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Applied Geochemistry Special Issue on Environmental geochemistry of modern mining

Environmental geochemistry is an integral part of the mine-life cycle, particularly for modern mining. The critical importance of environmental geochemistry begins with pre-mining baseline characterization and the assessment of environmental risks related to mining, continues through active mining especially in water and waste management practices, and culminates in mine closure. The enhanced significance of environmental geochemistry to modern mining has arisen from an increased knowledge of the impacts that historical and active mining can have on the environment, and from new regulations meant to guard against these impacts. New regulations are commonly motivated by advances in the scientific understanding of the environmental impacts of past mining. The impacts can be physical, chemical, and biological in nature. The physical challenges typically fall within the purview of engineers, whereas the chemical and biological challenges typically require a multidisciplinary array of expertise including geologists, geochemists, hydrologists, microbiologists, and biologists. The modern mine-permitting process throughout most of the world now requires that potential risks be assessed prior to the start of mining. The strategies for this risk assessment include a thorough characterization of pre-mining baseline conditions and the identification of risks specifically related to the manner in which the ore will be mined and processed, how water and waste products will be managed, and what the final configuration of the post-mining landscape will be. In the Fall 2010, the Society of Economic Geologists held a short course in conjunction with the annual meeting of the Geological Society of America in Denver, Colorado (USA) to examine the environmental geochemistry of modern mining. The intent was to focus on issues that are pertinent to current and future mines, as opposed to abandoned mines, which have been the focus of numerous previous short courses. The geochemical challenges of current and future mines share similarities with abandoned mines, but differences also exist. Mining and ore processing techniques have changed; the environmental footprint of waste materials has changed; environmental protection has become a more integral part of the mine planning process; and most historical mining was done with limited regard for the environment. The 17 papers in this special issue evolved from the Society of Economic Geologists’ short course. The relevant geochemical processes encompass the source, transport, and fate of contaminants related to the life cycle of a mine. Contaminants include metals and other inorganic species derived from geologic sources such as ore and solid mine waste, and substances brought to the site for ore processing, such as cyanide to leach gold. Factors, such as mine-waste mineralogy, hydrologic setting, mine-drainage chemistry, and microbial activity, that affect the hydrochemical risks from mining are reviewed by Nordstrom et al. In another paper, Nordstrom discusses baseline characterization at mine sites in a regulatory framework, and emphasizes the influence of mineral deposits in producing naturally elevated concentrations of many trace elements in surface water and groundwater. Surface water quality in mineralized watersheds is influenced by a number of processes that act on daily (diel) cycles and can produce dramatic variations in trace element concentrations as described by Gammons et al. Pre-mining baseline characterization studies should strive to capture the magnitude of these diel variations. Desbarats et al., using a case study of mine drainage from a gold mine, illustrate how elements that commonly occur as negatively charged species (anions) in solution, such as arsenic as arsenate, behave in an opposite fashion than most metals, which occur as positively charged species (cations). Significant improvement in the understanding of factors that influence the toxicity of metals to aquatic organisms in surface water has highlighted the importance of aqueous chemistry, particularly dissolved organic carbon, as described by Smith et al. Stream sediment contamination is another important pathway for affecting aquatic organisms, as reviewed by Besser et al. Understanding and predicting environmental consequences from mining begins with knowing the mineralogy and mineral reactivity of the ore, the wastes, and of secondary minerals formed later. Jamieson et al. review the importance of mineralogical studies in mine planning and remediation. A number of types of site-specific studies are needed to identify environmental risks related to individual mines. Lapakko reviews the general framework of mine waste characterization studies that are integral to the mine planning process. Hageman et al. present a comparative study of several static tests commonly used to characterize mine waste. The mining and ore processing practices employed at a specific mine site will vary on the basis of the commodities being targeted, the geology of the deposit, the geometry of the deposit, and the mining and ore processing methods used. Thus, these factors, in addition to the waste management practices used, can result in a variety of end-member mine waste features, each of which has its own set of challenges. Open pit mines and underground mines require waste rock to be removed to access ore. Waste rock presents unique problems because the rock is commonly mineralized at sub-economic grades and has not been processed to remove potentially problematic minerals, such as pyrite. Amos et al. examine the salient aspects of the geochemistry of waste rock. Mill tailings – the waste material after ore minerals have been removed – are a volumetrically important solid waste at many mine sites. Their fine grain size and the options for their management make their behavior in the environment distinct from that of waste rock. Lindsay et al. describe some of these differences through three case-study examples. Subaqueous disposal of tailings is another option described by Moncur et al. Cyanide leaching for gold extraction is a common method throughout the world. Johnson describes environmental aspects of cyanidation. Uranium mining presents unique environmental challenges, particularly since in-situ recovery has seen widespread use. Campbell et al. review the environmental geochemistry of uranium mining and current research on bioremediation. Ore concentrates from many types of metal mining undergo a pyrometallurgical technique known as smelting to extract the metal. Slag is the result of smelting, and it may be an environmental liability or a valuable byproduct, as described by Piatak et al. Finally, the open pits that result from surface mining commonly reach below the water table. At the end of mining, these pits may fill to form lakes that become part of the legacy of the mine. Castendyk et al., in two papers, review theoretical aspects of the environmental limnology of pit lakes. They also describe approaches that have been used to model pit lake water balance, wall-rock contributions to pit lake chemistry, pit lake water quality, and limnological processes, such as vertical mixing, through the use of three case studies.

Applied Geochemistry

Declining aluminum toxicity and the role of exposure duration on brook trout mortality in acidified streams of the Adirondack Mountains, New York, USA

Mortality of brook trout Salvelinus fontinalis and water chemistry were characterized in 6 headwater streams in the western Adirondacks of New York during spring 2015, 2016, and 2017 and compared with results from analogous tests done between 1980 and 2003 in many of the same streams, to assess temporal changes in toxicity and inorganic monomeric aluminum (Al i ) concentrations, and the role of Al i exposure duration on brook trout survival. The Al i concentrations of 2 and 4 µmol L –1 corresponded to low‐to‐moderate and high mortality thresholds, but prolonged exposure to ≥1 µmol Al i L –1 also produced mortality. The variability, mean, and highest Al i concentrations in Buck Creek year round, and in several other streams during spring, have decreased significantly over the past 3 decades. Logistic models indicate that Al i surpassed highly toxic concentrations in Buck Creek for 3 to 4 mo annually during 2001 to 2003 and for 2 to 3 wk annually during 2015 to 2017. The loss of extremely high Al i episodes indicates that toxicity has declined markedly between the 1989 to 1990, 2001 to 2003, and 2015 to 2017 test periods, yet Al i concentrations can still cause moderate‐to‐high and complete (100%) mortality. The logistic models illustrate how mortality of brook trout in several Adirondack streams likely decreased in response to the 1990 Amendments to the United States' Clean Air Act (which decreased acidity, Al i concentrations, and duration of toxic episodes) and offer a means to predict how changes in US regulations that limit emissions of NO x and SO x (and N and S deposition loads) could affect fish survival and stream ecosystems in this region and across the Northeast.

New York

Changes in stream chemistry and nutrient export following a partial harvest in the Catskill Mountains, New York, USA

Clearcut forest harvesting typically results in large changes in stream water chemistry in northeastern North America. The effects of partial forest harvests on stream chemistry have not received as much attention, even though partial cutting is a more common forestry practice than clearcutting in this region. Changes in stream water chemistry following a partial cut are reported here from a 10 ha study catchment in a northern hardwood forest in the Catskill Mountains of southern New York, and are compared to those of a nearby 48 ha reference catchment. The lower two thirds of the treatment catchment was harvested in February-April 2002 by a shelterwood method, such that 33% of the basal area of the catchment was removed. Stream NO3-, NH4+, Ca2+, K+, and total dissolved aluminum (Alto) concentrations increased significantly after the harvest. Stream Ca2+, Mg2+ and NH4+ concentrations peaked 5 months after the initiation of the harvest, NO 3- and K+ concentrations peaked 6 months after cutting, and Alto concentrations peaked 1 year after cutting. Streamflow was not significantly affected by the harvest when compared to the flow of three nearby streams. Export of NO3- in stream water increased five-fold the year after the cut, and briefly exceeded atmospheric inputs of inorganic nitrogen during 4 months in the fall of 2002. Changes in stream NO3- and K+ concentrations were less than predicted by the relative basal area removed compared with those of a recent nearby clearcut. In contrast, changes in Ca2+, Mg 2+ and Alto concentrations were approximately proportional to basal area removal in these two cuts. Stream chemistry returned to values close to those of the pre-cut period and to reference values by early spring of 2003, just over a year after the initiation of the harvest, except for NO 3- concentrations, which remained elevated above background 18-20 months after completion of the cut.

Forest Ecology and Management

Hydrostratigraphy, soil/sediment chemistry, and water quality, Potomac-Raritan-Magothy aquifer system, Puchack Well Field Superfund site and vicinity, Pennsauken Township, Camden County, New Jersey, 1997-2001

Drinking-water supplies from the Potomac-Raritan-Magothy aquifer system at the Puchack well field in Pennsauken Township, Camden County, New Jersey, have been contaminated by hexavalent chromium-the most toxic and mobile form-at concentrations exceeding the New Jersey maximum contaminant level of 100 micrograms per liter. Also, scattered but widespread instances of volatile organic compounds (primarily trichloroethylene) at concentrations that exceed their respective maximum contaminant levels in the area's ground water have been reported. Because inorganic and organic contaminants are present in the ground water underlying the Puchack well field, no water from there has been withdrawn for public supply since 1998, when the U.S. Environmental Protection Agency (USEPA) added the area that contains the Puchack well field to the National Priorities List. As part of the USEPA's investigation of the Puchack Well Field Superfund site, the U.S. Geological Survey (USGS) conducted a study during 1997-2001 to (1) refine previous interpretations of the hydrostratigraphic framework, hydraulic gradients, and local directions of ground-water flow; (2) describe the chemistry of soils and saturated aquifer sediments; and (3) document the quality of ground water in the Potomac-Raritan-Magothy aquifer system in the area. The four major water-bearing units of the Potomac-Raritan-Magothy aquifer system-the Upper aquifer (mostly unsaturated in the study area), the Middle aquifer, the Intermediate Sand (a local but important unit), and the Lower aquifer-are separated by confining units. The confining units contain areas of cut and fill, resulting in permeable zones that permit water to pass through them. Pumping from the Puchack well field during the past 3 decades resulted in downward hydraulic gradients that moved contaminants into the Lower aquifer, in which the production wells are finished, and caused ground water to flow northeast, locally. A comparison of current (1997-2001) water levels near the site of the former pumping center with data from previous investigations indicates that, since pumping at the Puchack well field ceased, the dominant local ground-water flow direction is to the southeast, aligned with regional flow. Chromium concentrations were highest (8,010 micrograms per liter in 2000-01) in water from the Middle aquifer immediately downgradient from a possible source; the extent of this chromium plume is unknown but appears to be small. A second, unrelated, localized chromium plume also was identified in the Middle aquifer. The Intermediate Sand was found to contain an areally extensive plume of chromium-contaminated water, with concentrations up to 6,310 micrograms per liter in 2000-01, and another plume of about the same size, with concentrations up to 4,810 micrograms per liter in 2000-01, was identified in the Lower aquifer. The previous USGS investigation indicated the approximate extent of the combined plumes; the current delineation indicates that their locations have shifted slightly to the southeast since 1998. Concentrations of chromium in ground water decreased at some well locations by as much as 60 percent between sampling rounds in 1997-98 and 1999-2001. The decrease in chromium concentration at a given well could be the result of the chemical reduction of hexavalent chromium and precipitation of the resulting trivalent chromium, the sorption of hexavalent chromium to aquifer materials, or the physical movement of the plumes. Available data indicate that all three processes likely have affected concentrations. The distribution of hexavalent and total chromium in the soils and sediments of a possible source area indicates that some hexavalent chromium has undergone chemical reduction in the soils, but the degree to which this process takes place in the aquifer currently is not known. Nor is it known whether contaminated soils continue to contribute chromium to the aquifer system. Contamination by vola

Scientific Investigations Report

The use of freshwater and saltwater animals to distinguish between the toxic effects of salinity and contaminants in irrigation drain water

Irrigation drain waters entering Stillwater Wildlife Management Area (SWMA) in south-western Nevada contain elevated levels of salinity and several inorganic contaminants (As, B, Cu, Li, Mo, and Sr). Mortalities of fish and waterfowl at the management area are believed to be associated with the poor water quality of the drains. The objective of the present study was to use fresh-water and saltwater animals to distinguish between the toxic effects of salinity and contaminants in effluent samples collected from irrigation drain waters. Static acute effluent tests were conducted with water collected from four sites at SWMA. Animals acclimated or cultured in fresh water (fathead minnows, Pimephales promelas ; amphipods, Hyalella azteca ; cladocerans, Daphnia magna ) and salt water (striped bass, Morone saxatilis ; amphipods, Hyalella azteca ; and cladocerans, Daphnia magna ) were used to separate toxic effects of salinity from the effects of inorganic contaminants in the drain water. One drain water (TJ drain, salinity 19 parts per thousand (grams per liter), osmolality 503 mmol/kg, hardness 3,780 mg/L as CaCO 3 ) was toxic only to freshwater animals and saltwater cultured daphnids; water from a receiving pond (Pintail Bay, salinity 23 g/L, osmolality 542 mmol/kg, hardness 830 mg/L as CaCO 3 ) was toxic to both freshwater and saltwater animals. Acute tests conducted with reconstituted waters representative of the Pintail Bay sample indicated that atypical ion ratios were toxic to striped bass and amphipods, even without the addition of inorganic contaminants. However, the addition of inorganic contaminants representative of the Pintail Bay sample increased the toxicity of this reconstituted water. These findings indicate that the toxicity of the TJ drain sample was related mainly to elevated salinity and that the toxicity of the Pintail Bay sample was a function of inorganic contamination and atypical ion ratios in combination with elevated salinity.

Environmental Toxicology and Chemistry

Ground-Water Quality Data in the Santa Clara River Valley Study Unit, 2007: Results from the California GAMA Program

Ground-water quality in the approximately 460-square-mile Santa Clara River Valley study unit (SCRV) was investigated from April to June 2007 as part of the statewide Priority Basin project of the Ground-Water Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The study was designed to provide a spatially unbiased assessment of the quality of raw ground water used for public water supplies within SCRV, and to facilitate a statistically consistent basis for comparing water quality throughout California. Fifty-seven ground-water samples were collected from 53 wells in Ventura and Los Angeles Counties. Forty-two wells were selected using a randomized grid-based method to provide statistical representation of the study area (grid wells). Eleven wells (understanding wells) were selected to further evaluate water chemistry in particular parts of the study area, and four depth-dependent ground-water samples were collected from one of the eleven understanding wells to help understand the relation between water chemistry and depth. The ground-water samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, potential wastewater-indicator compounds, and pharmaceutical compounds), a constituent of special interest (perchlorate), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial constituents. Naturally occurring isotopes (tritium, carbon-13, carbon-14 [abundance], stable isotopes of hydrogen and oxygen in water, stable isotopes of nitrogen and oxygen in nitrate, chlorine-37, and bromine-81), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks or replicates, or samples for matrix spikes) were collected from approximately 26 percent of the wells, and the analyses of these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control results showed that the quality of the environmental data was good, with low bias and low variability, and as a result, less than 0.1 percent of the analytes detected in ground-water samples were censored. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is delivered (or, supplied) to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with regulatory and non-regulatory thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Most constituents that were detected in ground-water samples were reported at concentrations below their established health-based thresholds. VOCs, pesticides and pesticide degradates, and potential wastewater-indicator compounds were detected in about 33 percent or less of the 42 SCRV grid wells. Concentrations of all detected organic constituents were below established health-based thresholds. Perchlorate was detected in approximately 12 percent of the SCRV grid wells; all concentrations reported were below the NL-CA threshold. Additional constituents, including major ions, trace elements, and nutrients were collected at 26 wells (16 grid wells and 10 understanding wells) of the 53 wells sampled f

Data Series

Decreases in aluminum toxicity and mortality of caged brook trout in Adirondack Mountain Streams

Mortality of juvenile brook trout and water chemistry were characterized in six western Adirondack streams in northern New York State during spring 2015, 2016, and 2017 and compared with results from comparable tests done between 1980 and 2003 in many of the same streams to assess temporal changes in inorganic monomeric aluminum (Ali) concentrations, Ali-toxicity, and the role of Ali-exposure duration on mortality. Ali concentrations of 2 and 4 micromoles per liter (µmol L-1) corresponded to chronic- and acute-mortality thresholds for brook trout, but prolonged exposure to ≥ 1 µmol Ali L-1 also produced low-to-moderate mortality levels. The variability, mean, and highest Ali concentrations in Buck Creek (BUC) year-round, and in several other streams during spring, decreased significantly over the past 30 years. Predictive models indicate that Ali surpassed highly toxic concentrations at BUC for three to four months annually during 2001–2003 but for only two to three weeks annually during 2015–2017. The current lack of extremely high Ali concentrations indicate toxicity has declined markedly between the 1989–1990, 2001–2003, and 2015–2017 test periods, yet acid- Ali episodes can still cause moderate-to-high levels of brook trout mortality during high springtime flows. Assembled models show how mortality of brook trout in several Adirondack streams likely declined in response to the 1990 Clean Air Act Amendments and offer a means to predict how changes in United States regulations that limit the atmospheric emissions of nitrogen (N) and sulfur (S) oxides, and the deposition of N and S, could affect brook trout survival and impaired stream ecosystems in the western Adirondack region.

New York

Biological and chemical recovery of acidified Catskill Mountain streams in response to the Clean Air Act Amendments of 1990

Decades of acidic deposition have adversely affected aquatic and terrestrial ecosystems in acid-sensitive watersheds in parts of the eastern United States. The national Acid Rain Program (Title IV of the 1990 Clean Air Act Amendments - CAAA) helped reduce emissions of sulfur dioxide (SO 2 ) and nitrogen oxides (NO x ) and resulted in sharp decreases in the acidity of atmospheric deposition. The decrease in acidic deposition produced a steady decline in the acidity of streams in many poorly buffered waters across the western Adirondacks and parts of the Catskill Mountains of New York. Until recently, however, there has been little evidence of biological recovery in most acid-sensitive streams in both regions. Long-term deposition and stream-chemistry records and fish-community data from quantitative surveys done during 1991–93 and again during 2012–19 at 13 sites in the upper Neversink River and its tributaries were evaluated to determine if chemical and biological recovery were evident in this Catskill Mountain watershed and if they could be linked to regional declines in acidic deposition. Between 1991 and 2019, large decreases in sulfate and nitrate deposition in the basin mirrored declines in total nationwide SO 2 and NO x emissions. There were corresponding decreases in sulfate and nitrate concentrations in deposition at a National Trends Network station at Frost Valley (NY68) and coincident declines in sulfate concentrations at four long-term monitoring sites in the Neversink River watershed. Mean acid neutralizing capacity and pH increased and inorganic aluminum (Al i ) concentrations from routine summertime samples decreased significantly at most moderately to severely acidified sites between the two study periods. Richness, density, and biomass of fish communities increased at most sites, while the density and biomass of brook trout Salvelinus fontinalis populations increased at fewer sites that were undergoing chemical recovery. Although recovery is far from complete, trends in deposition chemistry, water quality, and fish assemblages in streams of the upper Neversink watershed indicate that the 1990 CAAA is having positive impacts on aquatic ecosystems in the Catskill Mountain region, New York.

New York

Storm-scale and seasonal dynamics of carbon export from a nested subarctic watershed underlain by permafrost

Subarctic catchments underlain by permafrost sequester a major stock of frozen organic carbon (C), which may be mobilized as the Arctic warms. Warming can impact C export from thawing soils by altering the depth and timing of runoff related to changing storm and fire regimes and altered soil thaw depths. We investigated C export in a first order headwater stream (West Twin Creek) and its receiving third order river (Beaver Creek) in interior Alaska using discrete sampling of dissolved organic and inorganic C (DOC and DIC) and 15-min collection of specific conductance (SC), fluorescent dissolved organic matter (fDOM) and water discharge (Q). Storm SC-Q relationships displayed negative slopes, indicating solute limitation and limited influence of seasonal soil thaw on storm runoff chemistry. Concurrently, fDOM-Q displayed positive slopes that decreased over the summer, indicating flushing of a limited fDOM pool. Baseflow DIC increased over the season concurrent with soil thaw, with higher DIC at the larger scale indicating greater influence of deeper, mineral-rich flow paths. Storm and seasonal trends were generally similar at both scales. The biggest difference was in fDOM, which displayed higher concentrations and slower depletion in the first order stream. Improved process understanding from this study can be used to better predict carbon export and cycling by stream networks as northern forests and arctic regions continue to warm.

Alaska

Episodic acidification of small streams in the northeastern United States: Ionic controls of episodes

As part of the Episodic Response Project (ERP), we intensively monitored discharge and stream chemistry of 13 streams located in the Northern Appalachian region of Pennsylvania and in the Catskill and Adirondack Mountains of New York from fall 1988 to spring 1990. The ERP clearly documented the occurrence of acidic episodes with minimum episodic pH ≤ 5 and inorganic monomeric Al (Al im ) concentrations > 150 μg/L in at least two study streams in each region. Several streams consistently experienced episodes with maximum Al im concentrations >350 μg/L. Acid neutralizing capacity (ANC) depressions resulted from complex interactions of multiple ions. Base cation decreases often made the most important contributions to ANC depressions during episodes. Organic acid pulses were also important contributors to ANC depressions in the Adirondack streams, and to a lesser extent, in the Catskill and Pennsylvania streams. Nitrate concentrations were low in the Pennsylvania streams, whereas the Catskill and Adirondack study streams had high NO 3 - concentrations and large episodic pulses (≤ 54 μ eq/L). Most of the Pennsylvania study streams also frequently experienced episodic pulses of SO 4 2- (≤ 78 μ eq/L), whereas the Adirondack and Catskill streams did not. High baseline concentrations of SO 4 2- (all three study areas) and NO 3 - (Adirondacks and Catskills) reduced episodic minimum ANC, even when these ions did not change during episodes. The ion changes that controlled the most severe episodes (lowest minimum episodic ANC) differed from the ion changes most important to smaller, more frequent episodes. Pulses of NO 3 - (Catskills and Adirondacks), SO 4 2- (Pennsylvania), or organic acids became more important during major episodes. Overall, the behavior of streamwater SO 4 2- and NO 3 - is an indicator that acidic deposition has contributed to the severity of episodes in the study streams.

Ecological Applications

Evaluating the reliability of environmental concentration data to characterize exposure in environmental risk assessments

Environmental risk assessments often rely on measured concentrations in environmental matrices to characterize exposure of the population of interest—typically, humans, aquatic biota, or other wildlife. Yet, there is limited guidance available on how to report and evaluate exposure datasets for reliability and relevance, despite their importance to regulatory decision-making. This paper is the second of a four-paper series detailing the outcomes of a Society of Environmental Toxicology and Chemistry Technical Workshop that has developed Criteria for Reporting and Evaluating Exposure Datasets (CREED). It presents specific criteria to systematically evaluate the reliability of environmental exposure datasets. These criteria can help risk assessors understand and characterize uncertainties when existing data are used in various types of assessments and can serve as guidance on best practice for the reporting of data for data generators (to maximize utility of their datasets). Although most reliability criteria are universal, some practices may need to be evaluated considering the purpose of the assessment. Reliability refers to the inherent quality of the dataset and evaluation criteria address the identification of analytes, study sites, environmental matrices, sampling dates, sample collection methods, analytical method performance, data handling or aggregation, treatment of censored data, and generation of summary statistics. Each criterion is evaluated as “fully met,” “partly met,” “not met or inappropriate,” “not reported,” or “not applicable” for the dataset being reviewed. The evaluation concludes with a scheme for scoring the dataset as reliable with or without restrictions, not reliable, or not assignable, and is demonstrated with three case studies representing both organic and inorganic constituents, and different study designs and assessment purposes. Reliability evaluation can be used in conjunction with relevance evaluation (assessed separately) to determine the extent to which environmental monitoring datasets are “fit for purpose,” that is, suitable for use in various types of assessments. Integr Environ Assess Manag 2024;00:1–23. © 2024 Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Integrated Environmental Assessment and Management

Diatom diversity in chronically versus episodically acidified adirondack streams

The relationship between algal species richness and diversity, and pH is controversial. Furthermore, it is still unknown how episodic stream acidification following atmospheric deposition affects species richness and diversity. Here we analyzed water chemistry and diatom epiphyton dynamics and showed their contrasting behavior in chronically vs. episodically acidic streams in the Adirondack region. Species richness and diversity were significantly higher in the chronically acidic brown water stream, where organic acidity was significantly higher and the ratio of inorganic to organic monomeric aluminum significantly lower. Conversely, in the episodically acidic clear water stream, the inorganic acidity and pH were significantly higher and the diatom communities were very species-poor. This suggests that episodic acidification in the Adirondacks may be more stressful for stream biota than chronic acidity. Strong negative linear relationships between species diversity, Eunotia exigua, and dissolved organic carbon against pH were revealed after the influence of non-linear temporal trends was partialled out using a novel way of temporal modeling. ?? 2006 WILEY-VCH Verlag GmbH & Co. KGaA.

International Review of Hydrobiology

Diel biogeochemical processes and their effect on the aqueous chemistry of streams: A review

This review summarizes biogeochemical processes that operate on diel, or 24-h, time scales in streams and the changes in aqueous chemistry that are associated with these processes. Some biogeochemical processes, such as those producing diel cycles of dissolved O 2 and pH, were the first to be studied, whereas processes producing diel concentration cycles of a broader spectrum of chemical species including dissolved gases, dissolved inorganic and organic carbon, trace elements, nutrients, stable isotopes, and suspended particles have received attention only more recently. Diel biogeochemical cycles are interrelated because the cyclical variations produced by one biogeochemical process commonly affect another. Thus, understanding biogeochemical cycling is essential not only for guiding collection and interpretation of water-quality data but also for geochemical and ecological studies of streams. Expanded knowledge of diel biogeochemical cycling will improve understanding of how natural aquatic environments function and thus lead to better predictions of how stream ecosystems might react to changing conditions of contaminant loading, eutrophication, climate change, drought, industrialization, development, and other factors.

Chemical Geology

Geochemical and hydrological investigations of historical data collected at the Lee Acres Landfill and Giant Bloomfield Refinery, New Mexico, 1985–2020

The Lee Acres Landfill and Giant Bloomfield Refinery are adjacent properties near the City of Farmington, New Mexico, each having undergone monitoring and remediation related to historical site activities. At the landfill, site cleanup has included the installation of a capillary barrier over former liquid waste lagoons and periodic monitoring of groundwater elevations and groundwater quality. At the refinery, remediation has focused on several petrochemical and crude oil release areas and included soil excavation, groundwater treatment, and regular monitoring of groundwater elevations and quality. Groundwater at both sites has higher concentrations of volatile organic compounds and trace metals than background aquifer concentrations. In 2022, the U.S. Geological Survey compiled the Lee Acres-Giant Bloomfield Refinery Database (LAGBRD), which contains publicly available groundwater-elevation data and organic and inorganic groundwater-quality data from both sites, spanning from 1985 to 2020. Data from the LAGBRD and precipitation data from other sources were used to better understand the cause of relatively high manganese concentrations observed in some groundwater wells at the site through comparison of groundwater chemistry to chemical end members, interpretation of spatial and temporal patterns in the groundwater chemistry, and interpretation of groundwater flow properties. In this study, elevated chloride concentrations in groundwater downgradient from the landfill have been attributed to landfill leachate based on the temporal and spatial variability of chloride concentrations and chloride-to-bromide ratios. Installation of a capillary barrier and surface-water runoff controls at the landfill in 2005 appears to have altered infiltration patterns at that site, resulting in a decrease in chloride at some wells but an increase in chloride and dissolved manganese at others. The timing and relation among groundwater elevation, chloride concentration, and manganese concentration suggest that leachate stored in the vadose zone provides a continued source of contamination to groundwater.

New Mexico

Seasonal variation exceeds effects of salmon carcass additions on benthic food webs in the Elwha River

Dam removal and other fish barrier removal projects in western North America are assumed to boost freshwater productivity via the transport of marine-derived nutrients from recolonizing Pacific salmon ( Oncorhynchus spp.). In anticipation of the removal of two hydroelectric dams on the Elwha River in Washington State, we tested this hypothesis with a salmon carcass addition experiment. Our study was designed to examine how background nutrient dynamics and benthic food webs vary seasonally, and how these features respond to salmon subsidies. We conducted our experiment in six side channels of the Elwha River, each with a spatially paired reference and treatment reach. Each reach was sampled on multiple occasions from October 2007 to August 2008, before and after carcass placement. We evaluated nutrient limitation status; measured water chemistry, periphyton, benthic invertebrates, and juvenile rainbow trout ( O. mykiss ) response; and traced salmon-derived nutrient uptake using stable isotopes. Outside of winter, algal accrual was limited by both nitrogen and phosphorous and remained so even in the presence of salmon carcasses. One month after salmon addition, dissolved inorganic nitrogen levels doubled in treatment reaches. Two months after addition, benthic algal accrual was significantly elevated. We detected no changes in invertebrate or fish metrics, with the exception of 15 N enrichment. Natural seasonal variability was greater than salmon effects for the majority of our response metrics. Yet seasonality and synchronicity of nutrient supply and demand are often overlooked in nutrient enhancement studies. Timing and magnitude of salmon-derived nitrogen utilization suggest that uptake of dissolved nutrients was favored over direct consumption of carcasses. The highest proportion of salmon-derived nitrogen was incorporated by herbivores (18–30%) and peaked 1–2 months after carcass addition. Peak nitrogen enrichment in predators (11–16%) occurred 2–3 months after addition. All taxa returned to background δ 15 N levels by 7 months. Since this study was conducted, both dams on the Elwha River were removed over 2011–2014 to open over 90% of the basin to anadromous fishes. We anticipate that as the full portfolio of salmon species expands through the basin, nutrient supply and demand will come into better balance.

Ecosphere

Acidification impacts and goals for gauging recovery of Brook Trout populations and fish communities in streams of the Western Adirondack Mountains, New York, USA

Results from several long‐term monitoring programs in the western Adirondack Mountains, New York, indicate that acid–base chemistry of headwater streams has remained unchanged or improved only marginally since the 1990s. A paucity of quantitative fishery data, however, limits our understanding of the pre‐acidified communities as well as present‐day impacts of acidification on fish assemblages, which impedes efforts to evaluate temporal trends and biological recovery in streams of the region. Fish communities were characterized at 48 streams (chemistry was assessed at 47 streams) in the western Adirondacks at least once during summer 2014–2016 to assess present‐day effects of acidification on fish assemblages, refine important relations, and identify biological targets and chemical effect thresholds that could help gauge biological recovery across the region. Concentrations of inorganic aluminum (Al i ) exceeded chronic and acute toxicity thresholds (1.0 and 2.0 μmol/L) in 21.3% and 8.5%, respectively, of 47 study streams sampled during summer 2014–2016 and in 64.0% and 44.0% of 25 streams sampled during spring 2014–2015. In streams with summer Al i concentrations less than 1.0 μmol/L, community richness, density, and biomass averaged 2.0 species, 444.2 fish/0.1 ha, and 1,924.4 g/0.1 ha, respectively, whereas density and biomass of Brook Trout Salvelinus fontinalis populations averaged 280.8 fish/0.1 ha and 1,384.0 g/0.1 ha, respectively. These findings identify defensible targets for biological recovery and show that Al i toxicity is not a major concern for fish assemblages in most streams during summer base flow periods but is potentially a serious issue for fish in as many as two‐thirds of streams during spring high flows. Though additional data are needed to address several limitations and information gaps, results from this study provide a sound foundation to gauge biological recovery, detect future effects of climatic stressors, and help ensure that functional stream ecosystems can be sustained or restored in parts of the Adirondacks.

New York

Quality of groundwater in the Denver Basin aquifer system, Colorado, 2003-5

Groundwater resources from alluvial and bedrock aquifers of the Denver Basin are critical for municipal, domestic, and agricultural uses in Colorado along the eastern front of the Rocky Mountains. Rapid and widespread urban development, primarily along the western boundary of the Denver Basin, has approximately doubled the population since about 1970, and much of the population depends on groundwater for water supply. As part of the National Water-Quality Assessment Program, the U.S. Geological Survey conducted groundwater-quality studies during 2003–5 in the Denver Basin aquifer system to characterize water quality of shallow groundwater at the water table and of the bedrock aquifers, which are important drinking-water resources. For the Denver Basin, water-quality constituents of concern for human health or because they might otherwise limit use of water include total dissolved solids, fluoride, sulfate, nitrate, iron, manganese, selenium, radon, uranium, arsenic, pesticides, and volatile organic compounds. For the water-table studies, two monitoring-well networks were installed and sampled beneath agricultural (31 wells) and urban (29 wells) land uses at or just below the water table in either alluvial material or near-surface bedrock. For the bedrock-aquifer studies, domestic- and municipal-supply wells completed in the bedrock aquifers were sampled. The bedrock aquifers, stratigraphically from youngest (shallowest) to oldest (deepest), are the Dawson, Denver, Arapahoe, and Laramie-Fox Hills aquifers. The extensive dataset collected from wells completed in the bedrock aquifers (79 samples) provides the opportunity to evaluate factors and processes affecting water quality and to establish a baseline that can be used to characterize future changes in groundwater quality. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating constituents and tracers. This report discusses spatial and statistical distributions of chemical constituents and evaluates natural and human-related processes that affect water quality. Findings are synthesized to assess the vulnerability of the Denver Basin aquifer system to groundwater contamination. The chemistry of groundwater samples collected from the water-table wells was generally different from that of samples collected from the bedrock-aquifer wells. Samples from the water-table wells tended to have higher concentrations of total dissolved solids and most major ions. Concentrations of several constituents with potential human-health concerns, including nitrate, selenium, uranium, and arsenic, decreased with depth and were highest in samples from the water-table wells. Exceedances of drinking-water standards and water-quality benchmarks were more frequently associated with shallow groundwater samples; concentrations of total dissolved solids and sulfate exceeded water-quality benchmarks for about half or more of samples from the water-table wells. The sediments and rocks of the Denver Basin are natural sources of the trace elements selenium, uranium, and arsenic, which affect their concentrations in groundwater. Detections of organic contaminants, which are typically indicative of human sources of contamination to groundwater, were more frequent in samples from the water-table wells. Pesticide compounds and volatile organic compounds were detected in 33 and 62 percent, respectively, of water-table well samples. Detected organic contaminant concentrations were much less than the associated drinking-water standards. Samples collected from the bedrock aquifers had lower concentrations of total dissolved solids than did samples collected from the water-table wells, although within the bedrock-aquifer samples, concentrations increased from the Dawson to Denver to Arapahoe to Laramie-Fox Hills aquifers. Concentrations of total dissolved solids and many constituents varied spatially and with depth in the bedrock aquifers, likely as a result of ion-exchange and oxidation-reduction reactions, which are important processes affecting water quality. Major-ion chemistry generally evolved from a calcium-bicarbonate to calcium-sulfate composition, with some sodium-bicarbonate and sodium-sulfate facies in the deeper bedrock aquifers, likely resulting from longer residence times and more extensive water-rock interaction. Oxidation-reduction conditions generally evolved from oxic at the water table to anoxic with increasing depth in the bedrock aquifers. Most samples from the bedrock aquifers were anoxic. Exceedances of drinking-water standards and water-quality benchmarks for the bedrock aquifers occurred in 1 percent or less of samples for nitrate, selenium, or arsenic; there were no exceedances for uranium. Exceedances for total dissolved solids, sulfate, manganese, and iron were generally between about 10 and 20 percent for the bedrock-aquifer samples. Radon concentrations, which were only measured in samples collected from two of the bedrock aquifers, exceeded the lower proposed drinking-water standard for more than 90 percent of samples but exceeded the higher alternative standard for less than 5 percent of samples. Pesticide compounds and volatile organic compounds were detected in 3 and 22 percent, respectively, of bedrock-aquifer samples, all at concentrations that were that were much less than drinking-water standards. Water-quality data were synthesized to evaluate factors that affect spatial and depth variability in water quality and to assess aquifer vulnerability to contaminants from geologic materials and those of human origin. The quality of shallow groundwater in the alluvial aquifer and shallow bedrock aquifer system has been adversely affected by development of agricultural and urban areas. Land use has altered the pattern and composition of recharge. Increased recharge from irrigation water has mobilized dissolved constituents and increased concentrations in the shallow groundwater. Concentrations of most constituents associated with poor or degraded water quality in shallow groundwater decreased with depth; many of these constituents are not geochemically conservative and are affected by geochemical reactions such as oxidation-reduction reactions. Groundwater age tracers provide additional insight into aquifer vulnerability and help determine if young groundwater of potentially poor quality has migrated to deeper parts of the bedrock aquifers used for drinking-water supply. Age-tracer results were used to group samples into categories of young, mixed, and old groundwater. Groundwater ages transitioned from mostly young in the water-table wells to mostly mixed in the shallowest bedrock aquifer, the Dawson aquifer, to mostly old in the deeper bedrock aquifers. Although the bedrock aquifers are mostly old groundwater of good water quality, several lines of evidence indicate that young, contaminant-bearing recharge has reached shallow to moderate depths in some areas of the bedrock aquifers. The Dawson aquifer is the most vulnerable of the bedrock aquifers to contamination, but results indicate that the older (deeper) bedrock aquifers are also vulnerable to groundwater contamination and that mixing with young recharge has occurred in some areas. Heavy pumping has caused water-level declines in the bedrock aquifers in some parts of the Denver Basin, which has the potential to enhance the transport of contaminants from overlying units. Results of this study are consistent with the existing conceptual understanding of aquifer processes and groundwater issues in the Denver Basin and add new insight into the vulnerability of the bedrock aquifers to groundwater contamination.

Colorado

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: II. Field application to Haiwee reservoir sediment

Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.

Environmental Science & Technology