Geology topics

Larry B. Barber

Publications and source records attributed to Larry B. Barber.

At least 55 records · Page 3Linked to original sources

USGS2014

Riverbank filtration potential of pharmaceuticals in a wastewater-impacted stream

Pharmaceutical contamination of shallow groundwater is a substantial concern in effluent-dominated streams, due to high aqueous mobility, designed bioactivity, and effluent-driven hydraulic gradients. In October and December 2012, effluent contributed approximately 99% and 71%, respectively, to downstream flow in Fourmile Creek, Iowa, USA. Strong hydrologic connectivity was observed between surface-water and shallow-groundwater. Carbamazepine, sulfamethoxazole, and immunologically-related compounds were detected in groundwater at greater than 0.02 μg L −1 at distances up to 6 m from the stream bank. Direct aqueous-injection HPLC-MS/MS revealed 43% and 55% of 110 total pharmaceutical analytes in surface-water samples in October and December, respectively, with 16% and 6%, respectively, detected in groundwater approximately 20 m from the stream bank. The results demonstrate the importance of effluent discharge as a driver of local hydrologic conditions in an effluent-impacted stream and thus as a fundamental control on surface-water to groundwater transport of effluent-derived pharmaceutical contaminants.

Iowa↗

USGS2013

U.S. Geological Survey environmental health science strategy — Providing environmental health science for a changing world

Executive Summary America has an abundance of natural resources. We have bountiful clean water, fertile soil, and unrivaled national parks, wildlife refuges, and public lands. These resources enrich our lives and preserve our health and wellbeing. These resources have been maintained because of our history of respect for their value and an enduring commitment to their vigilant protection. Awareness of the social, economic, and personal value of the health of our environment is increasing. The emergence of environmentally driven diseases caused by exposure to contaminants and pathogens is a growing concern worldwide. New health threats and patterns of established threats are affected by both natural and anthropogenic changes to the environment. Human activities are key drivers of emerging (new and re-emerging) health threats. Societal demands for land and natural resources, quality of life, and economic prosperity lead to environmental change. Natural earth processes, climate trends, and related climatic events will compound the environmental impact of human activities. These environmental drivers will influence exposure to disease agents, including viral, bacterial, prion, and fungal pathogens, parasites, synthetic chemicals and substances, natural earth materials, toxins, and other biogenic compounds. The U.S. Geological Survey (USGS) defines environmental health science broadly as the interdisciplinary study of relations among the quality of the physical environment, the health of the living environment, and human health. The interactions among these three spheres are driven by human activities, ecological processes, and natural earth processes; the interactions affect exposure to contaminants and pathogens and the severity of environmentally driven diseases in animals and people. This definition provides USGS with a framework for synthesizing natural science information from across the Bureau and providing it to environmental, natural resource, agricultural, and public health managers. USGS specializes in science at the environment-health interface, by characterizing the processes that affect the interaction among the physical environment, the living environment, and people, and the resulting factors that affect ecological and human exposure to disease agents. The USGS is a Federal science agency with a broad range of natural science expertise relevant to environmental health. USGS provides scientific information and tools as a scientific basis for management and policy decisionmaking. This report describes a 10-year strategy that encompasses the portfolio of USGS environmental health science. It summarizes national environmental health priorities that USGS is best suited to address, and will serve as a strategic framework for USGS environmental health science goals, actions, and outcomes for the next decade. Implementation of this strategy is intended to aid coordination of USGS environmental health activities and to provide a focal point for disseminating information to stakeholders. The “One Health” paradigm advocated by the World Health Organization (WHO; World Health Organization, 2011), and the American Veterinary Medical Association (AVMA; American Veterinary Medical Association, 2008), among others, is based on a general recognition that the health of humans, animals, and the environment are inextricably linked. Thus, successful efforts to protect that health will require increased interdisciplinary research and increased communication and collaboration among the broader scientific and health community. This strategy is built upon that paradigm.

Circular↗

USGS2013

Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams

Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 μg L –1 ) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 μg L –1 ), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications.

Colorado, Iowa↗

USGS2013

Long-term groundwater contamination after source removal—The role of sorbed carbon and nitrogen on the rate of reoxygenation of a treated-wastewater plume on Cape Cod, MA, USA

The consequences of groundwater contamination can remain long after a contaminant source has been removed. Documentation of natural aquifer recoveries and empirical tools to predict recovery time frames and associated geochemical changes are generally lacking. This study characterized the long-term natural attenuation of a groundwater contaminant plume in a sand and gravel aquifer on Cape Cod, Massachusetts, after the removal of the treated-wastewater source. Although concentrations of dissolved organic carbon (DOC) and other soluble constituents have decreased substantially in the 15 years since the source was removed, the core of the plume remains anoxic and has sharp redox gradients and elevated concentrations of nitrate and ammonium. Aquifer sediment was collected from near the former disposal site at several points in time and space along a 0.5-km-long transect extending downgradient from the disposal site and analyses of the sediment was correlated with changes in plume composition. Total sediment carbon content was generally low (< 8 to 55.8 μmol (g dry wt)− 1) but was positively correlated with oxygen consumption rates in laboratory incubations, which ranged from 11.6 to 44.7 nmol (g dry wt)− 1 day− 1. Total water extractable organic carbon was < 10–50% of the total carbon content but was the most biodegradable portion of the carbon pool. Carbon/nitrogen (C/N) ratios in the extracts increased more than 10-fold with time, suggesting that organic carbon degradation and oxygen consumption could become N-limited as the sorbed C and dissolved inorganic nitrogen (DIN) pools produced by the degradation separate with time by differential transport. A 1-D model using total degradable organic carbon values was constructed to simulate oxygen consumption and transport and calibrated by using observed temporal changes in oxygen concentrations at selected wells. The simulated travel velocity of the oxygen gradient was 5–13% of the groundwater velocity. This suggests that the total sorbed carbon pool is large relative to the rate of oxygen entrainment and will be impacting groundwater geochemistry for many decades. This has implications for long-term oxidation of reduced constituents, such as ammonium, that are being transported downgradient away from the infiltration beds toward surface and coastal discharge zones.

Massachusetts↗

USGS2013

Chemical contaminants in water and sediment near fish nesting sites in the Potomac River basin: determining potential exposures to smallmouth bass (Micropterus dolomieu)

The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects. A total of 39 chemicals were detected at least once in the discrete-water samples, with atrazine, caffeine, deethylatrazine, simazine, and iso-chlorotetracycline being most frequently detected. Of the most frequently detected chemicals, only caffeine was detected in water from the reference site. No biogenic hormones/sterols were detected in the discrete-water samples. In contrast, 100 chemicals (including six biogenic hormones/sterols) were found in a least one passive-water sample, with 25 being detected at all such samples. In addition, 46 chemicals (including seven biogenic hormones/sterols) were found in the bed-sediment samples, with caffeine, cholesterol, indole, para-cresol, and sitosterol detected in all such samples. The number of herbicides detected in discrete-water samples per site had a significant positive relation to TO rank (a nonparametric indicator of TO), with significant positive relations between TO rank and atrazine concentrations in discrete-water samples and to total hormone/sterol concentration in bed-sediment samples. Such significant correlations do not necessarily imply causation, as these chemical compositions and concentrations likely do not adequately reflect total SMB exposure history, particularly during critical life stages.

Potomac River Basin↗

USGS2013

Widespread occurrence of neuro-active pharmaceuticals and metabolites in 24 Minnesota rivers and wastewaters

Concentrations of 17 neuro-active pharmaceuticals and their major metabolites (bupropion, hydroxy-bupropion, erythro-hydrobupropion, threo-hydrobupropion, carbamazepine, 10,11,-dihydro-10,11,-dihydroxycarbamazepine, 10-hydroxy-carbamazepine, citalopram, N -desmethyl-citalopram, fluoxetine, norfluoxetine, gabapentin, lamotrigine, 2-N-glucuronide-lamotrigine, oxcarbazepine, venlafaxine and O-desmethyl-venlafaxine), were measured in treated wastewater and receiving surface waters from 24 locations across Minnesota, USA. The analysis of upstream and downstream sampling sites indicated that the wastewater treatment plants were the major source of the neuro-active pharmaceuticals and associated metabolites in surface waters of Minnesota. Concentrations of parent compound and the associated metabolite varied substantially between treatment plants (concentrations ± standard deviation of the parent compound relative to its major metabolite) as illustrated by the following examples; bupropion and hydrobupropion 700 ± 1000 ng L − 1 , 2100 ± 1700 ng L − 1 , carbamazepine and 10-hydroxy-carbamazepine 480 ± 380 ng L − 1 , 360 ± 400 ng L − 1 , venlafaxine and O -desmethyl-venlafaxine 1400 ± 1300 ng L − 1 , 1800 ± 2300 ng L − 1 . Metabolites of the neuro-active compounds were commonly found at higher or comparable concentrations to the parent compounds in wastewater effluent and the receiving surface water. Neuro-active pharmaceuticals and associated metabolites were detected only sporadically in samples upstream from the effluent outfall. Metabolite to parent ratios were used to evaluate transformation, and we determined that ratios in wastewater were much lower than those reported in urine, indicating that the metabolites are relatively more labile than the parent compounds in the treatment plants and in receiving waters. The widespread occurrence of neuro-active pharmaceuticals and metabolites in Minnesota effluents and surface waters indicate that this is likely a global environmental issue, and further understanding of the environmental fate and impacts of these compounds is warranted.

Minnesota↗

USGS2012

Occurrence of triclosan, triclocarban, and its lesser chlorinated congeners in Minnesota freshwater sediments collected near wastewater treatment plants

The antimicrobial agents triclosan (TCS), triclocarban (TCC) and their associated transformation products are of increasing concern as environmental pollutants due to their potential adverse effects on humans and wildlife, including bioaccumulation and endocrine-disrupting activity. Analysis by tandem mass spectrometry of 24 paired freshwater bed sediment samples (top 10 cm) collected by the U.S. Geological Survey near 12 wastewater treatment plants (WWTPs) in Minnesota revealed TCS and TCC concentrations of up to 85 and 822 ng/g dry weight (dw), respectively. Concentrations of TCS and TCC in bed sediments collected downstream of WWTPs were significantly greater than upstream concentrations in 58% and 42% of the sites, respectively. Dichloro- and non-chlorinated carbanilides (DCC and NCC) were detected in sediments collected at all sites at concentrations of up to 160 and 1.1 ng/g dw, respectively. Overall, antimicrobial concentrations were significantly higher in lakes than in rivers and creeks, with relative abundances decreasing from TCC > TCS > DCC > NCC. This is the first statewide report on the occurrence of TCS, TCC and TCC transformation products in freshwater sediments. Moreover, the results suggest biological or chemical TCC dechlorination products to be ubiquitous in freshwater environments of Minnesota, but whether this transformation occurs in the WWTP or bed sediment remains to be determined.

Minnesota↗

USGS2012

Concentration of organic contaminants in fish and their biological effects in a wastewater-dominated urban stream

Data are presented on the concentrations of alkylphenol and alkylphenol ethoxylates (APEs) and persistent organic compounds in largemouth bass collected from a waste-water dominated stream in downtown Chicago. The fish residue concentrations of APEs are compared to concentrations of the APEs in the water that were collected at weekly intervals over two months bracketing the fall (2006) and a spring (2007) fish collection. The concentrations of APEs were significantly higher in the spring-collected fish (5.42 μg/g) versus the fall (0.99 μg/g) tand these differences were shared by differences in the water concentrations (spring — 11.47 versus fall — 3.44 μg/L). The differences in water concentration were negatively correlated with water temperatures observed over the two sampling times. Fish residue concentrations of persistent organic compounds (PCBs, PBDEs, toxaphene, and many legacy pesticides including the DDT family) did not vary from fall to spring. Some of these residue concentrations were comparable to the highest NPE (nonylphenol ethoxylate) homologue concentrations, e.g. NP1EO was 3.5 μg/g in the bass for the spring, the PBDE-congener 47 and p,p′-DDE averaged 1.0 μg/g and 0.5 μg/g, respectively, over both seasons. All the other persistent single-analyte concentrations were lower. Biological endpoints for endocrine effects measured in the same fish showed that there was an apparent positive correlation for physiological effects based on increased vitellogenin levels in males versus concentration of NPEs; however there were no observable histological differences in fall versus spring fish samples.

Science of the Total Environment↗

USGS2012

Groundwater-quality data for a treated-wastewater plume near the Massachusetts Military Reservation, Ashumet Valley, Cape Cod, Massachusetts, 2006-08

A plume of contaminated groundwater extends from former disposal beds at the Massachusetts Military Reservation's wastewater-treatment plant toward Ashumet Pond, coastal ponds, and Vineyard Sound, Cape Cod, Massachusetts. Treated sewage-derived wastewater was discharged to the rapid-infiltration beds for nearly 60 years before the disposal site was moved to a different location in December 1995. Water-quality samples were collected from monitoring wells, multilevel samplers, and profile borings to characterize the nature and extent of the contaminated groundwater and to observe the water-quality changes after the wastewater disposal ceased. Data are presented here for water samples collected in 2007 from 394 wells (at 121 well-cluster locations) and 780 multilevel-sampler ports (at 42 locations) and in 2006-08 at 306 depth intervals in profile borings (at 20 locations) in and near the treated-wastewater plume. Analyses of these water samples for field parameters (specific conductance, pH, dissolved oxygen and phosphate concentrations, and alkalinity); absorbance of ultraviolet/visible light; and concentrations of nitrous oxide, dissolved organic carbon, methylene blue active substances, selected anions and nutrients, including nitrate and ammonium, and selected inorganic solutes, including cations, anions, and minor elements, are presented in tabular format. The natural restoration of the sand and gravel aquifer after removal of the treated-wastewater source, along with interpretations of the water quality in the treated-wastewater plume, have been documented in several published reports that are listed in the references.

Massachusetts↗

USGS2012

USGS Environmental health science strategy: providing environmental health science for a changing world: Public review release

America has an abundance of natural resources. We have bountiful clean water, fertile soil, and unrivaled national parks, wildlife refuges, and public lands. These resources enrich our lives and preserve our health and wellbeing. These resources have been maintained because of our history of respect for their value and an enduring commitment to their vigilant protection. Awareness of the social, economic, and personal value of the health of our environment is increasing. The emergence of environmentally driven diseases caused by environmental exposure to contaminants and pathogens is a growing concern worldwide. New health threats and patterns of established threats are affected by both natural and anthropogenic changes to the environment. Human activities are key drivers of emerging (new and re-emerging) health threats. Societal demands for land and natural resources, a better quality of life, improved economic prosperity, and the environmental impacts associated with these demands will continue to increase. Natural earth processes, climate trends, and related climatic events will add to the environmental impact of human activities. These environmental drivers will influence exposure to disease agents, including viral, bacterial, prion, and fungal pathogens, parasites, natural earth materials, toxins and other biogenic compounds, and synthetic chemicals and substances. The U.S. Geological Survey (USGS) defines environmental health science broadly as the interdisciplinary study of relations among the quality of the physical environment, the health of the living environment, and human health. The interactions among these three spheres are driven by human activities, ecological processes, and natural earth processes; the interactions affect exposure to contaminants and pathogens and the severity of environmentally driven diseases in animals and people. This definition provides USGS with a framework for synthesizing natural science information from across the Bureau and providing it to environmental, natural resource, agricultural, and public-health managers. The USGS is a Federal science agency with a broad range of natural science expertise relevant to environmental health. USGS provides scientific information and tools as a scientific basis for management and policy decision making. USGS specializes in science at the environment-health interface, by characterizing the processes that affect the interaction among the physical environment, the living environment, and people, and the resulting factors that affect ecological and human exposure to disease agents. This report describes a 10-year strategy that encompasses the portfolio of USGS environmental health science. It summarizes national environmental health priorities that USGS is best suited to address, and will serve as a strategic framework for USGS environmental health science goals, actions, and outcomes for the next decade. Implementation of this strategy is intended to aid coordination of USGS environmental health activities and to provide a focal point for disseminating information to stakeholders. The "One Health" paradigm advocated by the World Health Organization (WHO, 2011), and the American Veterinary Medicine Association (AVMA, 2008), among others, is based on a general recognition that the health of humans, animals, and the environment are inextricably linked. Thus, successful efforts to protect that health will require increased interdisciplinary research and increased communication and collaboration among the broader scientific and health community. This strategy is built upon that paradigm. The vision, mission, and five cornerstone goals of the USGS Environmental Health Science Strategy were developed with significant input from a wide range of stakeholders. Vision - The USGS is a premier source of the environmental health science needed to safeguard the health of the environment, fish, wildlife, and people. Mission - The mission of USGS in environmental health science is to contribute scientific information to environmental, natural resource, agricultural, and public-health managers, who use that science to support sound decision making. USGS provides the science to: - Goal 1: Identify, prioritize, and detect contaminants and pathogens of emerging environmental concern. - Goal 2: Reduce the impact of contaminants on the environment, fish, wildlife, and people. - Goal 3: Reduce the impact of pathogens on the environment, fish, wildlife, and people. - Goal 4: Discover the complex interactions and combined effects of exposure to contaminants and pathogens. - Goal 5: Prepare for and respond to environmental impacts and related health threats of natural and anthropogenic disasters. Goals 1 through 4 are intended to provide science to address environmental health threats in a logical order, from informing prevention and preparedness, to supporting systematic management response to environmental health issues. Goal 4 addresses the interaction among contaminants and pathogens, an issue of emerging concern in environmental health science. Goal 5 acknowledges the fact that natural and anthropogenic disasters can cause immediate and prolonged adverse environmental health threats. This strategy proposes that USGS take the following strategic science actions to achieve each of the five goals of this strategy: Goal 1: Identify, prioritize, and detect contaminants and pathogens of emerging environmental concern. - Strategic Science Action 1. - Prioritize contaminants and pathogens of emerging concern to guide research, detection, and management activities. - Strategic Science Action 2. - Conduct surveillance and monitoring to provide early warning of emerging health threats. - Strategic Science Action 3. - Develop approaches and tools that identify vulnerable environmental settings, ecosystems, and species. Goal 2: Reduce the impact of contaminants on the environment, fish, wildlife, and people. - Strategic Science Action 1. - Systematically characterize the sources, occurrence, transport and fate of environmental contaminants to guide efforts to manage and mitigate contamination. - Strategic Science Action 2. - Evaluate the threats of contamination on the health of the environment, fish, wildlife, and people, and inform the associated management and protection efforts. - Strategic Science Action 3. - Characterize potential human exposure to support establishment of health-based standards or guidelines and contamination-reduction efforts. Goal 3: Reduce the impact of pathogens on the environment, fish, wildlife, and people. - Strategic Science Action 1. - Determine the biotic and abiotic factors that control the ecology of infectious diseases affecting natural populations of aquatic and terrestrial species and potential transmission to other animals and humans. - Strategic Science Action 2. - Establish how natural and anthropogenic environmental changes affect the distribution and severity of infectious diseases in natural populations of aquatic and terrestrial species and potential transmission to other animals and humans. - Strategic Science Action 3. - Develop surveillance systems to identify changing patterns of disease activity in priority geographic areas. Goal 4: Discover the complex interactions and combined effects of exposure to contaminants and pathogens. - Strategic Science Action 1. - Identify how exposure to one class of disease agents (contaminants or pathogens) can make an organism more susceptible to effects from exposure to the other class of disease agents. - Strategic Science Action 2. - Implement interdisciplinary studies that characterize the effects of combined exposure to pathogens and contaminants. Goal 5: Prepare for and respond to the environmental impacts and related health threats of natural and anthropogenic disasters. - Strategic Science Action 1. - Establish a formal interdisciplinary science capability to rapidly assess the environmental health risks associated with disasters. - Strategic Science Action 2. - Enhance methods to anticipate, prepare for, and identify environmental, ecological, and related health impacts of future disasters. This strategy is one of seven USGS science strategies developed concurrently: - Climate and Land Use Change - Core Science Systems - Ecosystems - Energy and Mineral Resources - Environmental Health - Natural Hazards - Water. This strategy describes how USGS will address the highest priority environmental health issues facing the Nation. The ultimate intended outcome of this science strategy is prevention and reduction of adverse impacts to the quality of the environment, the health of our living resources, and human health. Communication with, and receiving input from, partners and stakeholders regarding their science needs is essential for successful implementation of this strategy. It is incumbent on USGS to reach out to all stakeholders to ensure that USGS efforts are focused on the highest priority environmental health issues and that products are provided in the most timely and usable form to all those who can use them. USGS must reach out to the scientific community, internally and externally, to ensure that our efforts are integrated with and take full advantage of the activities of others.

Open-File Report↗

USGS2012

Endocrine disrupting chemicals in Minnesota lakes - Water-quality and hydrological data from 2008 and 2010

Understanding the sources, fate, and effects of endocrine disrupting chemicals in aquatic ecosystems is important for water-resource management. This study was conducted during 2008 and 2010 to establish a framework for assessing endocrine disrupting chemicals, and involved a statewide survey of their occurrence in 14 Minnesota lakes and a targeted study of different microhabitats on a single lake. The lakes ranged in size from about 0.1 to 100 square kilometers, varied in trophic status from oligotrophic to eutrophic, and spanned a range of land-uses from wetlands and forest to agricultural and urban use. Water and sediment samples were collected from the near-shore littoral environment and analyzed for endocrine disrupting chemicals, including trace elements, acidic organic compounds, neutral organic compounds, and steroidal hormones. In addition, polar organic compound integrative samplers were deployed for 21 days and analyzed for the same organic compounds. One lake was selected for a detailed microhabitat study of multiple near-shore environments. This report compiles the results from the field measurements and laboratory chemical analysis of water, sediment, and polar organic compound integrative sampler samples collected during 2008 and 2010. Most of the organic compounds measured were not detected in any of the water samples, although a few compounds were detected in several of the lakes.

Minnesota↗

USGS2012

Determination of steroid hormones and related compounds in filtered and unfiltered water by solid-phase extraction, derivatization, and gas chromatography with tandem mass spectrometry

A new analytical method has been developed and implemented at the U.S. Geological Survey National Water Quality Laboratory that determines a suite of 20 steroid hormones and related compounds in filtered water (using laboratory schedule 2434) and in unfiltered water (using laboratory schedule 4434). This report documents the procedures and initial performance data for the method and provides guidance on application of the method and considerations of data quality in relation to data interpretation. The analytical method determines 6 natural and 3 synthetic estrogen compounds, 6 natural androgens, 1 natural and 1 synthetic progestin compound, and 2 sterols: cholesterol and 3--coprostanol. These two sterols have limited biological activity but typically are abundant in wastewater effluents and serve as useful tracers. Bisphenol A, an industrial chemical used primarily to produce polycarbonate plastic and epoxy resins and that has been shown to have estrogenic activity, also is determined by the method. A technique referred to as isotope-dilution quantification is used to improve quantitative accuracy by accounting for sample-specific procedural losses in the determined analyte concentration. Briefly, deuterium- or carbon-13-labeled isotope-dilution standards (IDSs), all of which are direct or chemically similar isotopic analogs of the method analytes, are added to all environmental and quality-control and quality-assurance samples before extraction. Method analytes and IDS compounds are isolated from filtered or unfiltered water by solid-phase extraction onto an octadecylsilyl disk, overlain with a graded glass-fiber filter to facilitate extraction of unfiltered sample matrices. The disks are eluted with methanol, and the extract is evaporated to dryness, reconstituted in solvent, passed through a Florisil solid-phase extraction column to remove polar organic interferences, and again evaporated to dryness in a reaction vial. The method compounds are reacted with activated -methyl--trimethylsilyl trifluoroacetamide at 65 degrees Celsius for 1 hour to form trimethylsilyl or trimethylsilyl-enol ether derivatives that are more amenable to gas chromatographic separation than the underivatized compounds. Analysis is carried out by gas chromatography with tandem mass spectrometry using calibration standards that are derivatized concurrently with the sample extracts. Analyte concentrations are quantified relative to specific IDS compounds in the sample, which directly compensate for procedural losses (incomplete recovery) in the determined and reported analyte concentrations. Thus, reported analyte concentrations (or analyte recoveries for spiked samples) are corrected based on recovery of the corresponding IDS compound during the quantification process. Recovery for each IDS compound is reported for each sample and represents an absolute recovery in a manner comparable to surrogate recoveries for other organic methods used by the National Water Quality Laboratory. Thus, IDS recoveries provide a useful tool for evaluating sample-specific analytical performance from an absolute mass recovery standpoint. IDS absolute recovery will differ and typically be lower than the corresponding analyte’s method recovery in spiked samples. However, additional correction of reported analyte concentrations is unnecessary and inappropriate because the analyte concentration (or recovery) already is compensated for by the isotope-dilution quantification procedure. Method analytes were spiked at 10 and 100 nanograms per liter (ng/L) for most analytes (10 times greater spike levels were used for bisphenol A and 100 times greater spike levels were used for 3--coprostanol and cholesterol) into the following validation-sample matrices: reagent water, wastewater-affected surface water, a secondary-treated wastewater effluent, and a primary (no biological treatment) wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100 percent, with overall relative standard deviation of 28 percent. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples and analyzed in 2009–2010 ranged from 84–104 percent, with relative standard deviations of 6–36 percent. Concentrations for two analytes, equilin and progesterone, are reported as estimated because these analytes had excessive bias or variability, or both. Additional database coding is applied to other reported analyte data as needed, based on sample-specific IDS recovery performance. Detection levels were derived statistically by fortifying reagent water at six different levels (0.1 to 4 ng/L) and range from about 0.4 to 4 ng/L for 16 analytes. Interim reporting levels applied to analytes in this report range from 0.8 to 8 ng/L. Bisphenol A and the sterols (cholesterol and 3-beta-coprostanol) were consistently detected in laboratory and field blanks. The minimum reporting levels were set at 100 ng/L for bisphenol A and at 200 ng/L for the two sterols to prevent any bias associated with the presence of these compounds in the blanks. A minimum reporting level of 2 ng/L was set for 11-ketotestosterone to minimize false positive risk from an interfering siloxane compound emanating as chromatographic-column bleed, from vial septum material, or from other sources at no more than 1 ng/L.

Techniques and Methods↗

USGS2011

Fate of 4-nonylphenol and 17β-estradiol in the Redwood River of Minnesota

The majority of previous research investigating the fate of endocrine-disrupting compounds has focused on single processes generally in controlled laboratory experiments, and limited studies have directly evaluated their fate and transport in rivers. This study evaluated the fate and transport of 4-nonylphenol, 17β-estradiol, and estrone in a 10-km reach of the Redwood River in southwestern Minnesota. The same parcel of water was sampled as it moved downstream, integrating chemical transformation and hydrologic processes. The conservative tracer bromide was used to track the parcel of water being sampled, and the change in mass of the target compounds relative to bromide was determined at two locations downstream from a wastewater treatment plant effluent outfall. In-stream attenuation coefficients ( k stream ) were calculated by assuming first-order kinetics (negative values correspond to attenuation, whereas positive values indicate production). Attenuation of 17β-estradiol ( k stream = −3.2 ± 1.0 day –1 ) was attributed primarily due to sorption and biodegradation by the stream biofilm and bed sediments. Estrone ( k stream = 0.6 ± 0.8 day –1 ) and 4-nonylphenol ( k stream = 1.4 ± 1.9 day –1 ) were produced in the evaluated 10-km reach, likely due to biochemical transformation from parent compounds (17β-estradiol, 4-nonylphenolpolyethoxylates, and 4-nonyphenolpolyethoxycarboxylates). Despite attenuation, these compounds were transported kilometers downstream, and thus additive concentrations from multiple sources and transformation of parent compounds into degradates having estrogenic activity can explain their environmental persistence and widespread observations of biological disruption in surface waters.

Minnesota↗

USGS2011

Role of biofilms in sorptive removal of steroidal hormones and 4-nonylphenol compounds from streams

Stream biofilms play an important role in geochemical processing of organic matter and nutrients, however, the significance of this matrix in sorbing trace organic contaminants is less understood. This study focused on the role of stream biofilms in sorbing steroidal hormones and 4-nonylphenol compounds from surface waters using biofilms colonized in situ on artificial substrata and subsequently transferred to the laboratory for controlled batch sorption experiments. Steroidal hormones and 4-nonylphenol compounds readily sorb to stream biofilms as indicated by organic matter partition coefficients ( K om , L kg –1 ) for 17β-estradiol (10 2.5–2.8 L kg –1 ), 17α-ethynylestradiol (10 2.5–2.9 L kg –1 ), 4-nonylphenol (10 3.4–4.6 L kg –1 ), 4-nonylphenolmonoethoxylate (10 3.5–4.0 L kg –1 ), and 4-nonylphenoldiethoxylate (10 3.9–4.3 L kg –1 ). Experiments using water quality differences to induce changes in the relative composition of periphyton and heterotrophic bacteria in the stream biofilm did not significantly affect the sorptive properties of the stream biofilm, providing additional evidence that stream biofilms will sorb trace organic compounds under of variety of environmental conditions. Because sorption of the target compounds to stream biofilms was linearly correlated with organic matter content, hydrophobic partition into organic matter appears to be the dominant mechanism. An analysis of 17β-estradiol and 4-nonylphenol hydrophobic partition into water, biofilm, sediment, and dissolved organic matter matrices at mass/volume ratios typical of smaller rivers showed that the relative importance of the stream biofilm as a sorptive matrix was comparable to bed sediments. Therefore, stream biofilms play a primary role in attenuating these compounds in surface waters. Because the stream biofilm represents the base of the stream ecosystem, accumulation of steroidal hormones and 4-nonylphenol compounds in the stream biofilm may be an exposure pathway for organisms in higher trophic levels.

Environmental Science & Technology↗

USGS2011

Effect of dissolved organic carbon on the transport and attachment behaviors of Cryptosporidium parvum oocysts and carboxylate-modified microspheres advected through temperate humic and tropical volcanic agricultural soil

Transport of Cryptosporidium parvum oocysts and microspheres in two disparate (a clay- and Fe-rich, volcanic and a temperate, humic) agricultural soils were studied in the presence and absence of 100 mg L –1 of sodium dodecyl benzene sulfonate (SDBS), and Suwannee River Humic Acid (SRHA) at pH 5.0–6.0. Transport of carboxylate-modified, 1.8 μm microspheres in soil columns was highly sensitive to the nature of the dissolved organic carbon (DOC), whereas oocysts transport was more affected by soil mineralogy. SDBS increased transport of microspheres from 48% to 87% through the tropical soil and from 43% to 93% in temperate soil. In contrast, SRHA reduced transport of microspheres from 48% to 28% in tropical soil and from 43% to 16% in temperate soil. SDBS also increased oocysts transport through the temperate soil 5-fold, whereas no oocyst transport was detected in tropical soil. SRHA had only a nominal effect in increasing oocysts transport in tropical soil, but caused a 6-fold increase in transport through the temperate soil. Amendments of only 4 mg L –1 SRHA and SDBS decreased oocyst hydrophobicity from 66% to 20% and from 66% to 5%, respectively. However, SDBS increased microsphere hydrophobicity from 16% to 33%. Soil fines, which includes clays, and SRHA, both caused the oocysts zeta potential (ζ) to become more negative, but caused the highly hydrophilic microspheres to become less negatively charged. The disparate behaviors of the two colloids in the presence of an ionic surfactant and natural organic matter suggest that microspheres may not be suitable surrogates for oocysts in certain types of soils. These results indicate that whether or not DOC inhibits or promotes transport of oocysts and microspheres in agricultural soils and by how much, depends not only on the surface characteristics of the colloid, but the nature of the DOC and the soil mineralogy.

Environmental Science & Technology↗

USGS2011

Biodegradation and attenuation of steroidal hormones and alkylphenols by stream biofilms and sediments

Biodegradation of select endocrine-disrupting compounds (17β-estradiol, estrone, 17α-ethynylestradiol, 4-nonylphenol, 4-nonylphenolmonoexthoylate, and 4-nonylphenoldiethoxylate) was evaluated in stream biofilm, sediment, and water matrices collected from locations upstream and downstream from a wastewater treatment plant effluent discharge. Both biologically mediated transformation to intermediate metabolites and biologically mediated mineralization were evaluated in separate time interval experiments. Initial time intervals (0–7 d) evaluated biodegradation by the microbial community dominant at the time of sampling. Later time intervals (70 and 185 d) evaluated the biodegradation potential as the microbial community adapted to the absence of outside energy sources. The sediment matrix was more effective than the biofilm and water matrices at biodegrading 4-nonylphenol and 17β-estradiol. Biodegradation by the sediment matrix of 17α-ethynylestradiol occurred at later time intervals (70 and 185 d) and was not observed in the biofilm or water matrices. Stream biofilms play an important role in the attenuation of endocrine-disrupting compounds in surface waters due to both biodegradation and sorption processes. Because sorption to stream biofilms and bed sediments occurs on a faster temporal scale (<1 h) than the potential to biodegrade the target compounds (50% mineralization at >185 d), these compounds can accumulate in stream biofilms and sediments.

Environmental Science & Technology↗

USGS2011

Effects of the antimicrobial sulfamethoxazole on groundwater bacterial enrichment

The effects of “trace” (environmentally relevant) concentrations of the antimicrobial agent sulfamethoxazole (SMX) on the growth, nitrate reduction activity, and bacterial composition of an enrichment culture prepared with groundwater from a pristine zone of a sandy drinking-water aquifer on Cape Cod, MA, were assessed by laboratory incubations. When the enrichments were grown under heterotrophic denitrifying conditions and exposed to SMX, noticeable differences from the control (no SMX) were observed. Exposure to SMX in concentrations as low as 0.005 μM delayed the initiation of cell growth by up to 1 day and decreased nitrate reduction potential (total amount of nitrate reduced after 19 days) by 47% ( p = 0.02). Exposure to 1 μM SMX, a concentration below those prescribed for clinical applications but higher than concentrations typically detected in aqueous environments, resulted in additional inhibitions: reduced growth rates ( p = 5 × 10 −6 ), lower nitrate reduction rate potentials ( p = 0.01), and decreased overall representation of 16S rRNA gene sequences belonging to the genus Pseudomonas . The reduced abundance of Pseudomonas sequences in the libraries was replaced by sequences representing the genus Variovorax . Results of these growth and nitrate reduction experiments collectively suggest that subtherapeutic concentrations of SMX altered the composition of the enriched nitrate-reducing microcosms and inhibited nitrate reduction capabilities.

Environmental Science & Technology↗

USGS2011

Methods for evaluating in-stream attenuation of trace organic compounds

Wastewater treatment plants are often the most substantial contributor of trace organic compounds including pharmaceuticals, steroidal hormones, and surfactants to surface waters. Studying stream reaches below wastewater treatment plants provide valuable information on the environmental persistence of these compounds. Three methods for conducting field investigations to evaluate in-stream attenuation of trace organic compounds are presented: (1) using intrinsic tracers in wastewater, (2) environmental sampling coupled with dye studies to assess travel times between sample locations, and (3) Lagrangian sampling. Advantages and limitations of each method are discussed, along with key findings from several investigations.

Applied Geochemistry↗