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USGS2020

Trophodynamics of per- and polyfluoroalkyl substances in the food web of a large Atlantic slope river

Per- and polyfluoroalkyl substances (PFASs) have attracted scientific and regulatory attention due to their persistence, bioaccumulative potential, toxicity, and global distribution. We determined the accumulation and trophic transfer of 14 PFASs (5 short-chain and 9 long-chain) within the food web of the Yadkin-Pee Dee River of North Carolina and South Carolina, US. Food web components and pathways were determined by stable isotope analyses of producers, consumers, and organic matter. Analyses of water, sediment, organic matter, and aquatic biota revealed that PFASs were prevalent in all food web compartments. Biofilm, an aggregation of bacteria, fungi, algae, and protozoans and a basal resource for the aquatic food web, showed high PFAS accumulation (in 10 of 14 compounds), particularly for perfluorooctanoic acid, with the greatest mean concentration of 463.73 ng/g. The food web compartment with the most detections and greatest concentrations of PFASs was aquatic insects; all 14 PFASs were detected in individual aquatic insect samples (range of <limit of detection [<LOD] to 1670.10 ng/g of wet weight [WW]). These findings may suggest a trophic link between biofilm PFASs and aquatic insect PFASs. Individual fish tissue samples ranged from <LOD to 797.00 ng/g of WW, where perfluorooctanesulfonate (PFOS) was the dominant PFAS among all samples (64%). The ova of an imperiled fish, the robust redhorse ( Moxostoma robustum ), had concentrations of 10 PFASs (range of <LOD to 482.88 ng/g of WW) and the highest PFOS concentration (482.88 ng/g of WW), indicating a likely maternal transfer. The trophic magnification factors (TMFs) calculated in this study showed that various taxa accumulated PFAS compounds differently. PFBS, a short-chain PFAS compound that would presumably exhibit lesser TMFs, had nine values among our compartments and organisms >1.0 (range of 0.57 to 2.33); it is possible that an unmeasured PFBS precursor may be accumulating in biota and metabolizing to PFBS, leading to a higher than expected TMFs for this compound. Our findings demonstrate the prevalence of PFASs in a freshwater food web with potential implications for ecological and human health.

North Carolina, South Carolina↗

USGS2017

Expanded target-chemical analysis reveals extensive mixed-organic-contaminant exposure in USA streams

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66–84% of all sites. Detected contaminant concentrations varied from less than 1 ng L –1 to greater than 10 μg L –1 , with 77 and 278 having median detected concentrations greater than 100 ng L –1 and 10 ng L –1 , respectively. Cumulative detections and concentrations ranged 4–161 compounds (median 70) and 8.5–102 847 ng L –1 , respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log 10 concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71–82% of the variability in the total number of compounds detected (linear regression; p -values: < 0.001–0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at μg L –1 cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L –1 .

Environmental Science & Technology↗

USGS2006

History of the Fort Collins Science Center, U.S. Geological Survey

The U.S. Geological Survey’s Fort Collins Science Center ("the Center") has been a nucleus of research, technology development, and associated scientific activities within the Department of the Interior for more than 30 years. The Center’s historical activities are deeply rooted in federal biological resources research and its supporting disciplines, particularly as they relate to the needs of the U.S. Department of the Interior and its resource management agencies. The organizational framework and activities of the Center have changed and adapted over the years in response to shifts in the scientific issues and challenges facing the U.S. Department of the Interior and with the development of new strategies to meet these challenges. Thus, the history of the Center has been dynamic. The Center has been nested within the U.S. Geological Survey since 1996. From 1993 to 1996 the Center was a major unit of the National Biological Service (named the National Biological Survey at its inception). This was a period of great organizational flux. During that time the Center comprised multiple field stations and science functions that prior to 1993 had been scattered among the U.S. Bureau of Land Management, the U.S. Bureau of Reclamation, the National Park Service, and the U.S. Fish and Wildlife Service. In 1993, certain biological research components of these agencies were assigned to join with the National Ecology Research Center, formerly one of the major research and development hubs of the U.S. Fish and Wildlife Service. This was the year when biological resources research in the U.S. Department of the Interior was consolidated by the Secretary of the Interior, who in an April 1993 memo explaining his intentions wrote, "Our Department has, without doubt, the best biologists in the world." Soon after formation of the new agency, the Center was re-named the Midcontinent Ecological Science Center, reflecting its geographic location within the new Midcontinent administrative region of the National Biological Service (the other three original administrative regions were the eastern, western, and southern). The change in name to the Fort Collins Science Center took place in 2002, soon after the center moved to new facilities on the Colorado State University Natural Resources Research Campus. At various times during the period when it was part of the National Biological Service (1993–96), the Center served as the administrative and programmatic home base for a wide number of science activities in numerous Western states (table 1). This reflected the previous fragmentation of biological and related science efforts across resource management agencies in the U.S. Department of the Interior. The organization of the 2 Center within the National Biological Service was a manifestation of the desire of the Secretary of the Interior to consolidate its biological science activities in administratively independent entities that would ensure that the science retained its objectivity. Congress later recognized the need to maintain a hierarchical independence between biological science and resource management in the Department. However, Congress also saw that the U.S. Geological Survey, with its long history of objective science support to the nation in geology, water resources, geography, and remote sensing, was a suitable alternative home for these biological science functions. Thus, in 1996 Congress transferred the biological resources functions of the National Biological Service to the U.S. Geological Survey. Detailed overviews and opinions about the history and policy issues surrounding the formation and subsequent fate of the National Biological Service can be found elsewhere (for example Cohn, 1993, 2005; Kaufman, 1993; Kreeger, 1994; Pulliam, 1995, 1998a,b; Reichhardt, 1994; Wagner, 1999)

Open-File Report↗

USGS2002

Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: Evidence for the presence of nitrogenous binding site

Humic substances typically constitute 40−60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg·L - 1 , SUVA 254 = 2.4 L/mg·m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM, were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction (“transphilic” meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.

Colorado↗

USGS2007

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: I. Laboratory development

A gel probe equilibrium sampler has been developed to study arsenic (As) geochemistry and sorption behavior in sediment porewater. The gels consist of a hydrated polyacrylamide polymer, which has a 92% water content. Two types of gels were used in this study. Undoped (clear) gels were used to measure concentrations of As and other elements in sediment porewater. The polyacrylamide gel was also doped with hydrous ferric oxide (HFO), an amorphous iron (Fe) oxyhydroxide. When deployed in the field, HFO-doped gels introduce a fresh sorbent into the subsurface thus allowing assessment of in situ sorption. In this study, clear and HFO-doped gels were tested under laboratory conditions to constrain the gel behavior prior to field deployment. Both types of gels were allowed to equilibrate with solutions of varying composition and re-equilibrated in acid for analysis. Clear gels accurately measured solution concentrations (??1%), and As was completely recovered from HFO-doped gels (??4%). Arsenic speciation was determined in clear gels through chromatographic separation of the re-equilibrated solution. For comparison to speciation in solution, mixtures of As(III) and As(V) adsorbed on HFO embedded in gel were measured in situ using X-ray absorption spectroscopy (XAS). Sorption densities for As(III) and As(V) on HFO embedded in gel were obtained from sorption isotherms at pH 7.1. When As and phosphate were simultaneously equilibrated (in up to 50-fold excess of As) with HFO-doped gels, phosphate inhibited As sorption by up to 85% and had a stronger inhibitory effect on As(V) than As(III). Natural organic matter (>200 ppm) decreased As adsorption by up to 50%, and had similar effects on As(V) and As(III). The laboratory results provide a basis for interpreting results obtained by deploying the gel probe in the field and elucidating the mechanisms controlling As partitioning between solid and dissolved phases in the environment. ?? 2008 American Chemical Society.

Environmental Science & Technology↗

USGS2012

Examining spring wet slab and glide avalanche occurrence along the Going-to-the-Sun Road corridor, Glacier National Park, Montana, USA

Wet slab and glide snow avalanches are dangerous and yet can be particularly difficult to predict. Wet slab and glide avalanches are presumably triggered by free water moving through the snowpack and the subsequent interaction with layer or ground interfaces, and typically occur in the spring during warming and subsequent melt periods. In Glacier National Park (GNP), Montana, both types of avalanches can occur in the same year and affect the spring opening operations of the Going-to-the-Sun Road (GTSR). We investigated the timing of wet slab and glide avalanche occurrence along the GTSR from 2003 to 2011 using meteorological and snowpack data from two high-elevation weather stations, one SNOTEL site, and an avalanche database to characterize 55 wet slab and 182 glide avalanches. Daily wet slab and glide avalanche occurrence were combined to represent an avalanche day and were compared to non-avalanche days (no avalanche occurrence) for 60 variables (both direct and derived measurements) using a univariate analysis. A classification tree (CART) was then trained to capture the most important variables for examining specific meteorological and snowpack variables that contribute to these types of wet snow avalanches. The CART was 10-fold cross validated using the data for 2003–2010 seasons and resulted in overall predictive accuracy of 73%. We then used the statistically optimal CART as a predictive model for the spring avalanche season of 2011, which resulted in an overall predictive accuracy of 82% for both avalanche and non-avalanche days, and a predictive accuracy of 91% for avalanche days. The results suggest that the role of air temperature and snowpack settlement appear to be the most important variables in wet slab and glide avalanche occurrence. When applied to the 2011 season, the results of the CART model are encouraging and they enhance our understanding of some of the required meteorological and snowpack conditions for wet slab and glide avalanche occurrence.

Cold Regions Science and Technology↗

USGS2006

Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO 4 - ) concentrations of 0.12−1.8 μg/L. Because the water samples are mostly preanthropogenic in age (0−28 000 years) and there are no industrial sources in the study area, a natural source of the ClO 4 - is likely. Most of the samples have Br - , Cl - , and SO 4 2 - concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7−40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO 3 - /Cl - and ClO 4 - /Cl - ratios are more variable than those of Br - /Cl - or SO 4 2 - /Cl - . Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO 3 - /Cl - ratios and low δ 15 N values (+1 per mil (‰)) similar to those of modern bulk atmospheric N deposition. The δ 18 O values of the NO 3 - (−4 to 0 ‰) indicate that atmospheric NO 3 - was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO 3 - /Cl - ratios have relatively high ClO 4 - concentrations (1.0−1.8 μg/L) with a nearly constant ClO 4 - /Cl - mole ratio of (1.4 ± 0.1) × 10 - 4 , which would be consistent with an average ClO 4 - concentration of 0.093 ± 0.005 μg/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher δ 15 N values (+3 to +8 ‰), lower NO 3 - /Cl - ratios, and lower ClO 4 - /Cl - ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO 3 - also may have depleted ClO 4 - to varying degrees prior to recharge. If these interpretations are correct, then ClO 4 - concentrations of atmospheric origin as high as 4 μg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO 4 - concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO 4 - exist.

Environmental Science & Technology↗

USGS2003

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite-water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite−water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [ P CO 2 = 10 - 3.5 atm and ∼0; CO 2 -free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L - 1 , [As(V)] 0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L - 1 , [As(V)] 0 = 0.5 mM and I = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems ( P CO 2 = 10 - 3.5 atm) than in the CO 2 -free argon system at pH 4−7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (≈2.8 Å) and bidentate binuclear (≈3.3 Å) bonding at pH 4.5−8 and loading levels of 0.46−3.10 μM m - 2 . Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P CO 2 = 10 - 3.5 atm and the CO 2 -free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO 2 (g).

Environmental Science & Technology↗