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Patterns of host-associated fecal indicators driven by hydrology, precipitation, and land use attributes in Great Lakes watersheds

Fecal contamination from sewage and agricultural runoff is a pervasive problem in Great Lakes watersheds. Most work examining fecal pollution loads relies on discrete samples of fecal indicators and modeling land use. In this study, we made empirical measurements of human and ruminant-associated fecal indicator bacteria and combined these with hydrological measurements in eight watersheds ranging from predominantly forested to highly urbanized. Flow composited river samples were collected over low-flow ( n = 89) and rainfall or snowmelt runoff events ( n = 130). Approximately 90% of samples had evidence of human fecal pollution, with highest loads from urban watersheds. Ruminant indicators were found in ∼60–100% of runoff-event samples in agricultural watersheds, with concentrations and loads related to cattle density. Rain depth, season, agricultural tile drainage, and human or cattle density explained variability in daily flux of human or ruminant indicators. Mapping host-associated indicator loads to watershed discharge points sheds light on the type, level, and possible health risk from fecal pollution entering the Great Lakes and can inform total maximum daily load implementation and other management practices to target specific fecal pollution sources.

Environmental Science & Technology

Flood hydrology and methylmercury availability in Coastal Plain rivers

Mercury (Hg) burdens in top-predator fish differ substantially between adjacent South Carolina Coastal Plain river basins with similar wetlands coverage. In the Congaree River, floodwaters frequently originate in the Blue Ridge and Piedmont regions, where wetlands coverage and surface water dissolved methylmercury (MeHg) concentrations are low. Piedmont-driven flood events can lead to downward hydraulic gradients in the Coastal Plain riparian wetland margins, inhibiting MeHg transport from wetland sediments, and decreasing MeHg availability in the Congaree River habitat. In the adjacent Edisto River basin, floodwaters originate only within Coastal Plain sediments, maintaining upward hydraulic gradients even during flood events, promoting MeHg transport to the water column, and enhancing MeHg availability in the Edisto River habitat. These results indicate that flood hydrodynamics contribute to the variability in Hg vulnerability between Coastal Plain rivers and that comprehensive regional assessment of the relationship between flood hydrodynamics and Hg risk in Coastal Plain streams is warranted.

South Carolina

Uranium and radon in private bedrock well water in Maine: geospatial analysis at two scales

In greater Augusta of central Maine, 53 out of 1093 (4.8%) private bedrock well water samples from 1534 km 2 contained [U] >30 μg/L, the U.S. Environmental Protection Agency’s (EPA) Maximum Contaminant Level (MCL) for drinking water; and 226 out of 786 (29%) samples from 1135 km 2 showed [Rn] >4,000 pCi/L (148 Bq/L), the U.S. EPA’s Alternative MCL. Groundwater pH, calcite dissolution and redox condition are factors controlling the distribution of groundwater U but not Rn due to their divergent chemical and hydrological properties. Groundwater U is associated with incompatible elements (S, As, Mo, F, and Cs) in water samples within granitic intrusions. Elevated [U] and [Rn] are located within 5–10 km distance of granitic intrusions but do not show correlations with metamorphism at intermediate scales (100−101 km). This spatial association is confirmed by a high-density sampling (n = 331, 5–40 samples per km 2 ) at local scales (≤10 –1 km) and the statewide sampling (n = 5857, 1 sample per 16 km 2 ) at regional scales (10 2 –10 3 km). Wells located within 5 km of granitic intrusions are at risk of containing high levels of [U] and [Rn]. Approximately 48 800–63 900 and 324 000 people in Maine are estimated at risk of exposure to U (>30 μg/L) and Rn (>4000 pCi/L) in well water, respectively.

Maine

Value and validity of earth resources observations from space

Observations of the earth from space can provide overall repetitive views in various regions of the electromagnetic spectrum. Data from such surveys can be used as the basis for more detailed observations from aircraft and on the ground to guide resource exploration, development, and conservation activities. The value of earth resource observations from space has been demonstrated by the practical use of photographs from the Gemini and Apollo spaceflights and particularly by a series of multispectral photographs taken during the flight of Apollo 9. The analysis of those photographs has shown that the performance of the planned Earth Resources Technology Satellite will meet the needs of the resource and environmental community for small-scale repetitive images of the earth in the visible and solar infrared portions of the spectrum and has provided a limited base of material for earth scientists to work with in order to ready themselves for the ERTS data. The validity of earth resource observations from space can be derived by analogy from the successively closer observations of the moon, culminating in repeated physical sampling of the moon's surface. The method of inductive reasoning and analysis used for the moon is the opposite of the normal deductive analysis used on the earth. Adoption of the inductive methods and reasoning for earth observations will provide a framework of broad observations and conclusions leading to the identification of target areas for more detailed observation and will, in time, reduce the costs and time required for surveys dealing with resource and environmental problems.

Hydrological Sciences Bulletin

Overview of the Mars Pathfinder Mission: Launch through landing, surface operations, data sets, and science results

Mars Pathfinder successfully landed at Ares Vallis on July 4, 1997, deployed and navigated a small rover about 100 m clockwise around the lander, and collected data from three science instruments and ten technology experiments. The mission operated for three months and returned 2.3 Gbits of data, including over 16,500 lander and 550 rover images, 16 chemical analyses of rocks and soil, and 8.5 million individual temperature, pressure and wind measurements. Path‐finder is the best known location on Mars, having been clearly identified with respect to other features on the surface by correlating five prominent horizon features and two small craters in lander images with those in high‐resolution orbiter images and in inertial space from two‐way ranging and Doppler tracking. Tracking of the lander has fixed the spin pole of Mars, determined the precession rate since Viking 20 years ago, and indicates a polar moment of inertia, which constrains a central metallic core to be between 1300 and ∼2000 km in radius. Dark rocks appear to be high in silica and geochemically similar to anorogenic andesites; lighter rocks are richer in sulfur and lower in silica, consistent with being coated with various amounts of dust. Rover and lander images show rocks with a variety of morphologies, fabrics and textures, suggesting a variety of rock types are present. Rounded pebbles and cobbles on the surface as well as rounded bumps and pits on some rocks indicate these rocks may be conglomerates (although other explanations are also possible), which almost definitely require liquid water to form and a warmer and wetter past. Air‐borne dust is composed of composite silicate particles with a small fraction of a highly magnetic mineral, interpreted to be most likely maghemite; explanations suggest iron was dissolved from crustal materials during an active hydrologic cycle with maghemite freeze dried onto silicate dust grains. Remote sensing data at a scale of a kilometer or greater and an Earth analog correctly predicted a rocky plain safe for landing and roving with a variety of rocks deposited by catstrophic floods, which are relatively dust free. The surface appears to have changed little since it formed billions of years ago, with the exception that eolian activity may have deflated the surface by ∼3–7 cm, sculpted wind tails, collected sand into dunes, and eroded ventifacts (fluted and grooved rocks). Pathfinder found a dusty lower atmosphere, early morning water ice clouds, and morning near‐surface air temperatures that changed abruptly with time and height. Small scale vortices, interpreted to be dust devils, were observed repeatedly in the afternoon by the meteorology instruments and have been imaged.

Journal of Geophysical Research E: Planets

Vertical datum conversion process for the inland and coastal gage network located in the New England, Mid-Atlantic, and South Atlantic-Gulf hydrologic regions

Datum conversions from the National Geodetic Vertical Datum of 1929 to the North American Vertical Datum of 1988 among inland and coastal gages throughout the hydrologic regions of New England, the Mid-Atlantic, and the South Atlantic-Gulf have implications among river and storm surge forecasting, general commerce, and water-control operations. The process of data conversions may involve the application of a recovered National Geodetic Vertical Datum of 1929–North American Vertical Datum of 1988 offset, a simplistic datum transformation using VDatum or VERTCON software, or a survey, depending on a gaging network datum evaluation, anticipated uncertainties for data use among the cooperative water community, and methods used to derive the conversion. Datum transformations from National Geodetic Vertical Datum of 1929 to North American Vertical Datum of 1988 using VERTCON purport errors of ± 0.13 foot at the 95 percent confidence level among modeled points, claiming more consistency along the east coast. Survey methods involving differential and trigonometric leveling, along with observations using Global Navigation Satellite System technology, afford a variety of approaches to establish or perpetuate a datum during a survey. Uncertainties among leveling approaches are generally < 0.1 foot, and and Global Navigation Satellite System approaches may be categorized with uncertainties of ≤0.1 foot for a Level I quality category and ≥0.1 foot for Level II or III quality categories (defined by the U.S. Geological Survey) by observation and review of experienced practice. The conversion process is initiated with an evaluation of the inland and coastal gage network datum, beginning with altitude datum components and the history of those components queried through the U.S. Geological Survey Groundwater Site Inventory database. Subsequent edits to the Groundwater Site Inventory database may be required and a consensus reached among the U.S. Geological Survey Water Science Centers to identify the outstanding workload categorized as in-office datum transformations or offset applications versus out-of-office survey efforts. Datum conversions or datum establishment for the inland or coastal gaging network should meet datum uncertainty requirements among other Federal agencies. Datum uncertainty requirements are ±0.25 foot for U.S. Army Corps of Engineers water-control or construction projects and ±0.16 foot for Federal Emergency Management Agency field surveys and checkpoint surveys used for mapping. River level forecasts generally are defined as ± 0.10 foot among the National Oceanic and Atmospheric Administration–National Weather Service. Collaboration and communication among the cooperative water community is necessary during a datum conversion or datum change. Datum notification time-change requirements set by the National Oceanic and Atmospheric Administration–National Weather Service vary from 30 to 120 days, depending on datum conversion or datum-change case scenarios. Notification times associated with these case scenarios may be useful to the National Oceanic and Atmospheric Administration–National Weather Service and U.S. Army Corps of Engineers, because their daily operations are time sensitive, unlike the notification time change requirements of other entities that make up the cooperative water community. At the time of this writing, a future geopotential datum resulting from Gravity for the Redefinition of the American Vertical Datum is anticipated in 2022. A future version of VDatum and VERTCON is anticipated to provide a transformation among North American Vertical Datum of 1988 elevations to the new geopotential datum.

Techniques and Methods

Geochemical and hydrologic factors controlling subsurface transport of poly- and perfluoroalkyl substances, Cape Cod, Massachusetts

Growing evidence that certain poly- and perfluoroalkyl substances (PFASs) are associated with negative human health effects prompted the U.S. Environmental Protection Agency to issue lifetime drinking water health advisories for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in 2016. Given that groundwater is a major source of drinking water, the main objective of this work was to investigate geochemical and hydrological processes governing the subsurface transport of PFASs at a former fire training area (FTA) on Cape Cod, Massachusetts, where PFAS-containing aqueous film-forming foams were used historically. A total of 148 groundwater samples and 4 sediment cores were collected along a 1200-m-long downgradient transect originating near the FTA and analyzed for PFAS content. The results indicate that unsaturated zones at the FTA and at hydraulically downgradient former domestic wastewater effluent infiltration beds both act as continuous PFAS sources to the groundwater despite 18 and 20 years of inactivity, respectively. Historically different PFAS sources are evident from contrasting PFAS composition near the water table below the FTA and wastewater-infiltration beds. Results from total oxidizable precursor assays conducted using groundwater samples collected throughout the plume suggest that some perfluoroalkyl acid precursors at this site are transporting with perfluoroalkyl acids.

Massachusetts

U.S. Geological Survey Karst Interest Group Proceedings, Carlsbad, New Mexico, April 29-May 2, 2014

Karst aquifer systems are present throughout parts of the United States and some of its territories, and have developed in carbonate rocks (primarily limestone and dolomite) that span an interval of time encompassing more than 550 million years. The depositional environments, diagenetic processes, post-depositional tectonic events, and geochemical weathering processes that form karst aquifers are varied and complex, and involve biological, chemical, and physical changes. These factors, combined with the diverse climatic regimes under which karst development in these rocks has taken place, result in the unique dual- or triple-porosity nature of karst aquifers. These complex hydrogeologic systems typically represent challenging and unique conditions to scientists attempting to study groundwater flow and contaminant transport in these terrains. The dissolution of carbonate rocks and the subsequent development of distinct and beautiful landscapes, caverns, and springs has resulted in the most exceptional karst areas of the United States being designated as national or state parks; commercial caverns and known privately owned caves number in the tens of thousands. Both public and private properties provide access for scientists to study the flow of groundwater in situ. Likewise, the range and complexity of landforms and groundwater flow systems associated with karst terrains are enormous, perhaps more than for any other aquifer type. Karst aquifers and landscapes that form in tropical areas, such as the cockpit karst along the north coast of Puerto Rico, differ greatly from karst landforms in more arid climates, such as the Edwards Plateau in west-central Texas or the Guadalupe Mountains near Carlsbad, New Mexico, where hypogenic processes have played a major role in speleogenesis. Many of these public and private lands also contain unique flora and fauna associated with these karst hydrogeologic systems. As a result, numerous federal, state, and local agencies have a strong interest in the study of karst terrains. Many of the major springs and aquifers in the United States have developed in carbonate rocks, such as the Floridan aquifer system in Florida and parts of Alabama, Georgia, and South Carolina; the Ozark Plateaus aquifer system in parts of Arkansas, Kansas, Missouri, and Oklahoma; and the Edwards-Trinity aquifer system in west-central Texas. These aquifers, and the springs that discharge from them, serve as major water-supply sources and as unique ecological habitats. Competition for the water resources of karst aquifers is common, and urban development and the lack of attenuation of contaminants in karst areas can impact the ecosystem and water quality of these aquifers. The concept for developing a platform for interaction among scientists within the U.S. Geological Survey (USGS) working on karst-related studies evolved from the November 1999 National Ground-Water Meeting of the USGS. As a result, the Karst Interest Group (KIG) was formed in 2000. The KIG is a loose-knit, grass-roots organization of USGS and non-USGS scientists and researchers devoted to fostering better communication among scientists working on, or interested in, karst science. The primary mission of the KIG is to encourage and support interdisciplinary collaboration and technology transfer among scientists working in karst areas. Additionally, the KIG encourages collaborative studies between the different mission areas of the USGS as well as other federal and state agencies, and with researchers from academia and institutes. The KIG also encourages younger scientists by participation of students in the poster and oral sessions. To accomplish its mission, the KIG has organized a series of workshops that are held near nationally important karst areas. To date (2014) six KIG workshops, including the workshop documented in this report, have been held. The workshops typically include oral and poster sessions on selected karst-related topics and research, as well as field trips to local karst features. Proceedings of the workshops are published by the USGS and are available online at http://water.usgs.gov/ogw/karst/kig . The first KIG workshop was held in St. Petersburg, Florida, February 13–16, 2001, in the vicinity of the large springs and other karst features of the Floridan aquifer system. The second KIG workshop was held August 20–22, 2002, in Shepherdstown, West Virginia, in proximity to the carbonate aquifers of the northern Shenandoah Valley and highlighted an invited presentation on karst literature by the late Barry F. Beck of P.E. LaMoreaux and Associates. The third KIG workshop was held September 12–15, 2005, in Rapid City, South Dakota, nearby to karst features in evaporites and limestones of the Madison Group in the Black Hills of South Dakota, including Wind Cave National Park and Jewel Cave National Monument. The workshop also included a featured presentation by Thomas Casadevall, Central Region Director, USGS, on the status of earth science at the USGS and evening trips to Jewel Cave led by Mike Wiles, National Park Service (NPS) and Wind Cave led by Rod Horrocks, NPS. The fourth KIG workshop was held May 27–29, 2008, and hosted by the Hoffman Environmental Research Institute and Center for Cave and Karst Studies at Western Kentucky University in Bowling Green, Kentucky, near Mammoth Cave National Park and karst features of the Chester Upland and Pennyroyal Plateau. The workshop featured a late-night field trip into Mammoth Cave with Rickard Toomey and Rick Olsen, NPS. The fifth workshop was held April 26–29, 2011, and was a joint meeting of the USGS KIG and University of Arkansas HydroDays, hosted by the Department of Geosciences at the University of Arkansas in Fayetteville. The workshop featured an outstanding field trip to the unique karst terrain along the Buffalo National River of the southern Ozarks and a keynote presentation on paleokarst in the United States by Art and Peggy Palmer. This sixth and current 2014 KIG workshop is hosted by the National Cave and Karst Research Institute (NCKRI) in Carlsbad, New Mexico, with Director of NCKRI, George Veni, serving as co-chair of the workshop with Eve Kuniansky, USGS. The session planning committee for this sixth workshop includes Van Brahana, USGS retired and University of Arkansas Professor Emeritus; Tom Byl, USGS and Tennessee State University; Zelda Bailey, former Director of NCKRI and retired Director, National Institute of Standards and Technology, Boulder Laboratory, Colorado; Patrick Tucci, USGS retired; and Mike Bradley, Allan Clark, Geoff Delin, Daniel Doctor, James Kaufmann, Eve Kuniansky, Randy Orndorff, Larry Spangler, and Dave Weary of the USGS. The karst hydrology field trip on Thursday will be led by Lewis Land (NCKRI karst hydrologist) and the optional Friday field trip on the geology of Carlsbad Caverns National Park will be led by George Veni. The keynote speaker is Dr. Penelope Boston, Director of Cave and Karst Studies at New Mexico Tech, Socorro, and Academic Director at NCKRI, who will address the future of karst research. Additionally, there is a featured presentation “Irish karst and its management,” by Caoimhe Hickey, The Geological Survey of Ireland, preceding a panel discussion on “Collaboration During Times of Limited Resources.” The extended abstracts of USGS authors were peer reviewed and approved for publication by the U.S. Geological Survey. Articles submitted by university researchers and other federal and state agencies did not go through the formal USGS peer review and approval process, and therefore may not adhere to our editorial standards or stratigraphic nomenclature and is not research conducted or data collected by the USGS. However, all articles had at a minimum of two peer reviews, and all articles were edited for consistency of appearance in the published Proceedings. The use of trade, firm or product names in any article is for descriptive purposes only and does not imply endorsement by the U.S. Government. The USGS, Office of Groundwater, provides technical support for the Karst Interest Group website and public availability of the Proceedings from these workshops, and the USGS Groundwater Resources Program funds the publication costs. Finally, the cover illustration is the work of Ann Tihansky, USGS, used since the first KIG workshop in 2000.

Scientific Investigations Report

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Environmental Science & Technology

Hydrological controls on methylmercury distribution and flux in a tidal marsh

The San Francisco Estuary, California, contains mercury (Hg) contamination originating from historical regional gold and Hg mining operations. We measured hydrological and geochemical variables in a tidal marsh of the Palo Alto Baylands Nature Preserve to determine the sources, location, and magnitude of hydrological fluxes of methylmercury (MeHg), a bioavailable Hg species of ecological and health concern. Based on measured concentrations and detailed finite-element simulation of coupled surface water and saturated-unsaturated groundwater flow, we found pore water MeHg was concentrated in unsaturated pockets that persisted over tidal cycles. These pockets, occurring over 16% of the marsh plain area, corresponded to the marsh root zone. Groundwater discharge (e.g., exfiltration) to the tidal channel represented a significant source of MeHg during low tide. We found that nonchannelized flow accounted for up to 20% of the MeHg flux to the estuary. The estimated net flux of filter-passing (0.45 μm) MeHg toward estuary was 10 ± 5 ng m –2 day –1 during a single 12-h tidal cycle, suggesting an annual MeHg load of 1.17 ± 0.58 kg when the estimated flux was applied to present tidal marshes and planned marsh restorations throughout the San Francisco Estuary.

Environmental Science & Technology

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

Trends in concentrations and use of agricultural herbicides for Corn Belt rivers, 1996-2006

Trends in the concentrations and agricultural use of four herbicides (atrazine, acetochlor, metolachlor, and alachlor) were evaluated for major rivers of the Corn Belt for two partially overlapping time periods: 1996-2002 and 2000-2006. Trends were analyzed for 11 sites on the mainstems and selected tributaries in the Ohio, Upper Mississippi, and Missouri River Basins. Concentration trends were determined using a parametric regression model designed for analyzing seasonal variability, flow-related variability, and trends in pesticide concentrations(SEAWAVE-Q).TheSEAWAVE-Qmodel accounts for the effect of changing flow conditions in order to separate changes caused by hydrologic conditions from changes caused by other factors, such as pesticide use. Most of the trends in atrazine and acetochlor concentrations for both time periods were relatively small and nonsignificant, but metolachlor and alachlor were dominated by varying magnitudes of concentration downtrends. Overall, with trends expressed as a percent change per year, trends in herbicide concentrations were consistent with trends in agricultural use; 84 of 88 comparisons for different sites, herbicides, and time periods showed no significant difference between concentration trends and agricultural use trends. Results indicate that decreasing use appears to have been the primary cause for the concentration downtrends during 1996-2006 and that, while there is some evidence that nonuse management factors may have reduced concentrations in some rivers, reliably evaluating the influence of these factors on pesticides in large streams and rivers will require improved, basin-specific information on both management practices and use over time. ?? 2009 American Chemical Society.

Environmental Science & Technology

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: Groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally attenuated by a combination of active anaerobic and aerobic biotransformation processes. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology

Critical shifts in trace metal transport and remediation performance under future low river flows

Exceptionally low river flows are predicted to become more frequent and more severe across many global regions as a consequence of climate change. Investigations of trace metal transport dynamics across streamflows reveal stark changes in water chemistry, metal transformation processes, and remediation effectiveness under exceptionally low-flow conditions. High spatial resolution hydrological and water quality datasets indicate that metal-rich groundwater will exert a greater control on stream water chemistry and metal concentrations because of climate change. This is because the proportion of stream water sourced from mined areas and mineralized strata will increase under predicted future low-flow scenarios (from 25% under Q45 flow to 66% under Q99 flow in this study). However, mineral speciation modelling indicates that changes in stream pH and hydraulic conditions at low flow will decrease aqueous metal transport and increase sediment metal concentrations by enhancing metal sorption directly to streambed sediments. Solute transport modelling further demonstrates how increases in the importance of metal-rich diffuse groundwater sources at low flow could minimize the benefits of point source metal contamination treatment. Understanding metal transport dynamics under exceptionally low flows, as well as under high flows, is crucial to evaluate ecosystem service provision and remediation effectiveness in watersheds under future climate change scenarios.

Environmental Science & Technology

Acetochlor in the hydrologic system in the midwestern United States, 1994

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl)acetamide] was given conditional registration in the United States by the U.S. Environmental Protection Agency in March 1994. This registration provided a rare opportunity to investigate the occurrence of a pesticide during its first season of extensive use in the midwestern United States. Water samples collected and analyzed by the U.S. Geological Survey during 1994 documented the distribution of acetochlor in the hydrologic system; it was detected in 29% of the rain samples from four sites in Iowa, 17% of the stream samples from 51 sites across nine states, and 0% of the groundwater samples from 38 wells across eight states. Acetochlor exhibited concentration increases in rain and streams following its application to corn in the midwestern United States, with 75% of the rainwater and 35% of the stream samples having acetochlor detected during this time period. Acetochlor concentrations in rain decreased as the growing season progressed. Based on the limited data collected for this study, it is anticipated that acetochlor concentrations will have a seasonal pattern in rain and streams similar to those of other acetanilide herbicides examined. Possible explanations for the absence of acetochlor in groundwater for this study include the rapid degradation of acetochlor in the soil zone, insufficient time for this first extensive use of acetochlor to have reached the aquifers sampled, and the possible lack of acetochlor use in the recharge areas for the wells examined.

Environmental Science & Technology

De facto water reuse: Investigating the fate and transport of chemicals of emerging concern from wastewater discharge through drinking water treatment using non-targeted analysis and suspect screening

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K -means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Environmental Science & Technology

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

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