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Fractionation of fulvic acid by iron and aluminum oxides: influence on copper toxicity to Ceriodaphnia dubia

This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC 50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC 50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA 254 ), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.

Environmental Science & Technology↗

Occurrence of pesticides in shallow groundwater of the United States: initial results from the National Water-Quality Assessment program

The first phase of intensive data collection for the National Water-Quality Assessment (NAWQA) was completed during 1993−1995 in 20 major hydrologic basins of the United States. Groundwater land-use studies, designed to sample recently recharged groundwater (generally within 10 years) beneath specific land-use and hydrogeologic settings, are a major component of the groundwater quality as sessment for NAWQA. Pesticide results from the 41 land-use studies conducted during 1993−1995 indicate that pesticides were commonly detected in shallow groundwater, having been found at 54.4% of the 1034 sites sampled in agricultural and urban settings across the United States. Pesticide concentrations were generally low, with over 95% of the detections at concentrations less than 1 μg/L. Of the 46 pesticide compounds examined, 39 were detected. The compounds detected most frequently were atrazine (38.2%), deethylatrazine (34.2%), simazine (18.0%), metolachlor (14.6%), and prometon (13.9%). Statistically significant relations were observed between frequencies of detection and the use, mobility, and persistence of these compounds. Pesticides were commonly detected in both agricultural (56.4%; 813 sites) and urban (46.6%; 221 sites) settings. Frequent detections of pesticides in urban areas indicate that, as is the case with agricultural pesticide use in agricultural areas, urban and suburban pesticide use significantly contribute to pesticide occurrence in shallow groundwater. Although pesticides were detected in groundwater sampled in urban areas and all nine of the agricultural land-use categories examined, significant variations in occurrence were observed among these categories. Maximum contaminant levels (MCLs) established by the U.S. Environmental Protection Agency for drinking water were exceeded for only one pesticide (atrazine, 3 μg/L) at a single location. However, MCLs have been established for only 25 of the 46 pesticide compounds examined, do not cover pesticide degradates, and, at present, do not take into account additive or synergistic effects of combinations of pesticide compounds or potential effects on nearby aquatic ecosystems.

Environmental Science & Technology↗

Online bibliographic sources in hydrology

Traditional commercial bibliographic databases and indexes provide some access to hydrology materials produced by the government; however, these sources do not provide comprehensive coverage of relevant hydrologic publications. This paper discusses bibliographic information available from the federal government and state geological surveys, water resources agencies, and depositories. In addition to information in these databases, the paper describes the scope, styles of citing, subject terminology, and the ways these information sources are currently being searched, formally and informally, by hydrologists. Information available from the federal and state agencies and from the state depositories might be missed by limiting searches to commercially distributed databases.

Science and Technology Libraries↗

Biology: Integrating core to essential variables (Bio-ICE) task team report for hard corals

The Interagency Ocean Observation Committee (IOOC) is chartered by the White House Office of Science and Technology Policy (OSTP) Subcommittee on Ocean Science and Technology (SOST). The purpose of the IOOC is to advise, assist, and make recommendations to the SOST on matters related to ocean observations via task teams such as the Biology - Integrating Core to Essential Variables (Bio-ICE) task team. The goal of the Bio-ICE task team is to advance the integration of biological observations from local, regional, and federal sources using best practices to inform national needs and ultimately feed seamlessly into the Global Ocean Observing System (GOOS), as appropriate. To accomplish this goal, and for the first time at the U.S. federal government level, a subgroup of the Bio-ICE task team focused on tropical, shallow-water (0-30 m) hard corals to identify commonalities between the U.S. Integrated Ocean Observing System (IOOS) core biological variable1 of “coral species and abundance,” the GOOS Essential Ocean Variable2 (EOV) “hard coral cover and composition,” the Group on Earth Observations Biological Observation Network (GEO BON) Essential Biodiversity Variables3 (EBVs), and the Global Climate Observing System (GCOS) Essential Climate Variables4 (ECVs) (Figure 1). The EOV data allows production of EBVs such as time series of maps of genetic composition, species populations, etc. Recognizing the complementarity of the different essential variable frameworks helps to promote best practices in observing and information management to facilitate data interoperability (Figure 1). The task team was charged with identifying where there are synergies in terms of spatial and temporal observing requirements and existing observation infrastructure and data delivery, including best practices and standard operating procedures. The task team also made suggestions to improve pathways for data flow for observations of these variables from Regional Associations of the U.S. IOOS, other nonfederal partners, and federal sources. The focus of the task team was on identifying and implementing best practices surrounding standardized data collection and data delivery to make continued progress toward adhering to the Findability, Accessibility, Interoperability, and Reuse (FAIR) and Collective benefit, Authority to control, Responsibility, and Ethics (CARE) data principles.

Task Team Report↗

Free zinc ion and dissolved orthophosphate effects on phytoplankton from Coeur d'Alene Lake, Idaho

Coeur d'Alene Lake in northern Idaho is fed by two major rivers: the Coeur d'Alene River from the east and the St. Joe River from the south, with the Spokane River as its outlet to the north. This phosphorus-limited lake has been subjected to decades of mining (primarily for zinc and silver) and other anthropogenic inputs. A 32 full-factorial experimental design was used to examine the interactive effects of free (uncomplexed) zinc ion and dissolved-orthophosphate concentrations on phytoplankton that were isolated from two sites along a longitudinal zinc-concentration gradient in Coeur d'Alene Lake. The two sites displayed different dominant taxa. Chlorella minutissima, a dominant species near the southern St. Joe River inlet, exhibited greater sensitivity to free Zn ions than Asterionella formosa, collected nearer the Coeur d'Alene River mouth with elevated dissolved-zinc concentrations. Empirical phytoplankton-response models were generated to describe phytoplankton growth in response to remediation strategies in the surrounding watershed. If dissolved Zn can be reduced in the water column from >500 nM (i.e., current concentrations near and down stream of the Coeur d'Alene River plume) to <3 nM (i.e., concentrations near the southern St. Joe River inlet) such that the lake is truly phosphorus limited, management of phosphorus inputs by surrounding communities will ultimately determine the limnologic state of the lake.

Idaho↗

Geographic information systems, remote sensing, and spatial analysis activities in Texas, 2002-07

Geographic information system (GIS) technology has become an important tool for scientific investigation, resource management, and environmental planning. A GIS is a computer-aided system capable of collecting, storing, analyzing, and displaying spatially referenced digital data. GIS technology is particularly useful when analyzing a wide variety of spatial data such as with remote sensing and spatial analysis. Remote sensing involves collecting remotely sensed data, such as satellite imagery, aerial photography, or radar images, and analyzing the data to gather information or investigate trends about the environment or the Earth's surface. Spatial analysis combines remotely sensed, thematic, statistical, quantitative, and geographical data through overlay, modeling, and other analytical techniques to investigate specific research questions. It is the combination of data formats and analysis techniques that has made GIS an essential tool in scientific investigations. This document presents information about the technical capabilities and project activities of the U.S. Geological Survey (USGS) Texas Water Science Center (TWSC) GIS Workgroup from 2002 through 2007.

Fact Sheet↗

Riparian methylmercury production increases riverine mercury flux and food web concentrations

The production and uptake of toxic methylmercury (MeHg) impacts aquatic ecosystems globally. Rivers can be dynamic and difficult systems to study for MeHg production and bioaccumulation, hence identifying sources of MeHg to these systems is both challenging and important for resource management within rivers and main-stem reservoirs. Riparian zones, which are known biogeochemical hotspots for MeHg production, are understudied as potential sources of MeHg to rivers. Here, we present a comprehensive quantification of the hydrologic and biogeochemical processes governing MeHg concentrations, loads, and bioaccumulation at 16 locations along 164 km of the agriculturally intensive Snake River (Idaho, Oregon USA) during summer baseflow conditions, with emphasis on riparian production of MeHg. Approximately one-third of the MeHg load of the Snake River could not be attributed to inflowing waters (upgradient, tributaries, or irrigation drains). Across the study reach, increases in MeHg loads in surface waters were significantly correlated with MeHg concentrations in riparian porewaters, suggesting riparian zones were likely an important source of MeHg to the Snake River. Across all locations, MeHg concentrations in surface waters positively correlated with MeHg concentrations in benthic snails and clams, supporting that riparian produced MeHg was assimilated into local aquatic food webs. This study contributes new insights into riparian MeHg production within rivers which can inform mitigation efforts to reduce MeHg bioaccumulation in fish.

Idaho, Oregon↗

What goes up must come down: Integrating air and water quality monitoring for nutrients

Excess nitrogen and phosphorus (“nutrients”) loadings continue to affect ecosystem function and human health across the U.S. Our ability to connect atmospheric inputs of nutrients to aquatic end points remains limited due to uncoupled air and water quality monitoring. Where connections exist, the information provides insights about source apportionment, trends, risk to sensitive ecosystems, and efficacy of pollution reduction efforts. We examine several issues driving the need for better integrated monitoring, including: coastal eutrophication, urban hotspots of deposition, a shift from oxidized to reduced nitrogen deposition, and the disappearance of pristine lakes. Successful coordination requires consistent data reporting; collocating deposition and water quality monitoring; improving phosphorus deposition measurements; and filling coverage gaps in urban corridors, agricultural areas, undeveloped watersheds, and coastal zones.

Environmental Science and Technology↗

Comparing polychlorinated biphenyl concentrations and patterns in the Saginaw River using sediment, caged fish, and semipermeable membrane devices

Three techniques of assessing bioavailable polychlorinated biphenyls (PCBs) in the Saginaw River, MI, were compared: sediments, caged fish, and semipermeable membrane devices (SPMDs). SPMDs and caged fish were placed in the river for 28 days at five sites where sediments were also sampled. The samples were analyzed for PCB congeners to determine concentrations and patterns. Total PCB concentrations ranged from 33 to 280 ng/g (dry weight) in sediments, 46 to 290 ng/g (wet weight) in caged fish, and 77 to 790 ng/g in SPMDs. Previously reported rates of PCB accumulation by SPMDs were used to estimate aqueous concentrations from the PCB concentrations detected in the SPMDs. Sediment-water partition coefficients were used to estimate aqueous PCB concentrations from sediment. Steady-state bioconcentration factors and depuration rate constants were used to estimate dissolved PCB concentrations from caged channel catfish. Relative PCB patterns from the SPMDs, caged fish, and sediment were compared using principal components analysis. SPMD and sediment samples provide complementary information. Sediments reflect long-term accumulation and weathering, while SPMDs integrate water concentrations only during the sampling period. Because of higher water solubilities of lower-chlorinated PCBs these predominate in the SPMDs as compared to in the fish and sediments. Contaminant profile differences between caged fish and SPMDs are likely due to metabolism and depuration of certain PCB congeners by fish.Three techniques of assessing bioavailable polychlorinated biphenyls (PCBs) in the Saginaw River, Ml, were compared: sediments, caged fish, and semipermeable membrane devices (SPMDs). SPMDs and caged fish were placed in the river for 28 days at five sites where sediments were also sampled. The samples were analyzed for PCB congeners to determine concentrations and patterns. Total PCB concentrations ranged from 33 to 280 ng/g (dry weight) in sediments, 46 to 290 ng/g (wet weight) in caged fish, and 77 to 790 ng/g in SPMDs. Previously reported rates of PCB accumulation by SPMDs were used to estimate aqueous concentrations from the PCB concentrations detected in the SPMDs. Sediment-water partition coefficients were used to estimate aqueous PCB concentrations from sediment. Steady-state bioconcentration factors and depuration rate constants were used to estimate dissolved PCB concentrations from caged channel catfish. Relative PCB patterns from the SPMDs, caged fish, and sediment were compared using principal components analysis. SPMD and sediment samples provide complementary information. Sediments reflect long-term accumulation and weathering, while SPMDs integrate water concentrations only during the sampling period. Because of higher water solubilities of lower-chlorinated PCBs these predominate in the SPMDs as compared to in the fish and sediments. Contaminant profile differences between caged fish and SPMDs are likely due to metabolism and depuration of certain PCB congeners by fish.At five sites in the Saginaw River, MI, PCB concentrations were determined in the summer of 1993 using three methods: sediment analysis, concentrations in caged fish, and concentrations in semipermeable membrane devices (SPMDs). On average, total PCB concentrations in the SPMDs were twice those found in caged fish, and the SPMD-to-fish concentration ratios of di-, tri-, tetra-, and pentaCB homologues were 10.0, 3.0, 2.5, and 1.4, respectively. Average concentrations in the sediments were approximately half those in the SPMDs, and the caged fish showed a greater preponderance of higher log octanol-water partition coefficient PCBs similar to the sediment pattern. On average, the water PCB concentrations estimated from sediment concentrations were five times higher than those calculated from SPMDs and three times higher than those estimated from caged fish. The total PCB concentrations in sediment, caged fish, and SPMDs ranged 33-280, 46-290, and 77-790 ng/g, respectiv

Environmental Science & Technology↗

Effects of sampling strategies on estimates of annual mean herbicide concentrations in midwestern rivers

The effects of 10 sampling strategies on estimates of annual mean concentrations of the herbicides atrazine, alachlor, and cyanazine in selected midwestern rivers were tested. The accuracy of the strategies was computed by comparing time-weighted annual mean herbicide concentrations calculated from water samples collected from 17 locations on midwestern rivers, with simulated annual mean concentrations calculated for each sampling strategy, using Monte Carlo simulations. Monthly sampling was the most accurate strategy tested. The U.S. Environmental Protection Agency requires quarterly sampling for municipalities using surface water as a source of drinking water. Due to the seasonality of herbicide occurrence and transport, quarterly sampling underestimates annual mean herbicide concentrations in over 40% of the simulations. Three of the strategies tested showed that, relative to quarterly sampling, a more accurate representation of annual mean concentrations could be obtained by sampling more frequently during spring and early summer runoff and assuming zero herbicide concentration during late summer and winter months.

Environmental Science & Technology↗

Degradation of chloroacetanilide herbicides: The prevalence of sulfonic and oxanilic acid metabolites in Iowa groundwaters and surface waters

Water samples were collected from 88 municipal wells throughout Iowa during the summer and were collected monthly at 12 stream sites in eastern Iowa from March to December 1996 to study the occurrence of the sulfonic and oxanilic metabolites of acetochlor, alachlor, and metolachlor. The sulfonic and oxanilic metabolites were present in almost 75% of the groundwater samples and were generally present from 3 to 45 times more frequently than their parent compounds. In groundwater, the median value of the summed concentrations of acetochlor, alachlor, and metolachlor was less than 0.05 &mu;g/L, and the median value of the summed concentrations of the six metabolites was 1.2 &mu;g/L. All surface water samples contained at least one detectable metabolite compound. Individual metabolites were detected from 2 to over 100 times more frequently than the parent compounds. In surface water, the median value of the summed concentrations of the three parent compounds was 0.13 &mu;g/L, and the median value of the summed concentrations of the six metabolites was 6.4 &mu;g/L. These data demonstrate the importance of analyzing both parent compounds and metabolites to more fully understand the environmental fate and transport of herbicides in the hydrologic system.

Iowa↗

Seasonal differences and grazing pressure alter the fate of gold nanoparticles in a microcosm experiment

Gold nanoparticles (AuNPs) are used as models to track and predict NP fates and effects in ecosystems. Previous work found that aquatic macrophytes and their associated biofilm primarily drove the fate of AuNPs within aquatic ecosystems and that seasonality was an important abiotic factor in the fate of AuNPs. Therefore, the present work aims to study if grazers, by feeding on these interfaces, modify the AuNP fate and if this is altered by seasonal fluctuations. Microcosms were dosed with 44.8 μg/L of AuNP weekly for 4 weeks and maintained in environmental chambers simulating Spring and Fall light and temperature conditions. We discovered that seasonal changes and the presence of grazers significantly altered the fate of Au. Higher temperatures in the warmer season increased dissolved organic carbon (DOC) content in the water column, leading to stabilization of Au in the water column. Additionally, snail grazing on biofilm growing on the Egeria densa surface led to a transfer of Au from macrophytes to the organic matter above the sediments. These results demonstrate that climate and grazers significantly impacted the fate of Au from AuNPs, highlighting the role that grazers might have in a large and biologically more complex ecosystem.

Environmental Science & Technology↗

Effects of an extreme flood on trace elements in river water—From urban stream to major river basin

Major floods adversely affect water quality through surface runoff, groundwater discharge, and damage to municipal water infrastructure. Despite their importance, it can be difficult to assess the effects of floods on streamwater chemistry because of challenges collecting samples and the absence of baseline data. This study documents water quality during the September 2013 extreme flood in the South Platte River, Colorado, USA. Weekly time-series water samples were collected from 3 urban source waters (municipal tap water, streamwater, and wastewater treatment facility effluent) under normal-flow and flood conditions. In addition, water samples were collected during the flood at 5 locations along the South Platte River and from 7 tributaries along the Colorado Front Range. Samples were analyzed for 54 major and trace elements. Specific chemical tracers, representing different natural and anthropogenic sources and geochemical behaviors, were used to compare streamwater composition before and during the flood. The results differentiate hydrological processes that affected water quality: (1) in the upper watershed, runoff diluted most dissolved constituents, (2) in the urban corridor and lower watershed, runoff mobilized soluble constituents accumulated on the landscape and contributed to stream loading, and (3) flood-induced groundwater discharge mobilized soluble constituents stored in the vadose zone.

Colorado↗

Effect of calcium on the bioavailability of dissolved uranium(VI) in plant roots under circumneutral pH

We integrated field measurements, hydroponic experiments, microscopy, and spectroscopy to investigate the effect of Ca(II) on dissolved U(VI) uptake by plants in 1 mM HCO 3 – solutions at circumneutral pH. The accumulation of U in plants (3.1–21.3 mg kg –1 ) from the stream bank of the Rio Paguate, Jackpile Mine, New Mexico served as a motivation for this study. Brassica juncea was the model plant used for the laboratory experiments conducted over a range of U (30–700 μg L –1 ) and Ca (0–240 mg L –1 ) concentrations. The initial U uptake followed pseudo-second-order kinetics. The initial U uptake rate ( V 0 ) ranged from 4.4 to 62 μg g –1 h –1 in experiments with no added Ca and from 0.73 to 2.07 μg g –1 h –1 in experiments with 12 mg L –1 Ca. No measurable U uptake over time was detected for experiments with 240 mg L –1 Ca. Ternary Ca–U–CO 3 complexes may affect the decrease in U bioavailability observed in this study. Elemental X-ray mapping using scanning transmission electron microscopy–energy-dispersive spectrometry detected U–P-bearing precipitates within root cell walls in water free of Ca. These results suggest that root interactions with Ca and carbonate in solution affect the bioavailability of U in plants. This study contributes relevant information to applications related to U transport and remediation of contaminated sites.

Environmental Science & Technology↗

Bioremediation of uranium contamination with enzymatic uranium reduction

Enzymatic uranium reduction by Desulfovibrio desulfuricans readily removed uranium from solution in a batch system or when D. desulfuricans was separated from the bulk of the uranium-containing water by a semipermeable membrane. Uranium reduction continued at concentrations as high as 24 mM. Of a variety of potentially inhibiting anions and metals evaluated, only high concentrations of copper inhibited uranium reduction. Freeze-dried cells, stored aerobically, reduced uranium as fast as fresh cells. D. desulfuricans reduced uranium in pH 4 and pH 7.4 mine drainage waters and in uraniumcontaining groundwaters from a contaminated Department of Energy site. Enzymatic uranium reduction has several potential advantages over other bioprocessing techniques for uranium removal, the most important of which are as follows: the ability to precipitate uranium that is in the form of a uranyl carbonate complex; high capacity for uranium removal per cell; the formation of a compact, relatively pure, uranium precipitate.

Environmental Science & Technology↗

Migration of wood-preserving chemicals in contaminated groundwater in a sand aquifer at Pensacola, Florida

Operation of a wood-preserving facility for nearly 80 years at Pensacola, FL, contaminated the near-surface groundwater with creosote and pentachlorophenol. The major source of aquifer contamination was unlined surface impoundments that were in direct hydraulic contact with the groundwater. Episodes of overtopping the impoundments and overland flow of treatment liquor and waste were also significant to the migration and contamination of the groundwater. Solutes contaminating the ground-water are mainly naphthalene and substituted phenols. Sorption did not influence retardation of solutes in transport in the groundwater. Phenol and the mono substituted methylphenols appear to be undergoing bio-transformation. Pentachlorophenol (PCP) was not found in significant concentrations in the groundwater possibly because the solubility of PCP is approximately 5 mg/L at pH 6, near the average acidity for the groundwater.

Florida↗

Factors associated with sources, transport, and fate of volatile organic compounds and their mixtures in aquifers of the United States

Factors associated with sources, transport, and fate of volatile organic compounds (VOCs) in groundwater from aquifers throughout the United States were evaluated using statistical methods. Samples were collected from 1631 wells throughout the conterminous United States between 1996 and 2002 as part of the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey. Water samples from wells completed in aquifers used to supply drinking water were analyzed for more than 50 VOCs. Wells were primarily rural domestic water supplies (1184), followed by public water supplies (216); the remaining wells (231) supplied a variety of uses. The median well depth was 50 meters. Age-date information shows that about 60% of the samples had a fraction of water recharged after 1953. Chloroform, toluene, 1,2,4-trimethylbenzene, and perchloroethene were some of the frequently detected VOCs. Concentrations generally were less than 1 ??g/L. Source factors include, in order of importance, general land-use activity, septic/sewer density, and sites where large concentrations of VOCs are potentially released, such as leaking underground storage tanks. About 10% of all samples had VOC mixtures that were associated with concentrated sources; 20% were associated with dispersed sources. Important transport factors included well/screen depth, precipitation/groundwater recharge, air temperature, and various soil characteristics. Dissolved oxygen was strongly associated with VOCs and represents the fate of many VOCs in groundwater. Well type (domestic or public water supply) was also an important explanatory factor. Results of multiple analyses show the importance of (1) accounting for both dispersed and concentrated sources of VOCs, (2) measuring dissolved oxygen when sampling wells to help explain the fate of VOCs, and (3) limiting the type of wells sampled in monitoring networks to avoid unnecessary variance in the data, or controlling for this variance during data analysis.

Environmental Science & Technology↗

Choices in recreational water quality monitoring: new opportunities and health risk trade-offs

With the recent release of new recreational water quality monitoring criteria, there are more options for regulatory agencies seeking to protect beachgoers from waterborne pathogens. Included are methods that can reduce analytical time, providing timelier estimates of water quality, but the application of these methods has not been examined at most beaches for expectation of health risk and management decisions. In this analysis, we explore health and monitoring outcomes expected at Lake Michigan beaches using protocols for indicator bacteria including culturable Escherichia coli (E. coli; EC), culturable enterococci (ENT), and enterococci as analyzed by qPCR (QENT). Correlations between method results were generally high, except at beaches with historically high concentrations of EC. The “beach action value” was exceeded most often when using EC or ENT as the target indicator; QENT exceeded the limit far less frequently. Measured water quality between years was varied. Although methods with equivalent health expectation have been established, the lack of relationship among method outcomes and annual changes in mean indicator bacteria concentrations complicates the decision-making process. The monitoring approach selected by beach managers may be a combination of available tools that maximizes timely health protection, cost efficiency, and collaboration among beach jurisdictions.

Environmental Science & Technology↗