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A review of selected inorganic surface water quality-monitoring practices: are we really measuring what we think, and if so, are we doing it right?

Successful environmental/water quality-monitoring programs usually require a balance between analytical capabilities, the collection and preservation of representative samples, and available financial/personnel resources. Due to current economic conditions, monitoring programs are under increasing pressure to do more with less. Hence, a review of current sampling and analytical methodologies, and some of the underlying assumptions that form the bases for these programs seems appropriate, to see if they are achieving their intended objectives within acceptable error limits and/or measurement uncertainty, in a cost-effective manner. That evaluation appears to indicate that several common sampling/processing/analytical procedures (e.g., dip (point) samples/measurements, nitrogen determinations, total recoverable analytical procedures) are generating biased or nonrepresentative data, and that some of the underlying assumptions relative to current programs, such as calendar-based sampling and stationarity are no longer defensible. The extensive use of statistical models as well as surrogates (e.g., turbidity) also needs to be re-examined because the hydrologic interrelationships that support their use tend to be dynamic rather than static. As a result, a number of monitoring programs may need redesigning, some sampling and analytical procedures may need to be updated, and model/surrogate interrelationships may require recalibration.

Environmental Science & Technology

Assessing the impact of drought on arsenic exposure from private domestic wells in the conterminous United States

This study assesses the potential impact of drought on arsenic exposure from private domestic wells by using a previously developed statistical model that predicts the probability of elevated arsenic concentrations (>10 μg per liter) in water from domestic wells located in the conterminous United States (CONUS). The application of the model to simulate drought conditions used systematically reduced precipitation and recharge values. The drought conditions resulted in higher probabilities of elevated arsenic throughout most of the CONUS. While the increase in the probability of elevated arsenic was generally less than 10% at any one location, when considered over the entire CONUS, the increase has considerable public health implications. The population exposed to elevated arsenic from domestic wells was estimated to increase from approximately 2.7 million to 4.1 million people during drought. The model was also run using total annual precipitation and groundwater recharge values from the year 2012 when drought existed over a large extent of the CONUS. This simulation provided a method for comparing the duration of drought to changes in the predicted probability of high arsenic in domestic wells. These results suggest that the probability of exposure to arsenic concentrations greater than 10 μg per liter increases with increasing duration of drought. These findings indicate that drought has a potentially adverse impact on the arsenic hazard from domestic wells throughout the CONUS.

Conterminous United States

Influence of coal-tar sealcoat and other carbonaceous materials on polycyclic aromatic hydrocarbon loading in an urban watershed

Carbonaceous material (CM) particles are the principal vectors transporting polycyclic aromatic hydrocarbons (PAHs) into urban waters via runoff; however, characteristics of CM particles in urban watersheds and their relative contributions to PAH contamination remain unclear. Our objectives were to identify the sources and distribution of CM particles in an urban watershed and to determine the types of CMs that were the dominant sources of PAHs in the lake and stream sediments. Samples of soils, parking lot and street dust, and streambed and lake sediment were collected from the Lake Como watershed in Fort Worth, Texas. Characteristics of CM particles determined by organic petrography and a significant correlation between PAH concentrations and organic carbon in coal tar, asphalt, and soot indicate that these three CM particle types are the major sources and carriers of PAHs in the watershed. Estimates of the distribution of PAHs in CM particles indicate that coal-tar pitch, usedinsomepavementsealcoats, isadominant source of PAHs in the watershed, and contributes as much as 99% of the PAHs in sealed parking lot dust, 92% in unsealed parking lot dust, 88% in commercial area soil, 71% in streambed sediment, and 84% in surficial lake sediment. ?? 2010 American Chemical Society.

Environmental Science & Technology

Modeling the transport and inactivation of E. coli and enterococci in the near-shore region of Lake Michigan

To investigate the transport and fate of fecal pollution at Great Lakes beaches and the health risks associated with swimming, the near-shore waters of Lake Michigan and two tributaries discharging into it were examined for bacterial indicators of human fecal pollution. The enterococcus human fecal pollution marker, which targets a putative virulence factor the enterococcal surface protein (esp) in Enterococcus faecium , was detected in 2/28 samples (7%) in the tributaries draining into Lake Michigan and in 6/30 samples (20%) in Lake Michigan beaches. This was indicative of human fecal pollution being transported in the tributaries and occurrence at Lake Michigan beaches. To understand the relative importance of different processes influencing pollution transport and inactivation, a finite-element model of surf-zone hydrodynamics (coupled with models for temperature, E. coli and enterococci) was used. Enterococci appear to survive longer than E. coli , which was described using an overall first-order inactivation coefficient in the range 0.5−2.0 per day. Our analysis suggests that the majority of fecal indicator bacteria variation can be explained based on loadings from the tributaries. Sunlight is a major contributor to inactivation in the surf-zone and the formulation based on sunlight, temperature and sedimentation is preferred over the first-order inactivation formulation.

Environmental Science & Technology

Investigation of river eutrophication as part of a low dissolved oxygen total maximum daily load implementation

In the United States, environmentally impaired rivers are subject to regulation under total maximum daily load (TMDL) regulations that specify watershed wide water quality standards. In California, the setting of TMDL standards is accompanied by the development of scientific and management plans directed at achieving specific water quality objectives. The San Joaquin River (SJR) in the Central Valley of California now has a TMDL for dissolved oxygen (DO). Low DO conditions in the SJR are caused in part by excessive phytoplankton growth (eutrophication) in the shallow, upstream portion of the river that create oxygen demand in the deeper estuary. This paper reports on scientific studies that were conducted to develop a mass balance on nutrients and phytoplankton in the SJR. A mass balance model was developed using WARMF, a model specifically designed for use in TMDL management applications. It was demonstrated that phytoplankton biomass accumulates rapidly in a 88 km reach where plankton from small, slow moving tributaries are diluted and combined with fresh nutrient inputs in faster moving water. The SJR-WARMF model was demonstrated to accurately predict phytoplankton growth in the SJR. Model results suggest that modest reductions in nutrients alone will not limit algal biomass accumulation, but that combined strategies of nutrient reduction and algal control in tributaries may have benefit. The SJR-WARMF model provides stakeholders a practical, scientific tool for setting remediation priorities on a watershed scale.

Water Science and Technology

Real-time nowcasting of microbiological water quality at recreational beaches: A wavelet and artificial neural network-based hybrid modeling approach

The number of beach closings caused by bacterial contamination has continued to rise in recent years, putting beachgoers at risk of exposure to contaminated water. Current approaches predict levels of indicator bacteria using regression models containing a number of explanatory variables. Data-based modeling approaches can supplement routine monitoring data and provide highly accurate short-term forecasts of beach water quality. In this paper, we apply the nonlinear autoregressive network with exogenous inputs (NARX) method with explanatory variables to predict Escherichia coli concentrations at four Lake Michigan beach sites. We also apply the nonlinear input–output network (NIO) and nonlinear autoregressive neural network (NAR) methods in addition to a hybrid wavelet-NAR (WA-NAR) model and demonstrate their application. All models were tested using 3 months of observed data. Results revealed that the NARX models provided the best performance and that the WA-NAR model, which requires no explanatory variables, outperformed the NIO and NAR models; therefore, the WA-NAR model is suitable for application to data scarce regions. The models proposed in this paper were evaluated using multiple performance metrics, including sensitivity and specificity measures, and produced results comparable or superior to those of previous mechanistic and statistical models developed for the same beach sites. The relatively high R 2 values between data and the NARX models ( R 2 values of ∼0.8 for the beach sites and ∼0.9 for the river site) indicate that the new class of models shows promise for beach management.

Environmental Science & Technology

Predicting arsenic in drinking water wells of the Central Valley, California

Probabilities of arsenic in groundwater at depths used for domestic and public supply in the Central Valley of California are predicted using weak-learner ensemble models (boosted regression trees, BRT) and more traditional linear models (logistic regression, LR). Both methods captured major processes that affect arsenic concentrations, such as the chemical evolution of groundwater, redox differences, and the influence of aquifer geochemistry. Inferred flow-path length was the most important variable but near-surface-aquifer geochemical data also were significant. A unique feature of this study was that previously predicted nitrate concentrations in three dimensions were themselves predictive of arsenic and indicated an important redox effect at >10 μg/L, indicating low arsenic where nitrate was high. Additionally, a variable representing three-dimensional aquifer texture from the Central Valley Hydrologic Model was an important predictor, indicating high arsenic associated with fine-grained aquifer sediment. BRT outperformed LR at the 5 μg/L threshold in all five predictive performance measures and at 10 μg/L in four out of five measures. BRT yielded higher prediction sensitivity (39%) than LR (18%) at the 10 μg/L threshold–a useful outcome because a major objective of the modeling was to improve our ability to predict high arsenic areas.

California

Seasonal and annual load of herbicides from the Mississippi River Basin to the Gulf of Mexico

Water samples collected from rivers in the Mississippi River Basin were analyzed for selected herbicides to evaluate their discharge to the Gulf of Mexico and to identify their predominant source areas within the basin. Samples were collected from the Mississippi River at Baton Rouge, LA from 1991 to 1997 and from sites on the upper Mississippi, the Missouri, and the Ohio Rivers from 1996 to 1997. Atrazine, metolachlor, and alachlor ESA (an alachlor metabolite) were the most frequently detected herbicides in the Mississippi River at Baton Rouge, and, in general, were present in the largest concentrations. The peak annual herbicide load was in 1993 when about 640 metric tons of atrazine, 320 metric tons of cyanazine, 215 metric tons of metolachlor, 53 metric tons of simazine, and 50 metric tons of alachlor were discharged to the Gulf of Mexico. The annual load of atrazine and cyanazine was generally 1−3% of the amount annually applied in the Mississippi River drainage basin; the annual load of acetochlor, alachlor, and metolachlor was generally less than 1%. During 1996−1997 the Ohio River contributed about 50% of the discharge and 50% or more of the herbicide load to the Gulf of Mexico.

Environmental Science & Technology

An “EAR” on environmental surveillance and monitoring: A case study on the use of Exposure–Activity Ratios (EARs) to prioritize sites, chemicals, and bioactivities of concern in Great Lakes waters

Current environmental monitoring approaches focus primarily on chemical occurrence. However, based on concentration alone, it can be difficult to identify which compounds may be of toxicological concern and should be prioritized for further monitoring, in-depth testing, or management. This can be problematic because toxicological characterization is lacking for many emerging contaminants. New sources of high-throughput screening (HTS) data, such as the ToxCast database, which contains information for over 9000 compounds screened through up to 1100 bioassays, are now available. Integrated analysis of chemical occurrence data with HTS data offers new opportunities to prioritize chemicals, sites, or biological effects for further investigation based on concentrations detected in the environment linked to relative potencies in pathway-based bioassays. As a case study, chemical occurrence data from a 2012 study in the Great Lakes Basin along with the ToxCast effects database were used to calculate exposure–activity ratios (EARs) as a prioritization tool. Technical considerations of data processing and use of the ToxCast database are presented and discussed. EAR prioritization identified multiple sites, biological pathways, and chemicals that warrant further investigation. Prioritized bioactivities from the EAR analysis were linked to discrete adverse outcome pathways to identify potential adverse outcomes and biomarkers for use in subsequent monitoring efforts.

Great Lakes

Occurrence of cyanazine compounds in groundwater: Degradates more prevalent than the parent compound

A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.

Iowa

Machine learning models of arsenic in private wells throughout the conterminous United States as a tool for exposure assessment in human health studies

Arsenic from geologic sources is widespread in groundwater within the United States (U.S.). In several areas, groundwater arsenic concentrations exceed the U.S. Environmental Protection Agency maximum contaminant level of 10 μg per liter (μg/L). However, this standard applies only to public-supply drinking water and not to private-supply, which is not federally regulated and is rarely monitored. As a result, arsenic exposure from private wells is a potentially substantial, but largely hidden, public health concern. Machine learning models using boosted regression trees (BRT) and random forest classification (RFC) techniques were developed to estimate probabilities and concentration ranges of arsenic in private wells throughout the conterminous U.S. Three BRT models were fit separately to estimate the probability of private well arsenic concentrations exceeding 1, 5, or 10 μg/L whereas the RFC model estimates the most probable category (≤5, >5 to ≤10, or >10 μg/L). Overall, the models perform best at identifying areas with low concentrations of arsenic in private wells. The BRT 10 μg/L model estimates for testing data have an overall accuracy of 91.2%, sensitivity of 33.9%, and specificity of 98.2%. Influential variables identified across all models included average annual precipitation and soil geochemistry. Models were developed in collaboration with public health experts to support U.S.-based studies focused on health effects from arsenic exposure.

Environmental Science and Technology

Differential effects of dissolved organic carbon upon re-entrainment and surface properties of groundwater bacteria and bacteria-sized microspheres during transport through a contaminated, sandy aquifer

Injection-and-recovery studies involving a contaminated, sandy aquifer (Cape Cod, Massachusetts) were conducted to assess the relative susceptibility for in situ re-entrainment of attached groundwater bacteria ( Pseudomonas stuzeri ML2, and uncultured, native bacteria) and carboxylate-modified microspheres (0.2 and 1.0 μm diameters). Different patterns of re-entrainment were evident for the two colloids in response to subsequent injections of groundwater (hydrodynamic perturbation), deionized water (ionic strength alteration), 77 μM linear alkylbenzene sulfonates (LAS, anionic surfactant), and 76 μM Tween 80 (polyoxyethylene sorbitan monooleate, a very hydrophobic nonionic surfactant). An injection of deionized water was more effective in causing detachment of micrsopheres than were either of the surfactants, consistent with the more electrostatic nature of microsphere’s attachment, their extreme hydrophilicity (hydrophilicity index, HI, of 0.99), and negative charge (zeta potentials, ζ, of −44 to −49 mv). In contrast, Tween 80 was considerably more effective in re-entraining the more-hydrophobic native bacteria. Both the hydrophilicities and zeta potentials of the native bacteria were highly sensitive to and linearly correlated with levels of groundwater dissolved organic carbon (DOC), which varied modestly from 0.6 to 1.3 mg L −1 . The most hydrophilic (0.52 HI) and negatively charged (ζ −38.1 mv) indigenous bacteria were associated with the lowest DOC. FTIR spectra indicated the latter community had the highest average density of surface carboxyl groups. In contrast, differences in groundwater (DOC) had no measurable effect on hydrophilicity of the bacteria-sized microspheres and only a minor effect on their ζ. These findings suggest that microspheres may not be very good surrogates for bacteria in field-scale transport studies and that adaptive (biological) changes in bacterial surface characteristics may need to be considered where there is longer-term exposure to contaminant DOC.

Environmental Science & Technology

Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The transport and retention kinetics of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated packed columns that encompassed a range of humic acid concentrations (HA, 0–10 mg L –1 ), fractional surface coverage of iron oxyhydroxide coatings on sand grains (λ, 0–0.75), and pH (6.0–10.5). HA was found to have a marked effect on the electrokinetic properties of ARS-nHAP, and on the transport and retention of ARS-nHAP in granular media. The transport of ARS-nHAP was found to increase with increasing HA concentration because of enhanced colloidal stability and the reduced aggregate size. When HA = 10 mg L –1 , greater ARS-nHAP attachment occurred with increasing λ because of increased electrostatic attraction between negatively charged nanoparticles and positively charged iron oxyhydroxides, although alkaline conditions (pH 8.0 and 10.5) reversed the surface charge of the iron oxyhydroxides and therefore decreased deposition. The retention profiles of ARS-nHAP exhibited a hyperexponential shape for all test conditions, suggesting some unfavorable attachment conditions. Retarded breakthrough curves occurred in sands with iron oxyhydroxide coatings because of time-dependent occupation of favorable deposition sites. Consideration of the above effects is necessary to improve remediation efficiency of nHAP for metals and actinides in soils and subsurface environments.

Environmental Science & Technology

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

Effects of flow regime on metal concentrations and the attainment of water quality standards in a remediated stream reach, Butte, Montana

Low-flow synoptic sampling campaigns are often used as the primary tool to characterize watersheds affected by mining. Although such campaigns are an invaluable part of site characterization, investigations which focus solely on low-flow conditions may yield misleading results. The objective of this paper is to demonstrate this point and elucidate the mechanisms responsible for the release of metals during rainfall runoff. This objective is addressed using data from diel and synoptic sampling campaigns conducted over a two-day period. Low-flow synoptic sampling results indicate that concentrations of most constituents meet aquatic standards. This finding is in contrast to findings from a diel sampling campaign that captured dramatic increases in concentrations during rainfall runoff. Concentrations during the rising limb of the hydrograph were 2–23 times concentrations observed during synoptic sampling (most increases were >10-fold), remaining elevated during the receding limb of the hydrograph to produce a clockwise hysteresis loop. Hydrologic mechanisms responsible for the release of metals include increased transport due to resuspension of streambed solids, erosion of alluvial tailings, and overland flow. Rainfall also elevated the alluvial groundwater table and increased infiltration through the vadose zone, likely resulting in dissolution from alluvial tailings that were dry prior to the event.

Montana

Immediate and long-term fire effects on total mercury in forests soils of northeastern Minnesota

Within the Boundary Waters Canoe Area Wilderness in northeastern Minnesota, soils were collected from 116 sites in areas of primarily virgin forest with fire-origin stand years (year of last recognizable stand-killing wildfire) that range from the 1759 to 1976. Median concentrations for total mercury in soils for this span of 217 years range from 0.28 ± 0.088 ppm (1759) to 0.09 ± 0.047 ppm (1976) for A-horizon soils and from 0.23 ± 0.062 ppm (1759) to 0.09 ± 0.018 ppm (1976) for O-horizon soils. A separate study of soils collected from 30 sites within an area that burned in a 2004 wildfire at Voyageurs National Park, northern Minnesota, suggested that high soil burn severity resulted in significant mercury loss from both organic and mineral soils. Integrated data from these two studies and additional regional soil data demonstrate that older forests have progressively higher mercury concentrations in O-horizon soils (r 2 = 0.423) and A-horizon soils (r 2 = 0.456). These results support the hypotheses that an important factor for mercury concentrations in forest soils is time since stand-replacing fire and that high soil burn severity has the potential to reduce the concentration of mercury in burned soils for tens to hundreds of years.

Minnesota

Windows of susceptibility and consequences of early life exposures to 17β–estradiol on medaka (Oryzias latipes) reproductive success

Estrogens and estrogen mimics are commonly found in surface waters and are associated with deleterious effects in fish populations. Impaired fertility and fecundity in fish following chronic exposures to estrogens and estrogen mimics during critical windows in development are well documented. However, information regarding differential reproductive effects of exposure within defined developmental stages remains sparse. In this study, reproductive capacity was assessed in Japanese medaka ( Oryzias latipes ) after exposure to two concentrations of 17β–estradiol (E2β; 2 ng/L and 50 ng/L) during four distinct stages of development: gonad development, gonad differentiation, development of secondary sex characteristics (SSC) and gametogenesis. Exposure to E2β did not adversely impact survival, hatch success, growth, or genotypic ratios. In contrast, exposure to 50 ng/L E2β during SSC development altered phenotypic ratios and SSC. Exposure to both E2β treatments reduced reproductive capacity (fertility, fecundity) by 7.3–57.4% in adult medaka breeding pairs, with hindrance of SSC development resulting in the largest disruption in breeding capacity (51.6–57.4% decrease) in the high concentration. This study documents differential effects among four critical stages of development and provides insight into factors (window of exposure, exposure concentration and duration of exposure period) contributing to reproductive disruption in fish.

Environmental Science & Technology

Quantification of natural vapor fluxes of trichloroethene in the unsaturated zone at Picatinny Arsenal, New Jersey

The upward flux of trichloroethene (TCE) vapor through the unsaturated zone above a contaminated, water-table aquifer at Picatinny Arsenal, New Jersey, has been studied under natural conditions over a 12-month period. Vertical gas-phase diffusion fluxes were estimated indirectly by measuring the TCE vapor concentration gradient in the unsaturated zone and using Fick's law to calculate the flux. The total gas-phase flux (e.g., the sum of diffusion and advection fluxes) was measured directly with a vertical flux chamber (VFC). In many cases, the upward TCE vapor flux was several orders of magnitude greater than the upward TCE diffusion flux, suggesting that mechanisms other than steady-state vapor diffusion are contributing to the vertical transport of TCE vapors through the unsaturated zone. The measured total flux of TCE vapor from the subsurface to the atmosphere is approximately 50 kg/yr and is comparable in magnitude to the removal rate of TCE from the aquifer by an existing pump-and-treat system and by discharge into a nearby stream. The net upward flux of TCE is reduced significantly during a storm event, presumably due to the mass transfer of TCE from the soil gas to the infiltrating rainwater and its subsequent downward advection. Several potential problems associated with the measurement of total gas-phase fluxes are discussed.

Environmental Science & Technology