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At least 613 records · Page 34Linked to original sources

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr(VI) and Cr(VI) adsorbed onto γ-Al 2 O 3 and goethite is less than 0.04‰ ( 53 Cr/ 52 Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53 Cr/ 52 Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO 4 - and CrO 4 2 - was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in δ 53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Environmental Science & Technology↗

Incidence of the enterococcal surface protein ( esp ) gene in human and animal fecal sources

The occurrence of the enterococcal surface protein ( esp ) gene in the opportunistic pathogens Enterococcus faecalis and E. faecium is well-documented in clinical research. Recently, the esp gene has been proposed as a marker of human pollution in environmental waters; however, information on its relative incidence in various human and animal fecal sources is limited. We have determined the occurrence of the esp gene in enterococci from human ( n = 64) and animal ( n = 233) fecal samples by polymerase chain reaction using two primer sets: one presumably specific for E. faecium ( esp fm ) and the other for both E. faecalis and E. faecium ( esp fs/fm ). We believe that this research is the first to explore the use of esp fs/fm for the detection of human waste in natural environmental settings. The incidence in human sources was 93.1% esp fm and 100% esp fs/fm in raw sewage influent; 30% for both esp fm and esp fs/fm in septic waste; and 0% esp fm and 80% esp fs/fm in active pit toilets. The overall occurrence of the gene in animal feces was 7.7% ( esp fs/fm ) and 4.7% ( esp fm ); animal types with positive results included dogs (9/43, all esp fm ), gulls (10/34, esp fs/fm ; 2/34, esp fm ), mice (3/22, all esp fs/fm ), and songbirds (5/55, all esp fs/fm ). The esp gene was not detected in cat (0/34), deer (0/4), goose (0/18), or raccoon (0/23) feces. The inconsistent occurrence, especially in septic and pit toilet sewage, suggests a low statistical power of discrimination between animal and human sources, which means a large number of replicates should be collected. Both esp fm and esp fs/fm were common in raw sewage, but neither one efficiently differentiated between animal and other human sources.

Environmental Science & Technology↗

Natural chlorate in the environment: Application of a new IC-ESI/MS/MS method with a Cl18O3- internal standard

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO 3 − ) in environmental samples. The method involves the electro-chemical generation of isotopically labeled chlorate internal standard (Cl 18 O 3 − ) using 18 O water (H 2 18 O). The standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO 3 − was 2 ng L −1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO 3 − in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO 3 − analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO 4 − ) occurrence were analyzed using the proposed method and ClO 3 − was found to co-occur with ClO 4 − at concentrations ranging from <2 ng L −1 in precipitation from Texas and Puerto Rico to >500 mg kg −1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO 3 − in some natural groundwater samples (<0.1 μg L −1 ) analyzed in this work may indicate lower stability when compared to ClO 4 − in the subsurface. The high concentrations of ClO 3 − in caliches and soils (3−6 orders of magnitude greater) as compared to precipitation samples indicate that ClO 3 − , like ClO 4 − , may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Environmental Science & Technology↗

Tracking nonpoint source nitrogen pollution in human-impacted watersheds

Nonpoint source nitrogen (N) pollution is a leading contributor to U.S. water quality impairments. We combined watershed N mass balances and stable isotopes to investigate fate and transport of nonpoint N in forest, agricultural, and urbanized watersheds at the Baltimore Long-Term Ecological Research site. Annual N retention was 55%, 68%, and 82% for agricultural, suburban, and forest watersheds, respectively. Analysis of &delta; 15 N-NO 3 &ndash; , and &delta; 18 O-NO 3 &ndash; indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between &delta; 15 N-NO 3 &ndash; and &delta; 18 O-NO 3 &ndash; in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed &sim;50% at peak storm N loads). Positive correlations between &delta; 15 N-NO 3 &ndash; and &delta; 18 O-NO 3 &ndash; in watersheds suggested denitrification was removing septic system and agriculturally derived N, but N from belowground leaking sewers was less susceptible to denitrification. N transformations were also observed in a storm drain (no natural drainage network) potentially due to organic carbon inputs. Overall, nonpoint sources such as atmospheric deposition, wastewater, and fertilizer showed different susceptibility to watershed N export. There were large changes in nitrate sources as a function of runoff, and anticipating source changes in response to climate and storms will be critical for managing nonpoint N pollution.

Environmental Science & Technology↗

Geochemistry of inorganic nitrogen in waters released from coal-bed natural gas production wells in the Powder River Basin, Wyoming

Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs ( n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day −1 entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.

Wyoming↗

Metolachlor and alachlor breakdown product formation patterns in aquatic field mesocosms

The transformation of metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl)acetamide] and alachlor [2-chloro- N -(2,6-diethylphenyl)- N -(methoxymethyl)acetamide] in aquatic systems was investigated using outdoor tank mesocosms. Metolachlor and alachlor levels and their ethane sulfonic acid (ESA) and oxanillic acid breakdown products were monitored over time under five experimental treatments (each in quadruplicate). Background water conditions were identical in all treatments with each treatment differing based on the level and type(s) of herbicide present. Treatments included a no-herbicide control, 10 μg/L metolachlor, 25 μg/L metolachlor, 25 μg/L alachlor, and 25 μg/L alachlor plus 25 μg/L metolachlor in combination. The experiment was initiated by adding herbicide(s) to the units to the target concentrations; herbicide and breakdown product levels and other chemical parameters were then monitored for 85 days. In general, metolachlor half-lives were longer than alachlor half-lives under all treatments, although the differences were not statistically significant. Metolachlor half-lives (±95% confidence limits) ranged from 33.0 d (±14.1 d) to 46.2 d (±40.0 d), whereas alachlor half-lives ranged from 18.7 d (±3.5 d) to 21.0 d (±6.5 d) for different treatments. Formation patterns of ESA were similar in all treatments, whereas oxanillic acid formation differed for the two herbicides. Alachlor oxanillic acid was produced in larger quantities than metolachlor oxanillic acid and either ESA under equivalent conditions. Our results suggest that the transformation pathways for alachlor and metolachlor in aquatic systems are similar and resemble the acetochlor pathway in soils proposed by Feng ( Pestic. Biochem. Physiol . 1991 , 34 , 136); however, the oxanillic acid branch of the pathway is favored for alachlor as compared with metolachlor.

Environmental Science & Technology↗

Centurial persistence of forever chemicals at military fire training sites

Drinking water contamination by per- and polyfluoroalkyl substances (PFAS) is widespread near more than 300 United States (U.S.) military bases that used aqueous film-forming foams (AFFF) for fire training and firefighting activities. Much of the PFAS at these sites consist of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods. Here, we estimate the expected duration and contribution of precursor biotransformation to groundwater PFAS contamination at an AFFF-contaminated military base on Cape Cod, Massachusetts, United States, by optimizing a geochemical box model using measured PFAS concentrations from a multidecadal time series of groundwater and a soil survey in the source zone. A toolbox of analytical techniques used to reconstruct the mass budget of PFAS showed that precursors accounted for 46 ± 8% of the extractable organofluorine (a proxy for total PFAS) across years. Terminal PFAS still exceed regulatory limits by 2000-fold decades after AFFF use ceased. Measurements and numerical modeling show that sulfonamido precursors are retained in the vadose zone and their slow biotransformation into perfluoroalkyl sulfonates (half-life > 66 yr) sustains groundwater concentrations of perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS). The estimated PFAS reservoir in the vadose zone and modeled flux into groundwater suggest PFAS contamination above regulatory guidelines will persist for centuries without remediation.

Massachusetts↗

The role of the Everglades Mangrove Ecotone Region (EMER) in regulating nutrient cycling and wetland productivity in South Florida

The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height <3 m cover 49% of the EMER, particularly in the SE region. These scrub/dwarf mangroves are the result of a combination of low soil phosphorus (P < 59 μg P g dw −1 ) in the calcareous marl substrate and long hydroperiod. Phosphorus limits the EMER and its freshwater watersheds due to the lack of terrigenous sediment input and the phosphorus-limited nature of the freshwater Everglades. Reduced freshwater delivery over the past 50 years, combined with Everglades compartmentalization and a 10 cm rise in coastal sea level, has led to the landward transgression (∼1.5 km in 54 years) of the mangrove ecotone. Seasonal variation in freshwater input strongly controls the temporal variation of nitrogen and P exports (99%) from the Everglades to Florida Bay. Rapid changes in nutrient availability and vegetation distribution during the last 50 years show that future ecosystem restoration actions and land use decisions can exert a major influence, similar to sea level rise over the short term, on nutrient cycling and wetland productivity in the EMER.

Florida↗

Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, High Plains, U.S.A.

Mobilization of natural nitrate (NO 3 - ) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO 3 - concentrations. The use of isotopes to distinguish between natural and anthropogenic NO 3 - sources in these settings could be complicated by the wide range in δ 15 N values of natural NO 3 - . An ∼10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that δ 15 N values for NO 3 - derived from natural sources ranged from 1.3 to 12.3‰ and increased systematically from the northern to the southern High Plains. This collective range in δ 15 N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO 3 - ; however, the δ 15 N values for NO 3 - in modern recharge ( less than 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the δ 15 N[NO 3 - ] values and the NO 3 - /Cl - ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO 3 - are consistent with both NH 3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.

Environmental Science & Technology↗

Contaminant exposure and transport from three potential reuse waters within a single watershed

Global demand for safe and sustainable water supplies necessitates a better understanding of contaminant exposures in potential reuse waters. In this study, we compared exposures and load contributions to surface water from the discharge of three reuse waters (wastewater effluent, urban stormwater, and agricultural runoff). Results document substantial and varying organic-chemical contribution to surface water from effluent discharges (e.g., disinfection byproducts [DBP], prescription pharmaceuticals, industrial/household chemicals), urban stormwater (e.g., polycyclic aromatic hydrocarbons, pesticides, nonprescription pharmaceuticals), and agricultural runoff (e.g., pesticides). Excluding DBPs, episodic storm-event organic concentrations and loads from urban stormwater were comparable to and often exceeded those of daily wastewater-effluent discharges. We also assessed if wastewater-effluent irrigation to corn resulted in measurable effects on organic-chemical concentrations in rain-induced agricultural runoff and harvested feedstock. Overall, the target-organic load of 491 g from wastewater-effluent irrigation to the study corn field during the 2019 growing season did not produce substantial dissolved organic-contaminant contributions in subsequent rain-induced runoff events. Out of the 140 detected organics in source wastewater-effluent irrigation, only imidacloprid and estrone had concentrations that resulted in observable differences between rain-induced agricultural runoff from the effluent-irrigated and nonirrigated corn fields. Analyses of pharmaceuticals and per-/polyfluoroalkyl substances in at-harvest corn-plant samples detected two prescription antibiotics, norfloxacin and ciprofloxacin, at concentrations of 36 and 70 ng/g, respectively, in effluent-irrigated corn-plant samples; no contaminants were detected in noneffluent irrigated corn-plant samples.

Oklahoma↗

Association of toxin-producing Clostridium botulinum with the macroalga Cladophora in the Great Lakes

Avian botulism, a paralytic disease of birds, often occurs on a yearly cycle and is increasingly becoming more common in the Great Lakes. Outbreaks are caused by bird ingestion of neurotoxins produced by Clostridium botulinum, a spore-forming, gram-positive, anaerobe. The nuisance, macrophytic, green alga Cladophora (Chlorophyta; mostly Cladophora glomerata L.) is a potential habitat for the growth of C. botulinum. A high incidence of botulism in shoreline birds at Sleeping Bear Dunes National Lakeshore (SLBE) in Lake Michigan coincides with increasingly massive accumulations of Cladophora in nearshore waters. In this study, free-floating algal mats were collected from SLBE and other shorelines of the Great Lakes between June and October 2011. The abundance of C. botulinum in algal mats was quantified and the type of botulism neurotoxin (bont) genes associated with this organism were determined by using most-probable-number PCR (MPN-PCR) and five distinct bont gene-specific primers (A, B, C, E, and F). The MPN-PCR results showed that 16 of 22 (73%) algal mats from the SLBE and 23 of 31(74%) algal mats from other shorelines of the Great Lakes contained the bont type E (bont/E) gene. C. botulinum was present up to 15 000 MPN per gram dried algae based on gene copies of bont/E. In addition, genes for bont/A and bont/B, which are commonly associated with human diseases, were detected in a few algal samples. Moreover, C. botulinum was present as vegetative cells rather than as dormant spores in Cladophora mats. Mouse toxin assays done using supernatants from enrichment of Cladophora containing high densities of C. botulinum (>1000 MPN/g dried algae) showed that Cladophora-borne C. botulinum were toxin-producing species (BoNT/E). Our results indicate that Cladophora provides a habitat for C. botulinum, warranting additional studies to better understand the relationship between this bacterium and the alga, and how this interaction potentially contributes to botulism outbreaks in birds.

Great Lakes↗

Sorption of selected organic compounds from water to a peat soil and its humic-acid and humin fractions: Potential sources of the sorption nonlinearity

The sorption isotherms of ethylene dibromide (EDB), diuron (DUN), and 3,5-dichlorophenol (DCP) from water on the humic acid and humin fractions of a peat soil and on the humic-acid of a muck soil have been measured. The data were compared with those of the solutes with the whole peat from which the humic-acid (HA) and humin (HM) fractions were derived and on which the sorption of the solutes exhibited varying extents of nonlinear capacities at low relative concentrations (C(e)/S(w)). The HA fraction as prepared by the density-fractionated method is relatively pure and presumably free of high- surface-area carbonaceous material (HSACM) that is considered to be responsible for the observed nonlinear sorption for nonpolar solutes (e.g., EDB) on the peat; conversely, the base-insoluble HM fraction as prepared is presumed to be enriched with HSACM, as manifested by the greatly higher BET- (N2) surface area than that of the whole peat. The sorption of EDB on HA exhibits no visible nonlinear effect, whereas the sorption on HM shows an enhanced nonlinearity over that on the whole peat. The sorption of polar DUN and DCP on HA and HM display nonlinear effects comparable with those on the whole peat; the effects are much more significant than those with nonpolar EDB. These results conform to the hypothesis that adsorption onto a small amount of strongly adsorbing HSACM is largely responsible for the nonlinear sorption of nonpolar solutes on soils and that additional specific interactions with the active groups of soil organic matter are responsible for the generally higher nonlinear sorption of the polar solutes.

Environmental Science & Technology↗

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↗

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↗

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↗

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↗

Use case development for earth monitoring, analysis, and prediction (EarthMAP)—A road map for future integrated predictive science at the U.S. Geological Survey

Executive Summary The U.S. Geological Survey (USGS) 21st-century science strategy 2020–30 promotes a bureau-wide strategy to develop and deliver an integrated, predictive science capability that works at the scales and timelines needed to inform societally relevant resource management and protection and public safety and environmental health decisions (U.S. Geological Survey, 2021). This is the overarching goal of the USGS Earth Monitoring, Analysis, and Prediction (EarthMAP) vision, which consists of three components: (1) integrated data and information, (2) integrated predictive science, and (3) actionable information—all designed and delivered to respond to user needs. To launch this vision and help shape the design and implementation of integrated predictive science, the USGS Regional Offices each developed a set of use cases (hereafter Use Cases)—short descriptions of potential science applications that could clearly address high priority decision-making needs of our stakeholders and that align with an integrated science focus. Use Cases are not actionable science planning documents, nor stand-alone scholarly works, but should be considered as innovative, next-generation science ideas that can be considered as potential components of science plans still under development. The goal of Use Case development was to (1) identify and characterize existing USGS scientific capacities and expertise that can support science goals and products, (2) identify opportunities to leverage current capacities for next-generation science, and (3) foster engagement across the entire Bureau to further refine the USGS strategy for EarthMAP and integrated predictive science. The Use Case development effort documented in this report was coordinated by the Use Case Development Team (UCDT), consisting of representatives from each region. The UCDT undertook five tasks: (1) develop a unified approach to engage bureau scientists consistently across all regions in aspirational thinking about what can be accomplished; (2) work with the regions and their Science Centers to generate an initial set of Use Cases, authored directly by scientists; (3) characterize, summarize, and document the initial set of Use Case submissions from authors to illuminate bureau-level demand for integrated science; (4) compare existing and needed capacities from the Use Case descriptions with preliminary results of the EarthMAP Capacity Assessment (Keisman and others, 2021); and (5) describe lessons learned from the Use Case development process and provide recommendations to inform future efforts to generate integrated science activities. This report outlines the approach the UCDT developed to solicit Use Cases from the regions and summarizes the high-level qualitative findings from this first-round effort. The UCDT received 36 Use Cases from the regions and identified potential points of convergence and commonalities considered useful in making connections among the participating scientists. The Southwest (SW) Region and the Rocky Mountain (RM) Region asked scientists to give special consideration to Use Cases with applicability to the Colorado River Basin, and seven of the Use Cases specifically named that geographic area as a focus. Coastal hazards and coastal resilience were identified in Use Cases from the Alaska (AK), Northeast (NE), and Southeast (SE) Regions. Aspects of wildfire and post-wildfire response were part of Uses Cases from AK, RM, and SW Regions. The greatest convergence of Use Case themes was related to conservation of public lands and waters, which is a powerful linkage lending strength to future collaborative efforts. The most common type of stakeholder decisions that would be informed by the Use Case science applications were related to adaptation, mitigation, and response (for example, how to increase the resilience of coastal communities to climate-related stressors and how to prevent or respond to harmful algal blooms). Other common types of decisions included water and land management decisions (including operational water management decisions such as reservoir operations and land use planning in the sagebrush biome), decisions about how to manage and conserve habitats and species, and risk management decisions (such as managing the post-wildfire flood risks). These decision types are not exclusive because many Use Cases cross categories. Use Case authors identified existing and needed science and technology capabilities required for Use Case implementation, which were then aligned to capabilities assessed in the EarthMAP Capacity Assessment (Keisman and others, 2021). Strong alignment was found for data and information integration approaches, modeling and prediction approaches, and capabilities related to delivery of actionable information. A majority of Use Cases indicated insufficient current capacity for needed data collection methods, data integration, and modeling and prediction approaches, whereas only 25 percent indicated insufficient capacity for actionable information delivery. Overall, many Use Case capacity demand gaps could potentially be met by existing bureau-wide capacity. In addition, nearly half of the Use Cases could potentially be implemented within 3 years if funding, capabilities, and personnel impediments were removed and science priorities were realigned. Several challenges emerged during the Use Case development process. The first challenge was developing an approach that was flexible enough to accommodate regional differences in planning and implementation, while also ensuring enough guidance to promote meaningful summary analyses. The UCDT encountered a strong demand for continuous communication and education to improve overall understanding of the integrated predictive science strategy. Another challenge was managing expectations about EarthMAP activities as a design effort that was not aligned to an immediate funding opportunity. Connecting the Use Cases to stakeholder needs without the opportunity for direct stakeholder engagement was also challenging. The last notable challenge was in obtaining consistent interpretation and characterization of the qualitative data housed in the narrative descriptions of Use Cases, written in different styles. Overall, the 36 Use Cases can serve as components of a road map for advancing integrated monitoring and predictive science throughout the USGS by revealing opportunities to (1) encourage cross-region initiatives that address shared interests in common themes by integrating similar Use Cases and through direct involvement of stakeholders in identifying needs and designing effective responses, (2) leverage the Use Cases to target investments that are aligned with the Bureau and Department of the Interior (DOI) priorities, (3) connect Use Cases and the results of the companion EarthMAP Capacity Assessment (Keisman and others, 2021) to identify potential priorities for capacity building investments, and (4) raise awareness of common integrated and interdisciplinary science interests within and across the regions through Use Case and Capacity Assessment summary outreach activities.

Open-File Report↗

Fishway Entrance Palisade

This technical report summarizes the work that was conducted by the University of Massachusetts Amherst and the United States Geological Survey (USGS), along with other project partners, on the Fishway Entrance Palisade (EP), a projected funded through the Department of Energy’s (DOE) funding opportunity titled ‘Innovative Solutions for Fish Passage at Hydropower Dams’ (DE‐FOA‐0001662). The period of performance ranged from September 1, 2018 through September 30, 2021. The EP is a novel fish passage engineering technology designed to provide more favorable entry conditions for fish and to reduce costs relative to conventional fishway auxiliary water systems (AWS). The EP project has four primary components. First, the Northeast United States Auxiliary Water Systems Database was created (Northeast Fishway Auxiliary Water Systems Database Section). The database, developed with material provided by the U.S. Fish and Wildlife Service, contains information on fishway type (e.g., lift, Denil, pool and weir) and Auxiliary Water System (AWS) details (e.g., water conveyance method, diffuser type) for 60 hydroelectric sites in the region. Findings indicate that nearly 4 out of every 10 fishway in the region is a fish lift and approximately 1 out of every 4 is a Denil ladder. The remainder are a mix of vertical slot fishways, pool and weirs, and Ice Harbor fishways. Furthermore, over half of all AWS systems use floor diffusers to discharge the auxiliary (or attraction) water into the entrance of a fishway, whereas only 14% use wall diffusers. Second, limited experiments on a conventional AWS with live, actively migrating fish were conducted at the USGS Easter Ecological Science Center (EESC) S.O. Conte Research Laboratory (Conventional Auxiliary Water System Experiments Section). This study determined how water velocity through a wall diffuser, without turning vanes or timber baffles to distribute the flow, affects the behavior and passage of adult American shad, a conservative surrogate species for migratory fish on the East Coast. Two gross diffuser velocity treatments were examined, 0.5 ft/s and 1.0 ft/s. These wall diffuser velocities represented current (0.5 ft/s) and past (1.0 ft/s) design criteria guidelines set forth by the USFWS North Atlantic-Appalachian Region (Rojas 2020; USFWS 2019). Six trials with a total of 151 American Shad were conducted in June of 2019 for the two treatments. No differences in American shad passage efficiency were discovered between the two treatments, while approximately 3 in every 4 attempts were successful at passing the diffuser. While these results may appear to indicate that the generally accepted gross wall diffuser velocity criteria for American shad of 0.5 ft/s could be safely increased to 1.0 ft/s, further analysis is warranted. Furthermore, it is unknown how other migratory and resident fish species that traverse these structures would be impacted by such a change. Studying the wall diffuser hydraulics led to an important AWS observation. Without turning vanes or timber baffles in this study, doubling the diffuser area was insufficient at producing the type of flow field change one may expect by halving the gross diffuser velocity. Instead, the flow fields throughout each treatments study area were similar, which led to similar results in shad performance. This not only highlights the importance of installing flow guidance devices like turning vanes, but also to the importance of properly maintaining them, which can be costly. Third, more expansive experiments on the novel EP were conducted in the spring of 2019 and 2021 (Fishway Entrance Palisade Experiments). The goal of this study was to determine how adult American shad responded to a variety of conditions at a full-scale EP. A total of six treatments were examined by changing the average auxiliary channel velocity between 1.0 and 5.0 ft/s in intervals of 1.0 ft/s and by inserting/removing an entrance gate at the opening of the fishway. Thirty trials with a total of 1,273 shad were conducted over the two years. In all treatments, at least ~7 out of every 10 fish successfully passed the EP diffuser and swam into the entrance channel within the 3.5-hour long trial, highlighting the general effectiveness of the novel AWS technology. In both study years, lower velocities through the EP diffuser led to increased shad performance, though performance peaked for the 2 ft/s velocity treatment. This treatment condition represents an approximate six-fold increase in gross diffuser velocity relative to conventional auxiliary water systems, which in turn presents opportunities for cost savings (e.g., reduction in diffuser size). Shad performance, in general, was worse in 2019 than in 2021, potentially due to the different run timing when our trials were conducted (2019 trials occurred near the end of the migration season, unlike in 2021). Treatments in 2019 had approximately a 20% reduction in entrance efficiency by the trial end, including a 16.7% drop for the 3 ft/s velocity treatment in 2019 relative to 2021 (the only carryover treatment between years). Lastly, adding an entrance gate caused a significant delay to entry. The time to 25% entry raised ~20 minutes from the near instantaneous 25% entry that was reported for the other treatments conducted in the same year (2021). Though by the end of the 3.5-hour trial, the overall entrance efficiency nearly matched those of the other 2021 treatments. The fourth and final component of the EP project was an economic analysis that focused on the cost of attraction and environmental flows (Modeling Power Generation Losses Due to Environmental and Fish Passage Attraction Flows at a Run-Of-River Hydroelectric Operation in the Northeast). The study assessed the economic impact of meeting environmental flow requirements at a representative hydroelectric facility and fish lift in the Northeast. An initial finding of the study was that there is a paucity of published data on the costs of meeting attraction and environmental flows. This is due, in part, to the proprietary nature of this data. To explore the costs associated with these flows, three types of environmental flows were assessed: upstream fishway attraction flows, downstream fishway attraction flows, and habitat maintenance minimum flows. A physics-based model was developed and calibrated with three years of hourly generation and flow data as inputs. Gage flow inputs were adjusted and used to calculate power generated. To address hydrologic variability, the model was executed to simulate 30 years of historical flows. Results indicate that both interannual and seasonal climatic factors impact the costs of meeting environmental flow requirements. Generation potential is most strongly curtailed during dry years in terms of maximizing the capacity factor (the percent of time a plant generates at capacity). Dry years, and especially dry summers, have the most significant costs associated with mitigation flows. Of the three types of flows, habitat flows are most costly in terms of power production, followed by upstream attraction flows. Downstream attraction flows are least costly. This finding is the likely result of differences in both flow rates and duration of the seasonal requirement for each flow. Overall, environmental flows represented a 2-12% loss in annual generation, but losses during a dry summer can reach over 20%.

Final Technical Report↗