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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 among water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be adsorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rates 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 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 with concentrations determined during ongoing research. Finally, where data are sufficient, regional and temporal contamination trends in the United States are discussed.

Circular↗

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↗

Relations between land use and organochlorine pesticides, PCBs, and semi-volatile organic compounds in streambed sediment and fish on the island of Oahu, Hawaii

Bed-sediment and/or fish samples were collected from 27 sites around the island of Oahu (representing urban, agricultural, mixed, and forested land use) to determine the occurrence and distribution of hydrophobic organic compounds including organochlorine pesticides, polychlorinated biphenyls (PCBs), and semi-volatile organic compounds (SVOCs). Of the 28 organochlorine compounds analyzed in the fish, 14 were detected during this study. Nineteen of the 31 organochlorine compounds and 40 of the 65 SVOCs were detected in the sediment. Urban sites had the highest number of detections and tended to have the highest concentrations of pesticides. Chlordane compounds were the most frequently detected constituents at urban sites, followed by dieldrin, polycyclic aromatic hydrocarbons (PAHs), and DDT compounds. PAHs were the most frequently detected constituents in watersheds with mixed (urban and agricultural) land use. The only pesticides detected at agricultural sites were DDT and its degradation products, DDD and DDE. No pesticides or PCBs were detected at the forested sites, but a few ubiquitous SVOCs were found in sediments at some forested sites. In general, concentrations of the most frequently detected pesticides were higher in fish than in sediment. Following a trend that has been observed elsewhere in the nation, concentrations of most organochlorine pesticides and PCBs are decreasing in Hawaii.

Hawaii↗

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.

Rock Creek, Washington D.C.↗

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↗

Metagenomic analysis of planktonic microbial consortia from a non-tidal urban-impacted segment of James River

Knowledge of the diversity and ecological function of the microbial consortia of James River in Virginia, USA, is essential to developing a more complete understanding of the ecology of this model river system. Metagenomic analysis of James River's planktonic microbial community was performed for the first time using an unamplified genomic library and a 16S rDNA amplicon library prepared and sequenced by Ion PGM and MiSeq, respectively. From the 0.46-Gb WGS library (GenBank:SRR1146621; MG-RAST:4532156.3), 4 × 10 6 reads revealed >3 × 10 6 genes, 240 families of prokaryotes, and 155 families of eukaryotes. From the 0.68-Gb 16S library (GenBank:SRR2124995; MG-RAST:4631271.3; EMB:2184), 4 × 10 6 reads revealed 259 families of eubacteria. Results of the WGS and 16S analyses were highly consistent and indicated that more than half of the bacterial sequences were Proteobacteria , predominantly Comamonadaceae . The most numerous genera in this group were Acidovorax (including iron oxidizers, nitrotolulene degraders, and plant pathogens), which accounted for 10 % of assigned bacterial reads. Polaromonas were another 6 % of all bacterial reads, with many assignments to groups capable of degrading polycyclic aromatic hydrocarbons. Albidiferax (iron reducers) and Variovorax (biodegraders of a variety of natural biogenic compounds as well as anthropogenic contaminants such as polycyclic aromatic hydrocarbons and endocrine disruptors) each accounted for an additional 3 % of bacterial reads. Comparison of these data to other publically-available aquatic metagenomes revealed that this stretch of James River is highly similar to the upper Mississippi River, and that these river systems are more similar to aquaculture and sludge ecosystems than they are to lakes or to a pristine section of the upper Amazon River. Taken together, these analyses exposed previously unknown aspects of microbial biodiversity, documented the ecological responses of microbes to urban effects, and revealed the noteworthy presence of 22 human-pathogenic bacterial genera (e.g., Enterobacteriaceae , pathogenic Pseudomonadaceae , and ‘ Vibrionales' ) and 6 pathogenic eukaryotic genera (e.g., Trypanosomatidae and Vahlkampfiidae). This information about pathogen diversity may be used to promote human epidemiological studies, enhance existing water quality monitoring efforts, and increase awareness of the possible health risks associated with recreational use of James River.

Virginia↗

Carbon isotope systematics of individual hydrocarbons in hydrothermal petroleum from Escanaba Trough, Northeastern Pacific Ocean

We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7%, respectively) reflect a primarily terrestrial organic matter source.We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba Trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7 per mill, respectively) reflect a primarily terrestrial organic matter source.

Organic Geochemistry↗

Organic waste compounds in streams: Occurrence and aquatic toxicity in different stream compartments, flow regimes, and land uses in southeast Wisconsin, 2006–9

An assessment of organic chemicals and aquatic toxicity in streams located near Milwaukee, Wisconsin, indicated high potential for adverse impacts on aquatic organisms that could be related to organic waste compounds (OWCs). OWCs used in agriculture, industry, and households make their way into surface waters through runoff, leaking septic-conveyance systems, regulated and unregulated discharges, and combined sewage overflows, among other sources. Many of these compounds are toxic at elevated concentrations and (or) known to have endocrine-disrupting potential, and often they occur as complex mixtures. There is still much to be learned about the chronic exposure effects of these compounds on aquatic populations. During 2006–9, the U.S. Geological Survey, in cooperation with the Milwaukee Metropolitan Sewerage District (MMSD), conducted a study to determine the occurrence and potential toxicity of OWCs in different stream compartments and flow regimes for streams in the Milwaukee area. Samples were collected at 17 sites and analyzed for a suite of 69 OWCs. Three types of stream compartments were represented: water column, streambed pore water, and streambed sediment. Water-column samples were subdivided by flow regime into stormflow and base-flow samples. One or more compounds were detected in all 196 samples collected, and 64 of the 69 compounds were detected at least once. Base-flow samples had the lowest detection rates, with a median of 12 compounds detected per sample. Median detection rates for stormflow, pore-water, and sediment samples were more than double that of base-flow samples. Compounds with the highest detection rates include polycyclic aromatic hydrocarbons (PAHs), insecticides, herbicides, and dyes/pigments. Elevated occurrence and concentrations of some compounds were detected in samples from urban sites, as compared with more rural sites, especially during stormflow conditions. These include the PAHs and the domestic waste-water-indicator compounds, among others. Urban runoff and storm-related leaks of sanitary sewers and (or) septic systems may be important sources of these and other compounds to the streams. The Kinnickinnic River, a highly urbanized site, had the highest detection rates and concentrations of compounds of all the sampled sites. The Milwaukee River near Cedarburg—one of the least urban sites—and the Outer Milwaukee Harbor site had the lowest detection rates and concentrations. Aquatic-toxicity benchmarks were exceeded for 12 of the 25 compounds with known benchmarks. The compounds with the greatest benchmark exceedances were the PAHs, both in terms of exceedance frequency (up to 93 percent for some compounds in sediment samples) and magnitude (concentrations up to 1,024 times greater than the benchmark value). Other compounds with toxicity-benchmark exceedances include Bis(2-ethylhexyl) phthalate (a plasticizer), 2-Methylnapthalene (a component of fuel and oil), phenol (an antimicrobial disinfectant with diverse uses), and 4-Nonylphenol (sum of all isomers; a detergent metabolite, among other uses). Analyzed as a mixture, the suite of PAH compounds were found to be potentially toxic for most non-base-flow samples. Bioassay tests were conducted on samples from 14 streams: Ceriodaphnia dubia in base-flow samples, Ceriodaphnia dubia and Hyallela azteca in pore-water samples, and Hyallela azteca and Chironomus tentans in sediment samples. The greatest adverse effect was observed in tests with Chironomus tentans from sediment samples. The weight of Chironomus tentans after exposure to sediments decreased with increased OWC concentrations. This was most evident in the relation between PAH results and Chironomus tentans bioassay results for the majority of samples; however, solvents and flame retardants appeared to be important for one site each. These results for PAHs were consistent with assessment of PAH potency factors for sediment, indicating that PAHs were likely to have adverse effects on aquatic organisms in many of the streams studied.

Wisconsin↗

Investigation of hydrophobic contaminants in an urban slough system using passive sampling - Insights from sampling rate calculations

Semipermeable membrane devices (SPMDs) were deployed in the Columbia Slough, near Portland, Oregon, on three separate occasions to measure the spatial and seasonal distribution of dissolved polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds (OCs) in the slough. Concentrations of PAHs and OCs in SPMDs showed spatial and seasonal differences among sites and indicated that unusually high flows in the spring of 2006 diluted the concentrations of many of the target contaminants. However, the same PAHs - pyrene, fluoranthene, and the alkylated homologues of phenanthrene, anthracene, and fluorene - and OCs - polychlorinated biphenyls, pentachloroanisole, chlorpyrifos, dieldrin, and the metabolites of dichlorodiphenyltrichloroethane (DDT) - predominated throughout the system during all three deployment periods. The data suggest that storm washoff may be a predominant source of PAHs in the slough but that OCs are ubiquitous, entering the slough by a variety of pathways. Comparison of SPMDs deployed on the stream bed with SPMDs deployed in the overlying water column suggests that even for the very hydrophobic compounds investigated, bed sediments may not be a predominant source in this system. Perdeuterated phenanthrene (phenanthrene-d10). spiked at a rate of 2 ??g per SPMD, was shown to be a reliable performance reference compound (PRC) under the conditions of these deployments. Post-deployment concentrations of the PRC revealed differences in sampling conditions among sites and between seasons, but indicate that for SPMDs deployed throughout the main slough channel, differences in sampling rates were small enough to make site-to-site comparisons of SPMD concentrations straightforward. ?? Springer Science+Business Media B.V. 2007.

Environmental Monitoring and Assessment↗

A survey of benthic sediment contaminants in reaches of the Columbia River Estuary based on channel sedimentation characteristics

While previous studies have documented contaminants in fish, sediments, water, and wildlife, few specifics are known about the spatial distribution of contaminants in the Columbia River Estuary (CRE). Our study goal was to characterize sediment contaminant detections and concentrations in reaches of the CRE that were concurrently being sampled to assess contaminants in water, invertebrates, fish, and osprey (Pandion haliaetus) eggs. Our objectives were to develop a survey design based on sedimentation characteristics and then assess whether sediment grain size, total organic carbon (TOC), and contaminant concentrations and detections varied between areas with different sedimentation characteristics. We used a sediment transport model to predict sedimentation characteristics of three 16 km river reaches in the CRE. We then compartmentalized the modeled change in bed mass after a two week simulation to define sampling strata with depositional, stable, or erosional conditions. We collected and analyzed bottom sediments to assess whether substrate composition, organic matter composition, and contaminant concentrations and detections varied among strata within and between the reaches. We observed differences in grain size fractions between strata within and between reaches. We found that the fine sediment fraction was positively correlated with TOC. Contaminant concentrations were statistically different between depositional vs. erosional strata for the industrial compounds, personal care products and polycyclic aromatic hydrocarbons class (Indus–PCP–PAH). We also observed significant differences between strata in the number of detections of Indus–PCP–PAH (depositional vs. erosional; stable vs. erosional) and for the flame retardants, polychlorinated biphenyls, and pesticides class (depositional vs. erosional, depositional vs. stable). When we estimated mean contaminant concentrations by reach, we observed higher contaminant concentrations in the furthest downstream reach with a decreasing trend in the two upstream reaches. Contaminant survey designs that account for sedimentation characteristics could increase the probability that sampling is allocated to areas likely to be contaminated.

Columbia River Estuary↗

Exposure to runoff from coal-tar-sealed pavement induces genotoxicity and impairment of DNA repair capacity in the RTL-W1 fish liver cell line

Coal-tar-based (CTB) sealcoat, frequently applied to parking lots and driveways in North America, contains elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) and related compounds. The RTL-W1 fish liver cell line was used to investigate two endpoints (genotoxicity and DNA-repair-capacity impairment) associated with exposure to runoff from asphalt pavement with CTB sealcoat or with an asphalt-based sealcoat hypothesized to contain about 7% CTB sealcoat (AS-blend). Genotoxic potential was assessed by the Formamido pyrimidine glycosylase (Fpg)-modified comet assay for 1:10 and 1:100 dilutions of runoff samples collected from 5 h to 36 d following sealcoat application. DNA-repair capacity was assessed by the base excision repair comet assay for 1:10 dilution of samples collected 26 h and 36 d following application. Both assays were run with and without co-exposure to ultraviolet-A radiation (UVA). With co-exposure to UVA, genotoxic effects were significant for both dilutions of CTB runoff for three of four sample times, and for some samples of AS-blend runoff. Base excision repair was significantly impaired for CTB runoff both with and without UVA exposure, and for AS-blend runoff only in the absence of UVA. This study is the first to investigate the effects of exposure to the complex mixture of chemicals in coal tar on DNA repair capacity. The results indicate that co-exposure to runoff from CT-sealcoated pavement and UVA as much as a month after sealcoat application has the potential to cause genotoxicity and impair DNA repair capacity.

Science of the Total Environment↗

Contaminants of emerging concern in the Great Lakes: Science to inform management practices for protecting the health and integrity of wildlife populations from adverse effects: GLRI action plan I, focus area 1, goal 5

Executive Summary: Under Action Plan I (2010-2014) of the Great Lakes Restoration Initiative (GLRI), Federal and Academic partners began an investigation of the presence and distribution of contaminants of emerging concern (CECs) in the Great Lakes and potential impacts on fish and wildlife. The term CECs is applied to a broad range of chemicals that are currently in use but for which we currently lack good understanding of whether fish, wildlife, or humans are being exposed and/or whether negative health or environmental effects are expected if exposure occurs. Pharmaceuticals, personal care products, flame retardants, many current use pesticides, and poly- and perfluorinated chemicals are some well-known groups of CECs, but there is no definitive or comprehensive list that can be used to support the management of CECs to reduce impacts on the Great Lakes ecosystem. Four overarching goals were identified for this collaborative investigation: 1. Evaluate the sources, occurrence, and distribution of CECs across the Great Lakes Basin. 2. Examine associations between the distribution of CECs and land-use patterns. 3. Review both scientific literature and field-generated data to determine the potential for CECs to cause adverse effects on Great Lakes fish and wildlife populations. 4. Develop efficient strategies to survey and/or monitor for threats that CECs may pose in order to take effective management actions before those threats evolve into large scale impacts on Great Lakes ecosystems or the services they provide. Achievement of these goals ensures progress towards Focus Area 1: Toxic Substances and Areas of Concern from GLRI Action Plan I, Goal 5: “ The health and integrity of wildlife populations and habitat are protected from adverse chemical and biological effects associated with the presence of toxic substances in the Great Lakes Basin ”. This large-scale research effort was comprised of individual and collaborative projects from multiple federal agencies and academic institutions, involving over 85 investigators, and overseen by the U.S. Environmental Protection Agency (EPA) Region 5, Great Lakes National Program Office. Partners include the United States Geological Survey, the National Oceanic and Atmospheric Administration, U.S. Fish and Wildlife Service, Saint Cloud State University, the U.S. EPA Office of Research and Development, and the U.S. Army Corps of Engineers. Key findings: 1. Contaminants of emerging concern were found throughout the monitored Great Lakes tributaries, but types and concentrations vary in association with regional land use. CECs were detected in nearly all samples collected. The type and concentration of the specific contaminants detected varied considerably among field sites and in association with land use type, such as urban, agricultural, wetland, 2 or forest. Contaminants were detected in the water column, sediment, and tissues of all species surveyed in the current work (mussels, aquatic insects, fish, and insect-eating birds). 2. There were over 20 contaminants for which CEC concentrations approached or exceeded those reported to cause toxicity in laboratory experiments. This was based on detection in water, sediments and or biota at one or more field sites. These contaminants represent compounds that warrant further investigation and monitoring with respect to potential impacts in certain areas of the Great Lakes basin. Based on the present investigation, compounds of greatest concern include: polycyclic aromatic hydrocarbons, associated with oil-based products and combustion of organic matter; atrazine, an herbicide; dichlorvos, an insecticide; and ibuprofen and venlafaxine, both pharmaceuticals. 3. Results suggest that mixtures of CECs presently found in most Great Lakes tributary locations surveyed may elicit subtle biological effects, but likely are not, alone, causing obvious detriment to current communities of fish and wildlife. CECs detected in the Great Lakes were associated with subtle biological effects like changes in gene expression, altered circulating glucose, etc. in both wild-caught and laboratory-reared organisms. These effects were generally not indicative of reproductive failure or mortality. However, the effects may have more serious implications when combined with other sources of stress like habitat degradation, changing climate conditions, and competition with invasive species. Due to limited historical data, it is unknown whether severe CEC-related impacts have already affected aquatic communities in waterbodies that have received long-term inputs of these contaminants. Likewise, under Action Plan I, biological effects were not necessarily evaluated at the sites where CEC concentrations exceeding laboratory toxicity thresholds were detected. As a result, strategic, ongoing surveillance and monitoring of CECs is warranted. This collaborative investigation resulted in new tools, approaches, and data that can be used to inform and support the management of CECs to reduce their impacts on Great Lakes natural resources. The following products of this research effort are available through https://communities.geoplatform.gov/glri/ or by contacting the investigators (see technical chapters found in Appendices A-F): 1. Database of CEC occurrence and concentrations in US tributary streams. The database includes CEC detections in water, sediment, and fish and wildlife tissues, and represents the most comprehensive survey of CECs in the Great Lakes Region. 2. Synopses of results and key findings. Integrated summaries of results, conclusions, and management implications of the CEC research are available through reports, topical fact sheets, and presentations. 3. Technical publications: This collaborative research effort has resulted in over 50 peer-reviewed publications, agency reports, and data releases that can be of use to resource managers, the scientific community, and members of the public. 4. Innovative tools. Innovative monitoring devices, sampling equipment, conceptual frameworks, and software applications were developed over the course of this 3 research. These tools are transferable to stakeholders via internet accessibility or via specifications, instructions, and demonstration detailed in technical publications. Hypotheses to guide CECs research under Action Plan II. Findings from 2010-2014 were used to guide further research in 2015-2018 for basin-wide surveillance of CECs and for sites warranting further study of potential biological impacts of CECs. Additional surveillance included both evaluation of additional classes of contaminants and expanded lists for chemical classes shown to be of greatest concern. Mixtures of some of the most frequently detected contaminants were also tested in laboratory studies to understand whether long term exposures to multiple contaminants may result in effects not evident from uncontrolled, short-term field experiments.

Great Lakes↗

Potential for chemical transport beneath a storm-runoff recharge (retention) basin for an industrial catchment in Fresno, California

A wide variety of chemicals from urban runoff were found at elevated concentrations in sediment that accumulated in a storm-runoff recharge basin in an industrial part of the city of Fresno. The chemicals include as many as 20 inorganic elements and about the same number of organic compounds, primarily organochlorine pesticides and polycyclic aromatic hydrocarbons. Most of these contaminants were found to be sorbed to the upper 4 centimeters of sediment, which also is the maximum depth to which atmospheric lead-210 penetrated. None of the contaminants were detected above background concentrations in the sediment at depths greater than 16 centimeters. In shallow sediment, zinc is the inorganic element that showed the greatest enrichment; its concentration was 38 times higher in surface sediment (0-1 centimeter) than in deeper strata (below 16 centi- meters). Organic carbon enrichment in the surface sediment was nearly 1,000 times. Although batch- elutriation experiments demonstrated the potential for leaching of contaminants attached to sediments, a sharp decrease in concentrations with increasing sediment depth, and the extremely low level of contaminants in two monitor wells adjacent to the basin, confirmed the absence of contaminant transport to the water table. Continued long-term protection for ground water is afforded by an approximately 8-meter-thick unsaturated zone beneath the basin. On the basis of its hundredfold-higher concentration in the recharge pond then in ground water, zinc is indicated as the most sensitive surrogate for monitoring possible ground-water degradation by inorganic cations.

Water-Resources Investigations Report↗