationally.

Idaho, Utah, Wyoming

Mercury, trace elements and organic constituents in atmospheric fine particulate matter, Shenandoah National Park, Virginia, USA: A combined approach to sampling and analysis

Compliance with U.S. air quality regulatory standards for atmospheric fine particulate matter (PM 2.5 ) is based on meeting average 24 hour (35 μ m −3 ) and yearly (15 μg m −3 ) mass‐per‐unit‐volume limits, regardless of PM 2.5 composition. Whereas this presents a workable regulatory framework, information on particle composition is needed to assess the fate and transport of PM 2.5 and determine potential environmental/human health impacts. To address these important non‐regulatory issues an integrated approach is generally used that includes (1) field sampling of atmospheric particulate matter on filter media, using a size‐limiting cyclone, or with no particle‐size limitation; and (2) chemical extraction of exposed filters and analysis of separate particulate‐bound fractions for total mercury, trace elements and organic constituents, utilising different USGS laboratories optimised for quantitative analysis of these substances. This combination of sampling and analysis allowed for a more detailed interpretation of PM 2.5 sources and potential effects, compared to measurements of PM 2.5 abundance alone. Results obtained using this combined approach are presented for a 2006 air sampling campaign in Shenandoah National Park (Virginia, USA) to assess sources of atmospheric contaminants and their potential impact on air quality in the Park. PM 2.5 was collected at two sampling sites (Big Meadows and Pinnacles) separated by 13.6 km. At both sites, element concentrations in PM 25 were low, consistent with remote or rural locations. However, element/Zr crustal abundance enrichment factors greater than 10, indicating anthropogenic input, were found for Hg, Se, S, Sb, Cd, Pb, Mo, Zn and Cu, listed in decreasing order of enrichment. Principal component analysis showed that four element associations accounted for 84% of the PM 2.5 trace element variation; these associations are interpreted to represent: (1) crustal sources (Al, REE); (2) coal combustion (Se, Sb), (3) metal production and/or mobile sources (Mo, Cd, Pb, Cu, Zn) and (4) a transient marine source (Sr, Mg). Concentrations of Hg in PM 2.5 at background levels in the single pg m −3 were shown by collection and analysis of PM 2.5 on filters and by an automated speciation analyser set up at the Big Meadows air quality site. The speciation unit revealed periodic elevation of reactive gaseous mercury (RGM) that co‐occurred with peaks in SO 2 , indicating an anthropogenic source. GC/MS total ion current chromatograms for the two sites were quite similar indicating that organic signatures were regional in extent and/or that the same compounds were present locally at each site. Calculated carbon preference index values for n ‐alkanes indicated that plant waxes rather than anthropogenic sources, were the dominant alkane source. Polycyclic aromatic hydrocarbons (PAHs) were detected, with a predominance of non‐alkylated, and higher molecular weight PAHs in this fraction, suggestive of a combustion source (fossil fuel or forest fires).

Virginia

Organic contaminants in Great Lakes tributaries: Prevalence and potential aquatic toxicity

Organic compounds used in agriculture, industry, and households make their way into surface waters through runoff, leaking septic-conveyance systems, regulated and unregulated discharges, and combined sewer overflows, among other sources. Concentrations of these organic waste compounds (OWCs) in some Great Lakes tributaries indicate a high potential for adverse impacts on aquatic organisms. During 2010&ndash;13, 709 water samples were collected at 57 tributaries, together representing approximately 41% of the total inflow to the lakes. Samples were collected during runoff and low-flow conditions and analyzed for 69 OWCs, including herbicides, insecticides, polycyclic aromatic hydrocarbons, plasticizers, antioxidants, detergent metabolites, fire retardants, non-prescription human drugs, flavors/fragrances, and dyes. Urban-related land cover characteristics were the most important explanatory variables of concentrations of many OWCs. Compared to samples from nonurban watersheds (< 15% urban land cover) samples from urban watersheds (> 15% urban land cover) had nearly four times the number of detected compounds and four times the total sample concentration, on average. Concentration differences between runoff and low-flow conditions were not observed, but seasonal differences were observed in atrazine, metolachlor, DEET, and HHCB concentrations. Water quality benchmarks for individual OWCs were exceeded at 20 sites, and at 7 sites benchmarks were exceeded by a factor of 10 or more. The compounds with the most frequent water quality benchmark exceedances were the PAHs benzo[ a ]pyrene, pyrene, fluoranthene, and anthracene, the detergent metabolite 4-nonylphenol, and the herbicide atrazine. Computed estradiol equivalency quotients (EEQs) using only nonsteroidal endocrine-active compounds indicated medium to high risk of estrogenic effects (intersex or vitellogenin induction) at 10 sites. EEQs at 3 sites were comparable to values reported in effluent. This multifaceted study is the largest, most comprehensive assessment of the occurrence and potential effects of OWCs in the Great Lakes Basin to date.

Great Lakes