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Chemical characterization and mutagenic properties of polycyclic aromatic compounds in sediment from tributaries of the Great Lakes

Sediments from four inshore industrial sites and a reference site in the Great Lakes were extracted with solvents and characterized chemically for polycyclic aromatic compounds (PACs). An aqueous phase and a crude organic extract were obtained. The crude organic extract was further resolved into fractions A-2 (polycyclic aromatic hydrocarbons) and A-3 (nitrogen-containing polycyclic aromatic compounds), which were analyzed for PACs by gas chromatography and gas chromatography-mass spectrometry. The extracts and fractions were tested for mutagenicity in three assays: Ames, rat hepatocyte unscheduled DNA synthesis, and Chinese hamster ovary hypoxanthine-guanine phosphoribosyl transferase (CHO/HGPRT). Sediments from the industrial sites contained 27 to 363 μg/g total PACs; the reference site, less than 1 μg/g. Qualitative differences in the residue profiles among the sites were attributable to the probable sources of the PACs (petroleum versus combustion). Only one industrial site yielded measurable (0.1 μg/g or more) concentrations of individual nitrogen-containing PACs. In the Ames assay, only the highest doses of the A-2 fractions from two sites approached positive results. Conversely, the crude organic extract and A-2 and A-3 fractions from all sites induced unscheduled DNA synthesis. Crude organic extracts and the A-2 and A-3 fractions from all industrial sites gave well-defined dose-response relations in the CHO/HGPRT assay. We established the presence of chemical mutagens in sediment that could be correlated with neoplasms in fish from many of the sites; however, the mutagenicity of the sediment extracts was not completely related to the degree of contamination by PACs. We also discuss the utility of mutagenicity assays in the evaluation of complex chemical mixtures and recommend the use of a CHO/HGPRT-type assay in which cells are not required to proliferate in the presence of potential interfering chemicals.

Environmental Toxicology and Chemistry

Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia)

Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations.

Alaska, California, Washington

Investigation of the distribution of organochlorine and polycyclic aromatic hydrocarbon compounds in the Lower Columbia River using semipermeable-membrane devices

Organochlorine and polycyclic aromatic hydrocarbon compounds are of concern in the Columbia River Basin because of their adverse effects on fish and wildlife. Because these compounds can have important biological consequences at concentrations well below the detection limits associated with conventional water-sampling techniques, we used semipermeable membrane devices (SPMDs) to sample water, and achieved sub-parts-per-quintillion detection limits. We deployed SPMDs during 1997 low-flow conditions and 1998 high-flow conditions at nine main-stem sites and seven tributary sites, spanning approximately 700 miles of the Columbia River. We also collected streambed sediment from three sites. SPMD extracts and sediments were analyzed for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, polychlorinated biphenyls, organochlorine pesticides and related transformation products, and polycyclic aromatic hydrocarbons. Our data indicate that (1) in the absence of additional sources, mechanisms such as volatilization, dilution, and settling of suspended particles can act to significantly reduce concentrations of contaminants along the river's flow path, (2) elevated concentrations of contaminants in the Portland-Vancouver area are primarily from local rather than upstream sources, (3) elevated concentrations of many compounds tend to be diluted during periods of high discharge, (4) much higher discharge in the main stem considerably dilutes elevated concentrations entering from tributaries, (5) the distribution of hydrophobic organic compounds in streambed sediment is not necessarily indicative of their distribution in the dissolved-phase, and (6) SPMDs can reveal patterns of contaminant occurrence at environmentally relevant concentrations that are undetectable by conventional water-sampling techniques.

Oregon

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of polycyclic aromatic hydrocarbon compounds in sediment by gas chromatography/mass spectrometry

A method for the determination of 28 polycyclic aromatic hydrocarbons (PAHs) and 25 alkylated PAH homolog groups in sediment samples is described. The compounds are extracted from sediment by solvent extraction, followed by partial isolation using high-performance gel permeation chromatography. The compounds are identified and uantitated using capillary-column gas chromatography/mass spectrometry. The report presents performance data for full-scan ion monitoring. Method detection limits in laboratory reagent matrix samples range from 1.3 to 5.1 micrograms per kilogram for the 28 PAHs. The 25 groups of alkylated PAHs are homologs of five groups of isomeric parent PAHs. Because of the lack of authentic standards, these homologs are reported semiquantitatively using a response factor from a parent PAH or a specific alkylated PAH. Precision data for the alkylated PAH homologs are presented using two different standard reference manuals produced by the National Institute of Standards and Technology: SRM 1941b and SRM 1944. The percent relative standard deviations for identified alkylated PAH homolog groups ranged from 1.55 to 6.98 for SRM 1941b and from 6.11 to 12.0 for SRM 1944. Homolog group concentrations reported under this method include the concentrations of individually identified compounds that are members of the group. Organochlorine (OC) pesticides--including toxaphene, polychlorinated biphenyls (PCBs), and organophosphate (OP) pesticides--can be isolated simultaneously using this method. In brief, sediment samples are centrifuged to remove excess water and extracted overnight with dichloromethan (95 percent) and methanol (5 percent). The extract is concentrated and then filtered through a 0.2-micrometer polytetrafluoroethylene syringe filter. The PAH fraction is isolated by quantitatively injecting an aliquot of sample onto two polystyrene-divinylbenzene gel-permeation chromatographic columns connected in series. The compounds are eluted with dichloromethane, a PAH fraction is collected, and a portion of the coextracted interferences, including elemental sulfur, is separated and discarded. The extract is solvent exchanged, the volume is reduced, and internal standard is added. Sample analysis is completed using a gas chromatograph/mass spectrometer and full-scan acquisition.

Water-Resources Investigations Report

Contaminated sediments from tributaries of the Great Lakes: Chemical characterization and carcinogenic effects in medaka ( Oryzias latipes )

Sediments from four inshore industrial sites and a reference site in the Great Lakes were extracted with organic solvents to produce a crude extract, which was separated on alumina into two fractions: predominantly polycyclic aromatic hydrocarbons; and predominantly nitrogencontaining polycyclic aromatic compounds. Crude extracts were redissolved in acetone and analyzed by gas chromatography and gas chromatography-mass spectrometry. The acetone-redissolved crude extracts from the four industrialized sites contained 5.6–313.3 μg total polycyclic aromatic compounds/g sediment and 3.0–36.4 μg other compounds/g sediment. In addition to the typical EPA priority pollutants, a substantial amount (228.7 μg/g sediment) of alkyl-polycyclic-aromatic compounds was detected in sediments from one of the industrialized sites. Extracts from the reference site contained 1.55 μg total polycyclic aromatic compounds/ g sediment. Medaka ( Oryzias latipes ) were exposed to multiple pulse doses of acetone-redissolved extracts and fractions. Medaka were also exposed to a known carcinogen, methylazoxymethanol acetate, to verify that chemicals produced tumors in the test fish. Acetone-redissolved extracts and fractions from contaminated sediments were toxic to medaka. Fin erosion and non-neoplastic liver abnormalities were more prevalent in medaka after exposure to acetoneredissolved extracts and fractions from contaminated sediments. Neoplasms previously associated with chemical exposure in wild fishes were induced in medaka exposed to acetone-redissolved extracts and fractions from two of the contaminated sites, but not from the reference site or controls. These findings further support the hypothesis that chemical contaminants in sediments are involved in epizootics of neoplasms in wild fishes at contaminated sites.

Archives of Environmental Contamination and Toxico

Chapter 3. Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry

A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and passed through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry. Comparisons of PAH data for 28 sediment samples extracted by Soxhlet and the accelerated solvent extraction (ASE) method described in this report produced similar results. Extraction of PAH compounds from standard reference material using this method also compared favorably with Soxhlet extraction. The recoveries of PAHs less than molecular weight 202 (pyrene or fluoranthene) are higher by up to 20 percent using this ASE method, whereas the recoveries of PAHs greater than or equal to molecular weight 202 are equivalent. This ASE method of sample extraction of solids has advantages over conventional Soxhlet extraction by increasing automation of the extraction process, reducing extraction time, and using less solvent. Extract cleanup also is greatly simplified because SPE replaces commonly used gel permeation chromatography. The performance of the method (as expressed by mean recoveries and mean precision) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. Recoveries of PAH and semivolatile compounds in Ottawa sand samples fortified at 1.5 micrograms averaged 88 percent ? 9.4 percent relative standard deviation, and calculated initial method detection limits per compound averaged 14 micrograms per kilogram, assuming a 25-gram sample size. The recovery for 1,2,4-trichlorobenzene is less than 60 percent; thus, the concentration of this compound will always be reported as estimated with the E remark code. The analysis of 25 alkylated PAH homolog groups also can be determined with this method with extra data analysis and review, but because of the lack of authentic reference standard compounds, these results are considered to be semiquantitative. The PAH homolog groups are quantitated using the response factor of a parent PAH method compound, if available. Precision data for the alkylated PAH homologs detected in a marine sediment standard reference material (SRM 1944) also are presented to document and demonstrate method capability.

Techniques and Methods

Organic wastewater compounds in water and sediment in and near restored wetlands, Great Marsh, Indiana Dunes National Lakeshore, 2009–11

A cooperative investigation between the U.S. Geological Survey and the National Park Service was completed from 2009 through 2011 to understand the occurrence, distribution, and environmental processes affecting concentrations of organic wastewater compounds in water and sediment in and near Great Marsh at the Indiana Dunes National Lakeshore in Beverly Shores, Indiana. Sampling sites were selected to represent hydrologic inputs to the restored wetlands from adjacent upstream residential and less developed areas and to represent discharge points of cascading cells within the restored wetland. A multiphase approach was used for the investigation. Discrete water samples and time-integrated passive samples were analyzed for 69 organic wastewater compounds. Continuous water-level information and periodic streamflow measurements characterized flow conditions at discharge points from restored wetland cells. Wetland sediments were collected and analyzed for sorptive losses of organic wastewater compounds and to evaluate of the potential for wetland sediments to biotransform organic wastewater compounds. A total of 52 organic wastewater compounds were detected in discrete water samples at 1 or more sites. Detections of organic wastewater compounds were widespread, but concentrations were generally low and 95 percent were less than 2.1 micrograms per liter. Six compounds were detected at concentrations greater than 2.1 micrograms per liter—four fecal sterols (beta-sitosterol, cholesterol, beta-stigmastanol, and 2-beta coprostanol), one plasticizer (bis-2-ethylhex ylphthalate), and a non-ionic detergent (4-nonylphenol diethoxylate). Two 1-month deployments of time-integrative passive samplers, called polar organic chemical integrative samplers, detected organic wastewater compounds at lower concentrations than were possible with discrete water samples. Isopropyl benzene (solvent), caffeine (plant alkaloid, stimulant), and hexahydrohexamethyl cyclopentabenzopyran (fragrance) were detected in more than half of the extracts from passive samplers, but they were not detected in any discrete water sample. The Yeast Estrogen Screen assay identified measurable estrogenicity in one passive sampler extract from the most downstream wetland site in both the April and November–December 2011 deployments and in passive sampler extracts from one residential and one upstream site in the November–December 2011 deployment only. Surface-water levels in the restored wetland cells were monitored continuously using submersible pressure transducers in hand-driven well points screened in the surface water. Surface-water levels in the wetland cells responded quickly to precipitation and substantially receded within 2 days following the largest rainfall events. Seasonal patterns in water levels generally showed higher and more variable surface-water levels in the wetland cells during spring and early summer. Water levels in the wetland cells fell below the elevation of the control structures and ceased to flow over the spillways during extended dry periods (primarily late summer and early fall). Daily loads of seven organic wastewater compounds, as indicators of septic system effluent, were estimated for samples collected at wetland outlet spillways when flow measurements could be made. Median daily loads of the indicator organic wastewater compounds increased in downstream order, and the largest median loads were measured at the most downstream site. Median daily loads were higher for samples collected in spring and summer than those collected in fall, as the higher seasonal water levels increased streamflow at the wetland outlet spillways. Wetland sediment samples were analyzed for 84 organic wastewater compounds, polycyclic aromatic hydrocarbons, and semivolatile organic compounds to investigate the fate of contaminants in Great Marsh. The top five detected compounds by total mass in wetland sediment samples were beta-sitosterol, beta-stigmastanol, cholesterol, bis(2-ethylhexyl) phthalate, and phenol. Polycyclic aromatic hydrocarbons also were frequently detected in wetland sediment samples. Source apportionment of polycyclic aromatic hydrocarbon detections indicated atmospheric sources of pyrogenic compounds, rather than residential sources. Comparisons of polycyclic aromatic hydrocarbon concentrations in wetland sediment samples to sediment quality target guidelines indicated the potential for harmful effects on sediment-dwelling organisms at several sites. Biodegradation of select endocrine-disrupting compounds (17α-ethinylestradiol, 4-nonylphenol, triclocarban, and bisphenol A) in shallow wetland sediments was evaluated in laboratory experiments by using carbon-14 radiolabeled model contaminants. Substantial biodegradation of certain organic wastewater compounds were demonstrated, primarily in oxic (oxygen containing) environments. One of four modeled compounds, bisphenol A, was biodegraded in anoxic (oxygen free) environments. Only sediments collected nearest residential areas exhibited degradation of the synthetic birth control pharmaceutical, 17α-ethinylestradiol, possibly owing to adaptation and acclimation of the indigenous microbial community to septic discharge and the resultant selection of a microbial capability for biodegradation of 17α-ethinylestradiol.

Indiana

Occurrence and concentrations of selected trace elements, halogenated organic compounds, and polycyclic aromatic hydrocarbons in streambed sediments and results of water-toxicity testing in Westside Creeks and the San Antonio River, San Antonio, Texas, 2014

Sediment samples and samples for water-toxicity testing were collected during 2014 from several streams in San Antonio, Texas, known locally as the Westside Creeks (Alazán, Apache, Martínez, and San Pedro Creeks) and from the San Antonio River. Samples were collected during base flow and after periods of stormwater runoff (poststorm conditions) to determine baseline sediment- and water-quality conditions. Streambed-sediment samples were analyzed for selected constituents, including trace elements and organic contaminants such as pesticides, polychlorinated biphenyls (PCBs), brominated flame retardants, and polycyclic aromatic hydrocarbons (PAHs). Potential risks of contaminants in sediment were evaluated by comparing concentrations of contaminants in sediment to two effects-based sediment-quality guidelines: (1) a lower level, called the threshold effect concentration, below which, harmful effects to benthic biota are not expected, and (2) a higher level, the probable effect concentration (PEC), above which harmful effects are expected to occur frequently. Samples for water-toxicity testing were collected from each stream to provide information about fish toxicity in the study area. The trace metal lead was detected at potentially toxic concentrations greater than the PEC in both the base-flow and poststorm samples collected at two sites sampled on San Pedro Creek. The PECs for the pesticides dichlorodiphenyldichloroethane, dichlorodiphenyldichloroethylene, dichlorodiphenyltrichloroethane, and chlordane were exceeded in some of the samples at the same two sites on San Pedro Creek. Brominated flame retardants and polybrominated diphenyl ether (PBDE) 85, 153, and 154 were found in all streambed-sediment samples. Federal Environmental Quality Guidelines established by Environment Canada for PBDE 99 and PBDE 100 were exceeded in all samples in which PBDE 99 was detected and in a majority of the samples in which PBDE 100 was detected; the greatest concentrations occurred in samples collected at the same two sites on San Pedro Creek where the samples containing elevated lead and pesticide concentrations were collected. All concentrations of total PCBs (computed as the sum of the 18 reported PCB congeners) in the individual streambed-sediment samples were less than the threshold effect concentration, but the concentrations were elevated in the two sites on San Pedro Creek compared to concentrations at other sites. At one site on Apache Creek, 6 of the individual PAHs measured in the sample collected during base-flow conditions exceeded the PECs and 8 of the 9 PECs were exceeded in the sample collected during poststorm conditions. The total PAH concentration in the sample collected at the site during poststorm conditions was 3.3 times greater than the PEC developed for total PAHs. Average PAH profiles computed for base-flow samples and poststorm samples most closely resemble the parking lot coal-tar sealcoat dust PAH source profile, defined as the average PAH concentrations in dust swept from parking lots in six cities in the United States that were sealed with a black, viscous liquid containing coal-tar pitch. Six of ten water samples collected during base-flow conditions caused reductions in Pimephales promelas (fathead minnow) survival and were considered to be toxic.

Texas

Sediment and water chemistry of the San Juan River and Escalante River deltas of Lake Powell, Utah, 2010-2011

Recent studies have documented the presence of trace elements, organic compounds including polycyclic aromatic hydrocarbons, and radionuclides in sediment from the Colorado River delta and from sediment in some side canyons in Lake Powell, Utah and Arizona. The fate of many of these contaminants is of significant concern to the resource managers of the National Park Service Glen Canyon National Recreation Area because of potential health impacts to humans and aquatic and terrestrial species. In 2010, the U.S. Geological Survey began a sediment-core sampling and analysis program in the San Juan River and Escalante River deltas in Lake Powell, Utah, to help the National Park Service further document the presence or absence of contaminants in deltaic sediment. Three sediment cores were collected from the San Juan River delta in August 2010 and three sediment cores and an additional replicate core were collected from the Escalante River delta in September 2011. Sediment from the cores was subsampled and composited for analysis of major and trace elements. Fifty-five major and trace elements were analyzed in 116 subsamples and 7 composited samples for the San Juan River delta cores, and in 75 subsamples and 9 composited samples for the Escalante River delta cores. Six composited sediment samples from the San Juan River delta cores and eight from the Escalante River delta cores also were analyzed for 55 low-level organochlorine pesticides and polychlorinated biphenyls, 61 polycyclic aromatic hydrocarbon compounds, gross alpha and gross beta radionuclides, and sediment-particle size. Additionally, water samples were collected from the sediment-water interface overlying each of the three cores collected from the San Juan River and Escalante River deltas. Each water sample was analyzed for 57 major and trace elements. Most of the major and trace elements analyzed were detected at concentrations greater than reporting levels for the sediment-core subsamples and composited samples. Low-level organochlorine pesticides and polychlorinated biphenyls were not detected in any of the samples. Only one polycyclic aromatic hydrocarbon compound was detected at a concentration greater than the reporting level for one San Juan composited sample. Gross alpha and gross beta radionuclides were detected at concentrations greater than reporting levels for all samples. Most of the major and trace elements analyzed were detected at concentrations greater than reporting levels for water samples.

Utah

Creosote compounds in snails obtained from Pensacola Bay, Florida, near an onshore hazardous-waste site

Snails, Thais haemostoma, were collected from two areas offshore in Pensacola Bay, Florida, near an onshore hazardous-waste site. Tissue from the snails was extracted to isolate the lipophilic compounds and analyzed by gas chromatography/mass spectrometry. Along with naturally occurring compounds, the snail tissue contained large concentrations of polycyclic aromatic compounds, such as phenanthrene, acridine, dibenzothiophene, dibenzofuran, and benzo[a]pyrene. Many of these compounds were characteristic of creosote contamination associated with the onshore hazardous-waste site.

Florida

Geogenic organic contaminants in the low-rank coal-bearing Carrizo-Wilcox aquifer of East Texas, USA

The organic composition of groundwater along the Carrizo-Wilcox aquifer in East Texas (USA), sampled from rural wells in May and September 2015, was examined as part of a larger study of the potential health and environmental effects of organic compounds derived from low-rank coals. The quality of water from the low-rank coal-bearing Carrizo-Wilcox aquifer is a potential environmental concern and no detailed studies of the organic compounds in this aquifer have been published. Organic compounds identified in the water samples included: aliphatics and their fatty acid derivatives, phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, and phthalates. Many of the identified organic compounds (aliphatics, phenols, heterocyclic compounds, PAHs) are geogenic and originated from groundwater leaching of young and unmetamorphosed low-rank coals. Estimated concentrations of individual compounds ranged from about 3.9 to 0.01 μg/L. In many rural areas in East Texas, coal strata provide aquifers for drinking water wells. Organic compounds observed in groundwater are likely to be present in drinking water supplied from wells that penetrate the coal. Some of the organic compounds identified in the water samples are potentially toxic to humans, but at the estimated levels in these samples, the compounds are unlikely to cause acute health problems. The human health effects of low-level chronic exposure to coal-derived organic compounds in drinking water in East Texas are currently unknown, and continuing studies will evaluate possible toxicity.

Texas

Deposition and chemistry of bottom sediments in Cochiti Lake, north-central New Mexico

Bottom sediments were sampled at seven sites in Cochiti Lake in September 1996. Sediment cores penetrating the entire lacustrine sediment sequence were collected at one site near the dam. Surficial sediments were sampled at the near-dam site and six other sites located along the length of the reservoir. Analyses included grain size, major and trace elements, organochlorine compounds, polycyclic aromatic hydrocarbons (PAH's), and radionuclides. Concentrations of trace elements, organic compounds, and radionuclides are similar to those in other Rio Grande reservoirs and are low compared to published sediment-quality guidelines. Most elements and compounds that were detected did not show trends in the age estimated sediment cores with the exception of a decreasing trend in total DDT concentrations from about 1980 to 1992. The mixture of PAH's suggests that the increase is caused by inputs of fuel-related PAH and not combustion- related PAH.

New Mexico

Water- and air-quality monitoring of the Sweetwater Reservoir Watershed, San Diego County, California-Phase One results, continued, 1999-2001

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 with respect to chemical contamination. The study included regular sampling of air and water at Sweetwater Reservoir for chemical contaminants, including volatile organic compounds, polycyclic aromatic hydrocarbons, pesticides, and major and trace elements. Background water samples were collected at Loveland Reservoir for volatile organic compounds and pesticides. The purpose of this study was to monitor changes in contaminant composition and concentration in the air and water resulting from the construction and operation of State Route 125 near Sweetwater Reservoir. To accomplish this, the study was divided into two phases. Phase One sampling was designed to establish baseline conditions for target compounds in terms of detection frequency and concentration in air and water. Phase Two sampling is planned to continue at the established monitoring sites during and after construction of State Route 125 to assess the chemical impact this roadway alignment project may have on the water quality in the reservoir. In addition to the ongoing data collection, several special studies were initiated to assess the occurrence of specific chemicals of concern, such as low-use pesticides, trace metals, and wastewater compounds. This report describes the study design, and the sampling and analytical methods, and presents the results for the second and third years of the study (October 1999 to September 2001). Data collected during the first year of sampling (October 1998 to September 1999) were published in 2002.

California

Sediment-deposition rates and organic compounds in bottom sediment at four sites in Lake Mead, Nevada, May 1998

In May 1998 the U.S. Geological Survey, in cooperation with the University of Nevada, Las Vegas, investigated rates of sediment deposition and concentrations of selected synthetic organic compounds at four sites in Lake Mead. Sediment cores were extracted from two sites (one shallow and one deep) in Las Vegas Bay, from one site in the Overton Arm, and from one site near the historic confluence of the Colorado and Virgin Rivers. The sediment cores were age-dated using cesium-137 and were analyzed for the presence of organochlorine compounds (pesticides and degradation products, polychlorinated biphenyls, dioxins, and furans) and for semivolatile organic compounds (polycyclic aromatic hydrocarbons and phenols). Sediment-deposition rates after impoundment of the Colorado River by Hoover Dam were determined by measuring the accumulation of mass during three different periods: (1) from the approximate impoundment date for each site (1935-37) to the initial occurrence of cesium-137 in the atmosphere (1952); (2) from 1952 to the maximum concentration of cesium-137 in the atmosphere (1964); and (3) from 1964 to the collection date of the sample (1998). Sediment-deposition rates for the entire post-impoundment period (1935-98) averaged 1.45 (g/cm2)/yr (grams per square centimeter per year) at the Las Vegas Bay shallow site, 1.25 (g/cm2)/yr at the Las Vegas Bay deep site, 0.80 (g/cm2)/yr at the Overton Arm site, and 0.65 (g/cm2)/yr at the Colorado and Virgin Rivers confluence site. Sediment-deposition rates after impoundment of the Colorado River by Hoover Dam were determined by measuring the accumulation of mass during three different periods: (1) from the approximate impoundment date for each site (1935-37) to the initial occurrence of cesium-137 in the atmosphere (1952); (2) from 1952 to the maximum concentration of cesium-137 in the atmosphere (1964); and (3) from 1964 to the collection date of the sample (1998). Sediment-deposition rates for the entire post-impoundment period (1935-98) averaged 1.45 (g/cm2)/yr (grams per square centimeter per year) at the Las Vegas Bay shallow site, 1.25 (g/cm2)/yr at the Las Vegas Bay deep site, 0.80 (g/cm2)/yr at the Overton Arm site, and 0.65 (g/cm2)/yr at the Colorado and Virgin Rivers confluence site. Total numbers of synthetic organic compounds detected in sediment samples were 48 at the Las Vegas Bay shallow site, 57 at the Las Vegas Bay deep site, 26 at the Overton Arm site, and 31 at the Colorado and Virgin Rivers confluence site. The most commonly detected organochlorine pesticide and polychlorinated biphenyl compounds were dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene. The most commonly detected dioxin compounds were tetrachlorodibenzo-p-dioxin and octochlorodibenzo-p-dioxin. The most commonly detected furan compounds were tetrachlorodibenzofuran and octochlorodibenzofuran. The most commonly detected polycyclic aromatic hydrocarbons included perylene, benzo[g,h,i]perylene, 2,6-dimethylnaphthalene, and indeno[1,2,3-c,d]pyrene. The most commonly detected phenol compound was phenol.

Open-File Report

Embryotoxic and teratogenic effects of petroleum hydrocarbons in mallards (Anas platyrhynchos)

Egg surface applications of microliter quantities of crude and refined oils of high aromatic content are embryotoxic to mallards (Anas platyrhynchos) and other avian species; applications of aliphatic hydrocarbons have virtually no effect. Mallard eggs at 72 h of development were exposed to a mixture of aromatic hydrocarbons or to aromatic compounds representative to those present in crude oil to assess their toxicity. The class composition of the mixture was similar to that of South Louisiana crude oil, an American Petroleum Institute reference oil. Application of 20 microliter of the mixture reduced embryonic survival by nearly 70%. The temporal pattern of embryonic death was similar to that after exposure to South Louisiana crude oil. Embryonic growth was stunted, as reflected by weight, crown-rump length, and bill length, and there was a significant increase in the incidence of abnormal survivors. When individual classes of aromatic hydrocarbons were tested, tetracyclics caused some embryonic death at the concentrations in the mixture. When classes were tested in all possible combinations of two, no combination appeared to be as toxic as the entire mixture. Addition of the tetracyclic compound chrysene to the aromatic mixture considerably enhanced embryotoxicity, but could not completely account for the toxicity of the crude oil. The presence of additional unidentified polycyclic aromatic hydrocarbons as well as methylated derivatives of polycyclic aromatic compounds such as chrysene may further account for the embryotoxicity of the crude oil.

Journal of Toxicology and Environmental Health

Tumor prevalence and biomarkers of genotoxicity in brown bullhead (Ameiurus nebulosus) in Chesapeake Bay tributaries

We surveyed four Chesapeake Bay tributaries for skin and liver tumors in brown bullhead ( Ameiurus nebulosus ). We focused on the South River, where the highest skin tumor prevalence (53%) in the Bay watershed had been reported. The objectives were to 1) compare tumor prevalence with nearby rivers (Severn and Rhode) and a more remote river (Choptank); 2) investigate associations between tumor prevalence and polynuclear aromatic hydrocarbons (PAHs) and alkylating agents; and 3) statistically analyze Chesapeake Bay bullhead tumor data from 1992 through 2008. All four South River collections exhibited high skin tumor prevalence (19% to 58%), whereas skin tumor prevalence was 2%, 10%, and 52% in the three Severn collections; 0% and 2% in the Choptank collections; and 5.6% in the Rhode collection. Liver tumor prevalence was 0% to 6% in all but one South River collection (20%) and 0% to 6% in the three other rivers. In a subset of samples, PAH-like biliary metabolites and 32 P-DNA adducts were used as biomarkers of exposure and response to polycyclic aromatic compounds (PACs). Adducts from alkylating agents were detected as O6-methyl-2′-deoxyguanosine (O6Me-dG) and O6-ethyl-2′-deoxyguanosine (O6Et-dG) modified DNA. Bullheads from the contaminated Anacostia River were used as a positive control for DNA adducts. 32 P-DNA adduct concentrations were significantly higher in Anacostia bullhead livers compared with the other rivers. We identified alkyl DNA adducts in bullhead livers from the South and Anacostia, but not the Choptank. Neither the PAH-like bile metabolite data, sediment PAH data, nor the DNA adduct data suggest an association between liver or skin tumor prevalence and exposure to PACs or alkylating agents in the South, Choptank, Severn, or Rhode rivers. Logistic regression analysis of the Chesapeake Bay database revealed that sex and length were significant covariates for liver tumors and length was a significant covariate for skin tumors.

Chesapeake Bay watershed, South River

Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ 13 C-dissolved organic carbon (DOC) and Δ 14 C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ 14 C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA 254 ), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ 13 C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.

Environmental Science & Technology

Quantity and quality of stormwater collected from selected stormwater outfalls at industrial sites, Fort Gordon, Georgia, 2012

An assessment of the quantity and quality of stormwater runoff associated with industrial activities at Fort Gordon was conducted from January through August 2012. The assessment was provided to satisfy the requirements from a general permit that authorizes the discharge of stormwater under the National Pollutant Discharge Elimination System from a site associated with industrial activities. The stormwater quantity refers to the runoff discharge at the point and time of the runoff sampling. The study was conducted by the U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon. Stormwater runoff samples were collected from five stations at four industrial sites, including two landfills (SWR11–1 and SWR11–2) and three heating and cooling sites, SWR11–3, SWR11–4, and SWR11–5. The assessment included the collection of physical properties, such as dissolved oxygen and pH; the detection of suspended materials (total suspended solids, total fixed solids, and total volatile solids), nutrients and organic compounds, and major and trace inorganic compounds (metals); and for the three heating and cooling sites, the detection of volatile and semivolatile organic compounds. Landfill site SWR11–2 had the greatest total suspended solid concentration (214 milligrams per liter) of all sites and exceeded the daily maximum effluent limit for landfills. Heating and cooling site SWR11–3 had the greatest total suspended solid concentration (169 milligrams per liter), total fixed solids (101 milligrams per liter), and total volatile solids (68 milligrams per liter) when compared to the three heating and cooling sites. Total nitrogen and phosphorus concentrations were 1.02 and 0.09, and 1.74 and 0.21 milligrams per liter, respectively, at landfill sites SWR11–1 and SWR11–2. At heating and cooling sites, total nitrogen and phosphorus concentrations ranged from 0.53 to 1.08 milligrams per liter and 0.07 to 0.1 milligram per liter, respectively, with the highest concentrations measured at site SWR11–3. Additionally, oil and grease concentrations at all sites were compared to applicable benchmark standards; no sample concentrations exceeded these standards. The estimated dissolved concentrations of cadmium, lead, nickel, zinc, mercury, and silver, and the total recoverable concentrations of arsenic and selenium were compared to applicable benchmark levels and to acute and chronic effect aquatic-life criteria for further screening purposes. The estimated dissolved zinc concentration (105 micrograms per liter) at site SWR11–3 was the only constituent to exceed a benchmark standard (40 micrograms per liter). Estimated dissolved zinc concentrations at sites SWR11–4 and SWR11–5 exceeded acute and chronic effect aquatic-life criteria. Estimated dissolved concentrations of lead exceeded the chronic effect aquatic-life criteria at all sites and exceeded the acute effect criteria at site SWR11–3. Acute and chronic effect aquatic-life criteria for dissolved cadmium were exceeded at site SWR11–3. Samples from sites SWR11–3, SWR11–4, and SWR11–5 were analyzed for 83 volatile and semivolatile organic compounds. Eight polycyclic aromatic hydrocarbon compounds, benzo[ a ]pyrene, benzo[ b ]fluoranthene, benzo[ ghi ]perylene, benzo[ k ]fluoranthene, chrysene, indeno[1,2,3- cd ]pyrene, phenanthrene, and pyrene, were detected at all three sites. Of the 86 volatile and semivolatile organic compounds that were analyzed in stormwater samples from heating and cooling sites, 15 (18 percent) were detected at site SWR11–3, 12 (14 percent) were detected at site SWR11–4, and 17 (20 percent) were detected at site SWR11–5.

Georgia