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247 records · Page 14Linked to original sources
USGS1988

Concurrent mobile on-site and in situ striped bass contaminant and water quality studies in the Choptank River and upper Chesapeake Bay

In situ and mobile on-site striped bass prolarval and yearling survival studies were conducted in the Choptank River and in the Chesapeake and Delaware (C & D) Canal area of the Upper Chesapeake Bay. Extensive chemical analyses of both organic and inorganic contaminants in the habitat water were performed and water quality parameters were monitored during these experiments. Surviving yearling striped bass were subjected to histological examination. Prolarval survival data from both the in situ and mobile on-site studies were similar for each spawning area. Prolarval survival ranged from 30 to 45% after 96 h of exposure to Choptank River water in four separate experiments (two in situ , two on-site); control survival was greater than 74%. Based on a comparison of laboratory toxicity data and reported field concentrations in the Choptank River for various water quality and contaminant conditions, the following combination of conditions was potentially stressful to striped bass prolarvae: low hardness (36 to 48 mg/L CaCO 3 ), monomeric aluminum (0.150 mg/L), cadmium (0.003 mg/L) and copper (0.040 mg/L). Yearling survival in both in situ and on-site tests ranged from 93 to 100% in both the control and Choptank River water after 9 d of exposure. Survival of striped bass prolarvae in C & D Canal water ranged from 52.5 to 70% after 96 h of exposure in four separate experiments. Control survival of prolarvae was not significantly different. Survival of yearling striped bass in on-site and in situ tests was 95% or greater in C & D Canal water and control water. Acute contaminant effects were not verified in the C & D Canal area.

Environmental Toxicology and Chemistry↗
USGS2008

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter↗
USGS2009

Effects of egg order on organic and inorganic element concentrations and egg characteristics in tree swallows, tachycineta bicolor

The laying order of tree swallow eggs was identified from the Housatonic River, Berkshire County, Massachusetts, USA, and eggs were chemically analyzed individually to document possible effects of laying order on organic contaminant and inorganic element concentrations. Effects of laying order on other parameters such as egg weight, size, and lipid and moisture content also were assessed. Some effects of egg order on total polychlorinated biphenyls (PCBs) were detected, but the effect was not uniform across individual females or between years. In 2004, clutches with higher total PCBs tended to have concentrations decline across egg order, whereas clutches with lower concentrations of PCBs tended to increase across egg order. In contrast, in 2005, there was a tendency for concentrations to increase across egg order. Polychlorinated biphenyl concentrations were highly variable within and among clutches in both years. The directionality of egg order associations (i.e., slopes) for trace elements was element dependent, was positive for Mn and Zn, was negative for B, and had no slope for Cr. Whole egg weight increased across egg order. Percentage lipid was variable within a clutch, with no pattern common across all females. Percentage lipid was also correlated with organic contaminant concentration. In highly contaminated environments, higher lipid content could have the unanticipated corollary of having higher concentrations of lipophilic contaminants such as PCBs. To reduce the effect of high variation within a clutch when assessing contamination exposure, it is recommended that two eggs per clutch be collected and pooled for chemical analysis. We further recommend that, as long as the two eggs are randomly collected, the additional effort needed to identify and collect specific eggs is not warranted.

Massachusetts↗
USGS1998

Association of mercury and selenium with altered glutathione metabolism and oxidative stress in diving ducks from the San Francisco Bay region

Ault male greater scaup ( Aythya marila ), surf scoters ( Melanitta perspicillata ), and ruddy ducks ( Oxyurajamaicensis ) were collected from Suisun Bay and coastal Tomales Bay in the greater San Francisco Bay area to assess exposure to inorganic contaminants. Hepatic Se concentrations were highest in greater scaup (geometric mean = 67 ppm dry weight) and surf scoters (119 ppm) in Suisun Bay, whereas hepatic Hg was highest (19 ppm) in greater scaup and surf scoters from Tomales Bay. Hepatic Se and Hg were lower in ruddy ducks and did not differ between locations. Hepatic supernatants were assayed for enzymes related to glutathione metabolism and antioxidant activity, including glucose-6-phosphate dehydrogenase (G-6-PDH), glutathione peroxidase (GSH peroxidase), glutathione reductase (GSSG reductase), and glutathione- S -transferase (GSH transferase). Glutathione peroxidase activity was higher in surf scoters and ruddy ducks, and G-6-PDH was higher in greater scaup and surf scoters from Suisun Bay than Tomales Bay. Glutathione reductase (GSSG) was higher in SS from Suisun Bay. The ratio of oxidized glutathione (GSSG) to reduced glutathione (GSH) was greater in all species from Tomales Bay. The following significant relationships were found in one or more species with increasing hepatic Hg concentration: lower body, liver, and heart weights; decreased hepatic GSH concentration and G-6-PDH and GSH peroxidase activities; increased ratio of GSSG to GSH; and increased GSSG reductase activity. With increasing hepatic Se concentration, GSH peroxidase increased, but GSH decreased. It is concluded that measurement of associated enzymes in conjunction with thiol status may be a useful bioindicator to discriminate between Hg and Se effects. Concentrations of Hg and Se and the above variables affected have been associated with adverse effects on reproduction and neurological function in experimental studies with mallards.

Environmental Toxicology and Chemistry↗
USGS2011

Simultaneous speciation of arsenic, selenium, and chromium: species, stability, sample preservation, and analysis of ash and soil leachates

An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)-ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC-ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10° C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.

Analytical and Bioanalytical Chemistry↗
USGS2007

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)2, and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations.

Nevada↗
USGS1997

Geochemistry and microbiology of iron-related well-screen encrustation and aquifer biofouling in Suffolk County, Long Island, New York

Iron-related well-screen encrustation and aquifer biofouling has decreased the specific capacity of several production wells in Suffolk County, N.Y., and has forced the Suffolk County Water Authority to adopt a costly well-reconditioning and replacement program. The specific-capacity declines are the result of the precipitation of iron oxyhydroxides and the growth of iron bacteria on the well screens and in the pore spaces of the surrounding formation. Mineralogic and chemical analyses indicate that the inorganic part of the encrusting material consists primarily of amorphous ferric hydroxide (Fe(OH)3 ); minor components of the material include goethite (FeOOH), hematite (Fe2 O 3 ), and quartz (SiO 2 ). The weight percent of ferric hydroxide in the material ranged from 32.3 to 98.6 percent and averaged 64.3 percent. Equilibrium modeling indicated that during pumping the well waters were supersaturated with respect to goethite, hematite, magnetite, and quartz and were under-saturated with respect to ferric hydroxide. Theoretical Eh values computed for the ferrous/ferric-iron redox couple and the oxygen/water redox couple averaged 390 millivolts and 810 millivolts, respectively, indicating that the waters were in a state of redox disequilibrium. The disequilibrium condition arises from the mixing of ground water with a low dissolved-oxygen concentration with oxygenated ground water during operation of the well. The low pH of the ground water contributes to the disequilibrium condition by slowing the rate of iron oxidation after the introduction of oxygen. Chemical and mineralogical data indicate that most of the encrusting material in the wells was deposited while the wells were shut down, probably in response to the use of treated water of higher pH to keep pump turbines wet while the wells were not in operation; the increased pH of water in the static water column increases the rate of ferrous-iron oxidation and causes the well water to become increasingly saturated with respect to ferric hydroxide. The median half-time of oxidation in samples of untreated ground water (pH 4-5) was 4.19 days, whereas the average half-time of oxidation in treated water (pH 7-8) was 11.9 minutes Equilibrium modeling indicated that treated waters generally were supersaturated with respect to ferric hydroxide, whereas untreated well waters were not. Field and laboratory data indicate that iron bacteria play an important role in the encrustation and biofouling process in Suffolk County. Filamentous iron bacteria were common in the affected wells. The most common species was Gallionella ferruginea, an effective biofouling agent that prefers water with low, but detectable, dissolved-oxygen concentrations and high dissolved-iron concentrations; this species was more common in biofilm samples from the Magothy aquifer than in those from the upper glacial aquifer. Iron bacteria also were found in sediment cores from several locations in the aquifer and in drilling water. Lignite could act as a carbon source for heterotrophic iron bacteria, which could accelerate the formation of iron-bacteria biofilms in wells screened in some parts of the Magothy aquifer. Iron-bacteria biofilms alter the chemistry of well water by removing iron, manganese, and sulfate from solution and by increasing the pH. Sulfur-reducing bacteria and iron-sulfide mineral phases were observed in some samples of encrusting material, indicating that these bacteria could contribute to well-screen encrustation in some geochemical environments.

Water-Resources Investigations Report↗
USGS2018

Geochemistry and microbiology of groundwater and solids from extraction and monitoring wells and their relation to well efficiency at a Federally operated confined disposal facility, East Chicago, Indiana

In cooperation with the U.S. Army Corps of Engineers, Chicago District, the U.S. Geological Survey investigated the processes affecting water quality, geochemistry, and microbiology in representative extraction and monitoring wells at a confined disposal facility (CDF) in East Chicago, Indiana. The CDF is a 140-acre Federally-managed facility that was the former location of an oil refinery and is now used for the long-term disposal and storage of dredge material from the Indiana Harbor and Indiana Harbor Canal. Residual petroleum hydrocarbons and leachate from the CDF are contained within the facility by use of a groundwater cutoff wall. The wall consists of a soil-bentonite slurry and a gradient control system made up of an automated network of 96 extraction wells, 42 monitoring wells, and 2 ultrasonic sensors that maintain an inward hydraulic gradient at the site. The pumps in the extraction wells require vigilant maintenance and must be replaced when unable to withdraw water at a rate sufficient to maintain the required inward gradient. The wells are screened in the Calumet aquifer, a coarse-grained sand and gravel unit that extends approximately 35 feet below the land surface and is not utilized for drinking-water supply at the CDF or in the surrounding area. This study was initiated to identify the cause of decreased pump discharges and to identify potential mitigation strategies. For this study, the U.S. Geological Survey collected groundwater and solids from monitoring and extraction wells. Groundwater samples were collected during June 2014 for precautionary health screening and on four occasions during September 2014 through November 2014. Groundwater samples collected from two extraction wells during June 2014 were analyzed for concentrations of anthropogenic organic constituents. During September through November 2014, groundwater samples were collected from one additional extraction well, and samples from three monitoring wells were analyzed for concentrations of inorganic and organic constituents, dissolved gases, and bacterial abundance and diversity. Solid samples were collected during April 2014, during September 2014 through November 2014, and during November 2016. Solid samples were collected from the exterior of extraction-well pumps and as flocculent from water samples. Solid samples were collected from 10 wells, including 1 extraction well and 3 monitoring wells sampled for water quality. Solid samples were analyzed for mineralogy, solid-phase habit, geochemistry, and organic composition. The following is a list of observations that were made during this study: (1) the water quality is substantially variable among the six well locations sampled as part of this study—lower (more negative) redox values and higher concentrations of many constituents (including calcium, magnesium, sodium, and sulfate) and properties (including dissolved solids, hardness, and turbidity) were detected in sampled wells located near the extraction wells with the highest frequency of failure; (2) water-level drawdown is variable between extraction wells—wells with the greatest drawdown may pull deeper groundwater into the borehole; (3) dissolved gas results indicate reducing oxidation-reduction processes in the aquifer material that can feasibly contribute iron, carbon dioxide, and other byproducts from hydrocarbon degradation to precipitates and solids that accumulate on and impair pump operation; (4) crystalline and amorphous solid-phase minerals are precipitating in the borehole; (5) several types of bacteria are present in water pumped from extraction wells and are likely responsible for bonding mineral and microbiologic matter to the pump (and other well components); and (6) bacteria may create microenvironments that facilitate precipitation of solids or inhibit dissolution of unstable minerals once the bacteria adhere to biofilm attached to the pump. Results of the study indicate that bacteria may be accumulating and entrapping solid material on the exterior of pumps. This accumulation reduces heat transfer and water discharge from the pump and may lead to decreased efficiency or mechanical failure. Observations could not be made on the well screen, gravel pack, or surrounding geologic formation; therefore, mitigating measures in the borehole may not solve well-productivity issues. Remedies for the pump fouling problems were derived from the review and interpretation of data collected during this study and from information documented in other sources about groundwater well fouling. Potential remedies to problems associated with pump fouling at the CDF may include the following: (1) reducing attractiveness of the extraction wells for microbiological growth by modifying the chemical or physical environment of the well, (2) modifying the pump exterior to decrease microbiological adherence, (3) changing the pumping regime to control the chemistry of water entering the well from the surrounding aquifer material, (4) modifying the pumps to be less physically and thermally attractive, and (5) removing hydrocarbons from groundwater and the aquifer material surrounding the wells or adding surfactants to make them more mobile. Pilot scale testing may be necessary to identify the most effective treatment or combination of treatments.

Indiana↗
USGS2010

Effects of wastewater effluent discharge and treatment facility upgrades on environmental and biological conditions of the upper Blue River, Johnson County, Kansas and Jackson County, Missouri, January 2003 through March 2009

The Johnson County Blue River Main Wastewater Treatment Facility discharges into the upper Blue River near the border between Johnson County, Kansas and Jackson County, Missouri. During 2005 through 2007 the wastewater treatment facility underwent upgrades to increase capacity and include biological nutrient removal. The effects of wastewater effluent on environmental and biological conditions of the upper Blue River were assessed by comparing an upstream site to two sites located downstream from the wastewater treatment facility. Environmental conditions were evaluated using previously and newly collected discrete and continuous data, and were compared with an assessment of biological community composition and ecosystem function along the upstream-downstream gradient. This evaluation is useful for understanding the potential effects of wastewater effluent on water quality, biological community structure, and ecosystem function. In addition, this information can be used to help achieve National Pollution Discharge Elimination System (NPDES) wastewater effluent permit requirements after additional studies are conducted. The effects of wastewater effluent on the water-quality conditions of the upper Blue River were most evident during below-normal and normal streamflows (about 75 percent of the time), when wastewater effluent contributed more than 20 percent to total streamflow. The largest difference in water-quality conditions between the upstream and downstream sites was in nutrient concentrations. Total and inorganic nutrient concentrations at the downstream sites during below-normal and normal streamflows were 4 to 15 times larger than at the upstream site, even after upgrades to the wastewater treatment facility were completed. However, total nitrogen concentrations decreased in wastewater effluent and at the downstream site following wastewater treatment facility upgrades. Similar decreases in total phosphorus were not observed, likely because the biological phosphorus removal process was not optimized until after the study was completed. Total nitrogen and phosphorus from the wastewater treatment facility contributed a relatively small percentage (14 to 15 percent) to the annual nutrient load in the upper Blue River, but contributed substantially (as much as 75 percent) to monthly loads during seasonal low-flows in winter and summer. During 2007 and 2008, annual discharge from the wastewater treatment facility was about one-half maximum capacity, and estimated potential maximum annual loads were 1.6 to 2.4 times greater than annual loads before capacity upgrades. Even when target nutrient concentrations are met, annual nutrient loads will increase when the wastewater treatment facility is operated at full capacity. Regardless of changes in annual nutrient loads, the reduction of nutrient concentrations in the Blue River Main wastewater effluent will help prevent further degradation of the upper Blue River. The Blue River Main Wastewater Treatment Facility wastewater effluent caused changes in concentrations of several water-quality constituents that may affect biological community structure and function including larger concentrations of bioavailable nutrients (nitrate and orthophosphorus) and smaller turbidities. Streambed-sediment conditions were similar along the upstream-downstream gradient and measured constituents did not exceed probable effect concentrations. Habitat conditions declined along the upstream-downstream gradient, largely because of decreased canopy cover and riparian buffer width and increased riffle-substrate fouling. Algal biomass, primary production, and the abundance of nutrient-tolerant diatoms substantially increased downstream from the wastewater treatment facility. Likewise, the abundance of intolerant macroinvertebrate taxa and Kansas Department of Health and Environment aquatic-life-support scores, derived from macroinvertebrate data, significantly decreased downstream from the wastewater treatment facility. Ecosystem functional health, evaluated using a preliminary framework based on primary production and community respiration, downstream from the wastewater treatment facility was mildly impaired relative to the upstream site during summer 2008 but not during other times of the year. Upgrades to the Blue River Main Wastewater Treatment Facility improved wastewater effluent quality, but the wastewater effluent discharge still had negative effects on the water quality and biological conditions at the downstream sites. Wastewater effluent discharge into the upper Blue River likely contributed to changes in measures of ecosystem structure (streamflow, water chemistry, algal biomass, algal periphyton and macroinvertebrate community composition) and primary production, a measure of ecosystem function, along the upstream-downstream gradient. Because the Blue River Main Wastewater Treatment Facility is located in a rapidly urbanizing area, urbanization effects also may play a role in the decline in environmental and biological conditions along the upstream-downstream gradient. Despite these differences in environmental and biological conditions, ecosystem functional health was not impaired downstream from the WWTF during most times of the year, indicating the declines in environmental and biological conditions along the upstream-downstream gradient were not substantial enough to cause persistent changes in ecosystem function.

Kansas, Missouri↗
USGS2018

Deciphering the dynamics of inorganic carbon export from intertidal salt marshes using high-frequency measurements

The lateral export of carbon from coastal marshes via tidal exchange is a key component of the marsh carbon budget and coastal carbon cycles. However, the magnitude of this export has been difficult to accurately quantify due to complex tidal dynamics and seasonal cycling of carbon. In this study, we use in situ , high-frequency measurements of dissolved inorganic carbon (DIC) and water fluxes to estimate lateral DIC fluxes from a U.S. northeastern salt marsh. DIC was measured by a CHANnelized Optical Sensor (CHANOS) that provided an in situ concentration measurement at 15-min intervals, during periods in summer (July – August) and late fall (December). Seasonal changes in the marsh had strong effects on DIC concentrations, while tidally-driven water fluxes were the fundamental vehicle of marsh carbon export. Episodic events, such as groundwater discharge and mean sea water level changes, can impact DIC flux through altered DIC concentrations and water flow. Variability between individual tides within each season was comparable to mean variability between the two seasons. Estimated mean DIC fluxes based on a multiple linear regression (MLR) model of DIC concentrations and high-frequency water fluxes agreed reasonably well with those derived from CHANOS DIC measurements for both study periods, indicating that high-frequency, modeled DIC concentrations, coupled with continuous water flux measurements and a hydrodynamic model, provide a robust estimate of DIC flux. Additionally, an analysis of sampling strategies revealed that DIC fluxes calculated using conventional sampling frequencies (hourly to two-hourly) of a single tidal cycle are unlikely to capture a representative mean DIC flux compared to longer-term measurements across multiple tidal cycles with sampling frequency on the order of tens of minutes. This results from a disproportionately large amount of the net DIC flux occurring over a small number of tidal cycles, while most tides have a near-zero DIC export. Thus, high-frequency measurements (on the order of tens of minutes or better) over the time period of interest are necessary to accurately quantify tidal exports of carbon species from salt marshes.

Marine Chemistry↗
USGS2009

Mercury, methylmercury, and other constituents in sediment and water from seasonal and permanent wetlands in the Cache Creek settling basin and Yolo Bypass, Yolo County, California, 2005-06

This report presents surface water and surface (top 0-2 cm) sediment geochemical data collected during 2005-2006, as part of a larger study of mercury (Hg) dynamics in seasonal and permanently flooded wetland habitats within the lower Sacramento River basin, Yolo County, California. The study was conducted in two phases. Phase I represented reconnaissance sampling and included three locations within the Cache Creek drainage basin; two within the Cache Creek Nature Preserve (CCNP) and one in the Cache Creek Settling Basin (CCSB) within the creek's main channel near the southeast outlet to the Yolo Bypass. Two additional downstream sites within the Yolo Bypass Wildlife Area (YBWA) were also sampled during Phase I, including one permanently flooded wetland and one seasonally flooded wetland, which had began being flooded only 1–2 days before Phase I sampling. Results from Phase I include: (a) a negative correlation between total mercury (THg) and the percentage of methylmercury (MeHg) in unfiltered surface water; (b) a positive correlation between sediment THg concentration and sediment organic content; (c) surface water and sediment THg concentrations were highest at the CCSB site; (d) sediment inorganic reactive mercury (Hg(II) R ) concentration was positively related to sediment oxidation-reduction potential and negatively related to sediment acid volatile sulfur (AVS) concentration; (e) sediment Hg(II) R concentrations were highest at the two YBWA sites; (f) unfiltered surface water MeHg concentration was highest at the seasonal wetland YBWA site, and sediment MeHg was highest at the permanently flooded YBWA site; (g) a 1,000-fold increase in sediment pore water sulfate concentration was observed in the downstream transect from the CCNP to the YBWA; (h) low sediment pore water sulfide concentrations (<1 µmol/L) across all sites; and (i) iron (Fe) speciation data suggest a higher potential for microbial Fe(III)-reduction in the YBWA compared to the CCSB. Phase II sampling did not include the original three Cache Creek sites, but instead focused on the original two sites within the YBWA and a similarly paired set of seasonally and permanently flooded wetland sites within the CCSB. Sediment sampling at the YBWA and CCSB occurred approximately 28 days and 52 days, respectively, after the initial flooding of the respective seasonal wetlands, and again towards the end of the seasonal flooding period (end of May 2006). Results from Phase II sampling include: (a) sediment MeHg concentration and the percentage of THg as MeHg (%MeHg) in unfiltered surface waters were generally higher in the YBWA compared to the CCSB; (b) suspended sediment concentration (SCC) in surface water was positively correlated with both THg and MeHg in unfiltered water across all sites, although the relationship between SCC and MeHg differed for the two regions, suggesting local MeHg sources; (c) MeHg concentration in unfiltered surface water was positively correlated to sediment MeHg concentrations across all sites, supporting the suggestion of unique local (sediment) sources of MeHg to the water column; (d) THg concentration in filtered water was positively correlated with both total Fe and dissolved organic carbon (DOC), offering additional support for the role of these constituents in the partitioning of THg between particulate and dissolved phases; (e) flooding of the YBWA seasonal wetland resulted in a rapid and significant (5-fold) rise in sediment MeHg concentration within 3–4 weeks following inundation; and (f) temporal changes in sediment S and Fe speciation suggest that rates of both microbial sulfate reduction and Fe(III)-reduction were significantly higher at YBWA, compared to CCSB, during the period between flooding and drying. The geochemical data presented in this report indicate that (a) strong spatial and temporal differences in Hg speciation and transformations can occur within the range of wetland habitats found in the lower Sacramento River basin; (b) flooding of seasonal wetlands can be accompanied by a rapid increase in benthic MeHg production and the release of previously formed MeHg (generated during or since the previous flooding season) to the overlying water column; (c) S and Fe chemistry, and associated microbial reduction pathways, play an important role in mediating the speciation and transformation of Hg in these wetland habitats; (d) hydroperiod is a primary forcing function in mediating MeHg production among various wetland types; and (e) MeHg production appears to be more active in the YBWA compared to the CCSB.

California↗
USGS2022

Potential effects of energy development on environmental resources of the Williston Basin in Montana, North Dakota, and South Dakota—Water resources

The Williston Basin has been a leading oil and gas producing area for more than 50 years. While oil production initially peaked within the Williston Basin in the mid-1980s, production rapidly increased in the mid-2000s, largely because of improved horizontal (directional) drilling and hydraulic fracturing methods. In 2012, energy development associated with the Bakken Formation was identified as a priority requiring collaboration toward improved timeliness of issuing permits for new wells combined with reasonable measures to maintain environmental quality. Shortly thereafter, the Bakken Federal Executive Group was created to address common challenges associated with energy development. The Bakken Federal Executive Group partner agencies identified a gap in current understanding of the cumulative environmental challenges attributed to energy development throughout the area, resulting in an effort to aggregate scientific data and identify additional research and information needs related to natural resources within areas of energy development in the Williston Basin. As part of this effort, water resources in the area (including groundwater; streams and rivers; and lakes, reservoirs, and wetlands) were characterized and described in terms of physical occurrence, flow characteristics, recharge, water quality, and water use. Similarly, waters produced during energy-development activities also were characterized even though these waters are not considered usable resources within the area. Groundwater resources were characterized by the major hydrogeologic units, or aquifers, identifying the units that supply most groundwater used for domestic, stock, agricultural, and industrial purposes. The groundwater characterization included other deeper hydrogeologic units in the Williston Basin that may be a useable source of water with treatment, have utility as a reservoir for reinjection of produced waters, or be a source of minerals and energy resources. A generalized groundwater budget and flow system identifying the sources of recharge (stream infiltration, precipitation, and movement [leakage] from other aquifers) and the general groundwater flow direction is included for each of the major hydrogeologic units. Rivers and streams within the Williston Basin with 10 or more years of continuous streamflow data were identified. For a subset of these sites, streamflow characteristics, including the monthly and annual mean flow, were generated to identify seasonal and interannual changes in streamflow and thus provide information on the drivers and reliability of streamflow at the seasonal or multiyear scale. Daily streamflow and annual extreme flows (peak and low flow) also were estimated for the subset of sites. The daily streamflow and annual extreme flow values provide information on short-term or extreme events that are relevant to infrastructure design and evaluating spills, leaks, or accidental discharges of water or petroleum products. Surface-water features (lakes, ponds, and wetlands) were classified using the Cowardin system and identified on the National Wetlands Inventory maps generated by the U.S. Fish and Wildlife Service. The spatial distribution of the surface-water features was analyzed by State, county, and specifically in comparison to the Prairie Pothole Region. The proximity of the surface-water features to energy development infrastructure (specifically oil or gas well pads) was evaluated. It was determined that, although oil or gas wells are often near a surface-water feature, most surface-water features do not have wells nearby, with the exception of wells in the Prairie Pothole Region. Water-quality data were aggregated from two data sources: (1) the Water-Quality Portal, sponsored by the U.S. Geological Survey (USGS), U.S. Environmental Protection Agency (EPA), and National Water Quality Monitoring Council; and (2) a data compilation completed as part of the USGS National Water-Quality Assessment project. The Water-Quality Portal integrates publicly available water-quality data from databases maintained by the USGS, EPA, and U.S. Department of Agriculture, including water-quality data from Tribal, State, and local databases. Water-quality data for 15 commonly measured water-quality constituents were aggregated for groundwater, rivers and streams, and lakes and reservoirs. For each aggregated dataset (groundwater, rivers and streams, and lakes and reservoirs), analyses of the water-quality data included summary statistics, maps of spatial distribution of constituent values, boxplots of constituent values by timeframe or hydrogeologic unit, spatial comparisons of site locations and constituent values to petroleum well density, and comparisons of the constituent values measured to EPA drinking-water standards/guidelines. Produced water includes all fluids brought to the surface along with the targeted hydrocarbons as part of the oil and gas exploration and extraction processes. These fluids may include formation water (waters that co-exist with rock/oil/gas), hydraulic fracturing fluids, and other combinations of water and chemicals used during oil and gas well drilling, development, treatments, recompletions, and workovers. Produced water datasets were aggregated from two sources: the USGS National Produced Waters Geochemical database (ver. 2.1) and a series of projects focused specifically on sampling produced water in the Williston Basin from 2010 to 2014. The National Produced Waters Geochemical database was useful for a general understanding of produced-water chemistry. Produced waters are characterized by extreme salinity and contain elevated concentrations of other constituents (including arsenic, barium, cadmium, lead, zinc, radium-226/radium-228, and ammonium) that could negatively affect water and aquatic resources if released. Produced waters also have a generally unique chemical (isotopic) signature that may be useful in tracking water from different geologic units; for example, the oxygen/deuterium and strontium ratio values measured in brine waters from the Bakken Formation are distinct from brines collected from other geologic units in the Williston Basin. Water-use information related to energy production in the area also was aggregated and summarized. The summary of water use is not limited to oil and gas production but includes water used to produce all types of energy resources in the Williston Basin, including coal/lignite, thermoelectric power, oil and gas, hydropower, biomass and biofuels, wind, geothermal, and solar. Each State has its own methods for regulating and reporting water usage within its jurisdiction. These methods can introduce problems when examining water use from sources, such as the Missouri River or Fox Hills aquifer, that are shared across political boundaries. Without the one-to-one match for usage types and amounts used from a water source, it is difficult to develop a comprehensive water budget for the water source being evaluated. A large amount of freshwater is required to prepare a well for oil and gas well production; in some cases, 3 to 7 million gallons of water are needed per well. The EPA estimates that hydraulic fracturing in the Williston Basin uses between 70 to 140 billion gallons per year. Water also is used for myriad other purposes related to ancillary oil and gas extraction. In addition to water used for immediate energy development, the expanded human workforce migrating into the area and other support staff who have moved into the area during the development also use water. Research and information needs were identified that could be relevant in the evaluation of the effects of energy development on water resources. Information needs related to the evaluation of groundwater resources include the following: improved potentiometric-surface maps for glacial units; availability of a uniform stream network digital geographic coverage that spans the international boundary with Canada; enhanced surface-water use information with regards to the gain and loss of streamflow to shallow groundwater, which would increase understanding groundwater and surface-water interactions; and expanded geophysical assessments. Gaps in the availability of streamflow data include the lack of information on ice-jam flooding despite potential for effects to infrastructure (pipelines, roads, and facilities) and an understanding of the cumulative effects of largely undocumented stock and diversion dams. Although this study resulted in the aggregation of a large quantity of water-quality data, the availability of consistently collected, systematically processed and reported data over large parts of the Williston Basin is sparse. Few samples have been analyzed for constituents that may indicate the effect of energy development on water resources. Constituents that could be considered include boron, chloride, bromide, iodine, fluoride, manganese, lithium, radium, strontium isotopes, volatile organic compounds, and isotopes of inorganic ions (such as hydrogen and carbon). Collaboration between Tribal, Federal, State, and local entities to identify a common study design, common monitoring constituents, and consistent sampling locations would generate datasets with broad utility and would likely result in overall cost savings for monitoring over time. Similarly, there is a need for standardized sample collection, processing, laboratory analytical methods, and the collection of ancillary data for produced waters sampling. Additional characterization of the range of chemical, microbial, and isotopic compositions and quantities of “end-member” produced waters, and the collection of time-series datasets to document the changes in produced waters during and after well development also were needs identified during this study. Water-use estimates would be improved through the implementation of comprehensive studies of water use from groundwater and surface-water sources using consistent methodologies across the Williston Basin. The submission of chemical and water data related to hydraulic fracturing collected by the oil and gas industry would add to the quantity of available data. Consistent implementation of regulations and monitoring controls across political boundaries (State, county, and international) would further improve the consistency of data available for the estimates of water use.

Montana, North Dakota, South Dakota↗
USGS2017

Fluorine

Fluorine compounds are essential in numerous chemical and manufacturing processes. Fluorspar is the commercial name for fluorite (isometric CaF 2 ), which is the only fluorine mineral that is mined on a large scale. Fluorspar is used directly as a fluxing material and as an additive in different manufacturing processes. It is the source of fluorine in the production of hydrogen fluoride or hydrofluoric acid, which is used as the feedstock for numerous organic and inorganic chemical compounds. The United States was the world’s leading producer of fluorspar until the mid-1950s. In the mid-1970s, the U.S. fluorspar mining industry began to decline because of foreign competition. By 1982, there was essentially only a single U.S. producer left, and that company ceased mining in 1996. Consumption of fluorspar in the United States peaked in the early 1970s, which was also the peak period of U.S. steel production. Since then, U.S. fluorspar consumption has decreased substantially; the United States has nonetheless increased its imports of downstream fluorine compounds, such as, in order of tonnage imported, hydrofluoric acid, aluminum fluoride, and cryolite. This combination of no U.S. production (until recently) and high levels of consumption has made the United States the world’s leading fluorspar-importing country, in all its various forms. The number of fluorspar-exporting countries has decreased substantially in recent decades, and, as a result, the United States has become dependent on just a few countries to supply its needs. In 2013, the United States imported the majority of its fluorspar from three countries, which were, in descending order of the amount imported, Mexico, China, and South Africa. Geologically, in igneous systems, fluorine is one of a number of elements that are “incompatible.” These incompatible elements become concentrated in the residual magma while the common silicates crystallize upon magma ascent and cooling, leading to relatively high fluorine concentrations in the more evolved or differentiated igneous rocks and in hydrothermal deposits associated with those evolved igneous rocks. In sedimentary rocks, fluorine’s highest concentrations are found in phosphorites because fluorine substitutes for hydroxyl ions in apatite, which leads to fluorine concentrations of, typically, from 2 to 4 weight percent in phosphorites. Because of the presence of fluorine, phosphate fertilizer manufacturers can produce a fluorosilicic acid byproduct. Most deposits mined for fluorine are hydrothermal, however, and consist of fluorine minerals that precipitated from hot water. Magmatic brines and brines from deep within sedimentary basins that have high concentrations of dissolved fluoride are the mineralizing fluids for various types of hydrothermal fluorspar deposits. Relatively dilute hydrothermal fluids that formed in some volcanic rocks can also transport sufficient fluoride to form a high-grade fluorspar deposit. Fluorite has low solubility in a common range of hydrothermal temperatures, particularly from about 160 degrees Celsius (°C) down to 60 °C. The increasing fluorite solubility below 60 °C partly explains why some water with exceptionally high levels of dissolved fluorine are found even at ambient temperatures in evaporitic lake basins in some East African Rift valleys in Kenya and Tanzania. The geologic conditions that led to the high concentrations there are known to exist in a number of other places in the world as well, including, perhaps, places in the Basin and Range province of the United States. Eight minerals or mineral groups have sufficient fluorine in their structures to be considered as possible ores of the element; they are bastnaesite (also spelled bastnäsite; and other fluorocarbonates), cryolite, sellaite, villiaumite, fluorite, fluorapatite (in phosphorites), various phyllosilicates, and topaz. Fluorite is currently the only mineral that is mined for fluorine, and nomineral except fluorite is likely to become a source of commercially produced fluorine as a primary product as long as supplies from relatively thick and high-grade fluorite deposits continue to be available. At least seven classes (which include one subclass) of hydrothermal fluorite deposits are recognized; they are classified according to their tectonic and (or) magmatic settings, as follows: (1) carbonatite-related fluorspar deposits; (2) alkaline-intrusion-related fluorspar deposits; (3) alkaline-volcanic-related epithermal fluorspar deposits; (4) Mississippi Valley-type fluorspar deposits (and a subclass of salt-related carbonate-hosted fluorspar deposits); (5) fluorspar deposits related to strongly differentiated granites; (6) subalkaline-volcanic-related epithermal fluospar deposits; and (7) fluorspar deposits that appear to be conformable within tuffaceous limy lacustrine sediments. An eighth class (not hydrothermal) is that of fluorspar deposits concentrated in soils and weathered zones; that is, residual fluorspar deposits. Generally, fluorspar deposits related to strongly differentiated granites have larger tonnages and lower grades than carbonatite-related fluorspar deposits, which, in turn, have larger tonnages and lower grades than fluorspar vein deposits from various other classes. The United States has a few identified resources of fluorspar, most notably the Klondike II property in the Illinois- Kentucky fluorspar district located about 8 kilometers southwest of Salem, Kentucky, which has a large vein that contains at least 1.6 million metric tons at a grade of 60 percent CaF 2 (Feytis, 2009). Additional fluorspar resources of lower grade but larger tonnage have been identified at Hicks Dome in the Illinois-Kentucky fluorspar district and at Lost River near the western tip of the Seward Peninsula in Alaska, along with a couple of dozen smaller, higher grade resources. Internationally, new mines that either opened before the beginning of 2013 or were scheduled to open soon after that time include the Nui Phao tungsten-fluorspar-bismuth-copper-gold deposit in northern Vietnam; the St. Lawrence project in Newfoundland, Canada, which is located in a well-known fluorspar district; the Bamianshan deposit, which is related to a strongly differentiated granite in northwestern Zhejiang Province, China, near some of that Province’s large, subalkaline-volcanic-related epithermal veins; and the Nokeng project in South Africa, which is also related to a strongly differentiated granite. Other deposits in northwestern Australia, Nevada (United States), Norway, South Africa, and Sweden have been identified and could be put into production within just a few years. Among undiscovered resources, an interesting possibility might be to produce a fluorine product from evaporitic, high-fluorine, high-pH sodium-carbonate brines like Lake Magadi (Kenya) and Lake Natron (Tanzania) in Africa’s Eastern Rift Valley. In addition, apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments, such as those in Italy, are likely to occur in similar young alkalic volcanic settings elsewhere in the world. Modern geophysical and geochemical exploration techniques have typically not been brought to bear in exploration for new fluorspar deposits, although such techniques are likely to be used in future exploration. The tendency for fluorine to dissolve in significant concentrations in water at low temperature allows both surface water and groundwater to be used as sampling media in geochemical exploration. Evolved granite-related fluorspar deposits may be particularly susceptible to geophysical exploration methods because crystalline rocks that form a basement to sedimentary sections can be approximately defined with gravity and magnetic methods, and magnetite-bearing skarns can be directly detected with magnetic surveys. Environmental considerations of fluorine mining focus especially on drinking water, where high fluorine concentrations can lead to tooth decay; dental and skeletal fluorosis; and bone and cartilage conditions, including genu valgum, which is the crippling bone deformity more commonly known as knock knee. Trace amounts of other elements in fluorspar ores are a concern at some deposits; for example, high beryllium concentrations in alkaline-volcanic-related epithermal deposits or high cadmium concentrations associated with Mississippi Valley-type and salt-related carbonate-hosted fluorspar deposits. Future research might include testing whether fluorine can be extracted economically from high-pH, sodium-carbonate brines and exploring for new occurrences of apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments outside of the Latium Region of Italy. Other promising new areas of research could be studies of fluorspar deposit fluid inclusion compositions by quadrupole mass spectrometry, by noble gas mass spectrometry on irradiated fluid inclusions, or by chlorine isotopes, while also measuring the chemistry of the same fluid inclusions either by bulk crush-and-leach methods or by laser ablation-inductively coupled plasma mass spectrometry. Advanced studies of fluid inclusion chemistry could be applied beneficially to some of the enigmatic large epithermal fluorspar veins at various places in the world, where they might determine those deposits’ possible relationships to igneous intrusions, or to dissolved salt, or to heated meteoric water in volcanic sections, or perhaps to all three. This knowledge could help focus new exploration.

Professional Paper↗