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USGS2013

The influence of global climate change on the scientific foundations and applications of Environmental Toxicology and Chemistry: Introduction to a SETAC international workshop

This is the first of seven papers resulting from a Society of Environmental Toxicology and Chemistry (SETAC) international workshop titled “The Influence of Global Climate Change on the Scientific Foundations and Applications of Environmental Toxicology and Chemistry.” The workshop involved 36 scientists from 11 countries and was designed to answer the following question: How will global climate change influence the environmental impacts of chemicals and other stressors and the way we assess and manage them in the environment? While more detail is found in the complete series of articles, some key consensus points are as follows: (1) human actions (including mitigation of and adaptation to impacts of global climate change [GCC]) may have as much influence on the fate and distribution of chemical contaminants as does GCC, and modeled predictions should be interpreted cautiously; (2) climate change can affect the toxicity of chemicals, but chemicals can also affect how organisms acclimate to climate change; (3) effects of GCC may be slow, variable, and difficult to detect, though some populations and communities of high vulnerability may exhibit responses sooner and more dramatically than others; (4) future approaches to human and ecological risk assessments will need to incorporate multiple stressors and cumulative risks considering the wide spectrum of potential impacts stemming from GCC; and (5) baseline/reference conditions for estimating resource injury and restoration/rehabilitation will continually shift due to GCC and represent significant challenges to practitioners.

Environmental Toxicology and Chemistry↗

USGS1999

Evaluating sediment chemistry and toxicity data using logistic regression modeling

This paper describes the use of logistic-regression modeling for evaluating matching sediment chemistry and toxicity data. Contaminant- specific logistic models were used to estimate the percentage of samples expected to be toxic at a given concentration. These models enable users to select the probability of effects of concern corresponding to their specific assessment or management objective or to estimate the probability of observing specific biological effects at any contaminant concentration. The models were developed using a large database (n = 2,524) of matching saltwater sediment chemistry and toxicity data for field-collected samples compiled from a number of different sources and geographic areas. The models for seven chemicals selected as examples showed a wide range in goodness of fit, reflecting high variability in toxicity at low concentrations and limited data on toxicity at higher concentrations for some chemicals. The models for individual test endpoints (e.g., amphipod mortality) provided a better fit to the data than the models based on all endpoints combined. A comparison of the relative sensitivity of two amphipod species to specific contaminants illustrated an important application of the logistic model approach.

Environmental Toxicology and Chemistry↗

USGS1996

Controls on surface water chemistry in the upper Merced River basin, Yosemite National Park, California

Surface water draining granitic bedrock in Yosemite National Park exhibits considerable variability in chemical composition, despite the relative homogeneity of bedrock chemistry. Other geological factors, including the jointing and distribution of glacial till, appear to exert strong controls on water composition. Chemical data from three surface water surveys in the upper Merced River basin conducted in August 1981, June 1988 and August 1991 were analysed and compared with mapped geological, hydrological and topographic features to identify the solute sources and processes that control water chemistry within the basin during baseflow. Water at most of the sampling sites was dilute, with alkalinities ranging from 26 to 77 μequiv. l −1 . Alkalinity was much higher in two subcatchments, however, ranging from 51 to 302 μequiv. l −1 . Base cations and silica were also significantly higher in these two catchments than in the rest of the watershed. Concentrations of weathering products in surface water were correlated to the fraction of each subcatchment underlain by surficial material, which is mostly glacial till. Silicate mineral weathering is the dominant control on concentrations of alkalinity, silica and base cations, and ratios of these constituents in surface water reflect the composition of local bedrock. Chloride concentrations in surface water samples varied widely, ranging from <1 to 96 μequiv. l −1 . The annual volume-weighted mean chloride concentration in the Merced River at the Happy Isles gauge from 1968 to 1990 was 26 μequiv. l −1 , which was five times higher than in atmospheric deposition (4–5 μequiv. l −1 ), suggesting that a source of chloride exists within the watershed. Saline groundwater springs, whose locations are probably controlled by vertical jointing in the bedrock, are the most likely source of the chloride. Sulphate concentrations varied much less than most other solutes, ranging from 3 to 14 μequiv. l −1 . Concentrations of sulphate in quarterly samples collected at the watershed outlet also showed relatively little variation, suggesting that sulphate may be regulated to some extent by a within-watershed process, such as sulphate adsorption.

Hydrological Processes↗

USGS1997

Effects of basin size on low-flow stream chemistry and subsurface contact time in the neversink river watershed, New York

The effects of basin size on low-flow stream chemistry and subsurface contact time were examined for a part of the Neversink River watershed in southern New York State. Acid neutralizing capacity (ANC), the sum of base cation concentrations (SBC), pH and concentrations of total aluminum (Al), dissolved organic carbon (DOC) and silicon (Si) were measured during low stream flow at the outlets of nested basins ranging in size from 0·2 to 166·3 km 2 . ANC, SBC, pH, Al and DOC showed pronounced changes as basin size increased from 0·2 to 3 km 2 , but relatively small variations were observed as basin size increased beyond 3 km 2 . An index of subsurface contact time computed from basin topography and soil hydraulic conductivity also showed pronounced changes as basin size increased from 0·2 to 3 km 2 and smaller changes as basin size increased beyond 3 km 2 . These results suggest that basin size affects low-flow stream chemistry because of the effects of basin size on subsurface contact time.

Hydrological Processes↗

USGS2011

Establishing spatial trends in water chemistry and stable isotopes (δ 15 N and δ 13 C) in the Elwha River prior to dam removal and salmon recolonization

Two high-head dams on the Elwha River in Washington State (USA) have changed the migratory patterns of resident and anadromous fish, limiting Pacific salmon to the lower 7.9 km of a river that historically supported large Pacific salmon runs. To document the effects of the dams prior to their removal, we measured carbon and nitrogen stable isotope ratios of primary producers, benthic macroinvertebrates, and fish, and water chemistry above, between and below the dams. We found that δ 15 N was significantly higher in fish, stoneflies, black flies, periphyton and macroalgae where salmon still have access. Fish and chloroperlid stoneflies were enriched in δ 13 C, but the values were more variable than in δ 15 N. For some taxa, there were also differences between the two river sections that lack salmon, suggesting that factors other than marine-derived nutrients are structuring longitudinal isotopic profiles. Consistent with trophic theory, macroalgae had the lowest δ 15 N, followed by periphyton, macroinvertebrates and fish, with a range of 6.9, 6.2 and 7.7‰ below, between, and above the dams, respectively. Water chemistry analyses confirmed earlier reports that the river is oligotrophic. Phosphorous levels in the Elwha were lower than those found in other regional rivers, with significant differences among regulated, unregulated and reference sections. The removal of these dams, among the largest of such projects ever attempted, is expected to facilitate the return of salmon and their marine-derived nutrients (MDN) throughout the watershed, possibly altering the food web structure, nutrient levels and stable isotope values that we documented.

Washington↗

USGS2007

Identifying biotic integrity and water chemistry relations in nonwadeable rivers of Wisconsin: Toward the development of nutrient criteria

We sampled 41 sites on 34 nonwadeable rivers that represent the types of rivers in Wisconsin, and the kinds and intensities of nutrient and other anthropogenic stressors upon each river type. Sites covered much of United States Environmental Protection Agency national nutrient ecoregions VII-Mostly Glaciated Dairy Region, and VIII-Nutrient Poor, Largely Glaciated upper Midwest. Fish, macroinvertebrates, and three categories of environmental variables including nutrients, other water chemistry, and watershed features were collected using standard protocols. We summarized fish assemblages by index of biotic integrity (IBI) and its 10 component measures, and macroinvertebrates by 2 organic pollution tolerance and 12 proportional richness measures. All biotic and environmental variables represented a wide range of conditions, with biotic measures ranging from poor to excellent status, despite nutrient concentrations being consistently higher than reference concentrations reported for the regions. Regression tree analyses of nutrients on a suite of biotic measures identified breakpoints in total phosphorus (~0.06 mg/l) and total nitrogen (~0.64 mg/l) concentrations at which biotic assemblages were consistently impaired. Redundancy analyses (RDA) were used to identify the most important variables within each of the three environmental variable categories, which were then used to determine the relative influence of each variable category on the biota. Nutrient measures, suspended chlorophyll a, water clarity, and watershed land cover type (forest or row-crop agriculture) were the most important variables and they explained significant amounts of variation within the macroinvertebrate (R 2 = 60.6%) and fish (R 2 = 43.6%) assemblages. The environmental variables selected in the macroinvertebrate model were correlated to such an extent that partial RDA analyses could not attribute variation explained to individual environmental categories, assigning 89% of the explained variation to interactions among the categories. In contrast, partial RDA attributed much of the explained variation to the nutrient (25%) and other water chemistry (38%) categories for the fish model. Our analyses suggest that it would be beneficial to develop criteria based upon a suite of biotic and nutrient variables simultaneously to deem waters as not meeting their designated uses. ?? 2007 Springer Science+Business Media, LLC.

Environmental Management↗

USGS2007

Trends in summer chemistry linked to productivity in lakes recovering from acid deposition in the Adirondack region of New York

The US Environmental Protection Agency established the Adirondack Effects Assessment Program (AEAP) to evaluate and monitor the status of biological communities in lakes in the Adirondack region of New York that have been adversely affected by acid deposition. This program includes chemical analysis of 30 lakes, sampled two to three times each summer. Results of trends analysis for lake chemistry and chlorophyll a (chlor a) are presented for 1994 to 2003, and a general comparison is made with recent results of the Adirondack Long-Term Monitoring (ALTM) Program, which included chemical analysis of all but two of these lakes (plus an additional 24 lakes) monthly, year-round for 1992-2004. Increases in pH were found in 25 of the 30 AEAP lakes (P < 0.05) and increases in acid-neutralizing capacity (ANC) were found in 12 of the 30 lakes (P < 0.05). Concentrations of both SO 42- and Mg 2+ decreased in 11 lakes (P < 0.05), whereas concentrations of NO 3- decreased in 20 lakes (P < 0.05). Concentrations of NH 4+ decreased in 10 lakes at a significance level of P < 0.05 and in three other lakes based on P < 0.1. Concentrations of inorganic and organic monomeric aluminum generally were below the reporting limit of 1.5 ??mol L-1, but decreases were detected in four and five lakes, respectively (P < 0.1). Concentrations of chlor a increased in seven lakes at a significance level of P < 0.05 and two lakes at a significance level of P < 0.1. A significant inverse correlation was also found between chlor a and NO 3- concentrations in nine lakes at a significance level of P < 0.05 and two lakes at a significance level of P < 0.1. Results of AEAP analysis of lake chemistry were similar to those of the ALTM Program, although decreases in SO 42- concentrations were more evident in the year-round ALTM record. Overall, the results suggest (a) a degree of chemical recovery from acidification during the summer, (b) an increase in phytoplankton productivity, and (c) a decreasing trend in NO 3- concentrations resulting from the increased productivity. ?? 2007 Springer Science+Business Media, Inc.

Ecosystems↗

USGS1978

Correction of ground-water chemistry and carbon isotopic composition for effects of CO2 outgassing

Direct P co 2 "> P co2 measurements on water samples from several CO 2 -charged warm springs are significantly higher than P co 2 "> P co2 values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO 2 outgassing during pH measurement. Because samples for direct P co 2 "> P co2 measurement can be taken with minimal disturbance to the water chemistry, we have used the measured P co 2 "> P co2 to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of δ 13 C "> δ 13 C , pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, P co 2 "> P co2 measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.

Geochimica et Cosmochimica Acta↗

USGS1990

Coupled variations in helium isotopes and fluid chemistry: Shoshone Geyser Basin, Yellowstone National Park

Early studies of 3 He/ 4 He variations in geothermal systems have generally attributed these fluctuations to either differences in the source of the magmatic 3 He-rich helium or to local differences in the deep flux of magmatic 3 He-rich helium. Kennedy et al. (1987), however, show that near-surface processes such as boiling and dilution may also drastically affect 3 He 4 "> 3 He 4 He ratios of geothermal vapors. Helium isotope ratios were determined for several hot springs at Shoshone Geyser Basin of Yellowstone National Park for this study, along with other noble gas data. Stable isotope data and water and gas chemistry data for each spring were also compiled. The water chemistry indicates that there is one deep, hot thermal water in the area which is mixing with dilute meteoric water that has entered the system at depth. Spring HCO 3 − concentrations correlate with 3 He 4 He "> 3 He 4 He values, as in nearby Lower Geyser Basin. This correlation is attributed to variable amounts of deep dilution of thermal waters with a relatively cool water that inhibits boiling at depth, thus preventing the loss of CO 2 (and therefore HCO 3 − ) and magmatic He in the most diluted samples. Oxygen and hydrogen isotope data also support a boiling and dilution model, but to produce the observed fractionations, the boiling event would have to be extensive, with steam loss at the surface, whereas the boiling that affected the helium isotope ratios was probably a small scale event with steam loss at depth. It is possible that deep boiling occurred in the basin and that small amounts of steam escaped along fractures at about 500 m below the surface while all subsequently produced steam was lost near or at the surface.

Geochimica et Cosmochimica Acta↗

USGS1990

Modelling streamwater chemistry as a mixture of soilwater end-members - A step towards second-generation acidification models

In present acidification models, soilwater characteristics, though modelled, are seldom checked against field observations. Given that such data are now collected as part of many catchment studies, a technique is developed whereby stream water can be predicted as a mixture of the observed soilwater classes or end-members. Provided that a sufficient set of end-members has been identified, a least-squares technique can be used to estimate the contribution to the stream from each end-member, whenever streamwater samples have been taken. For two catchments, Birkenes in southern Norway and Plynlimon in Mid-Wales, the analysis indicates that the soilwater end-members observed to date are insufficient to explain streamwater chemistry. However, properties of the missing soil waters have been identified, thus facilitating future field work. When an adequate set of soilwater end-members has been established, long-term predictions of changes in streamwater chemistry reduce to the problem of predicting the fate of each end-member. Thus, a separate hydrological submodel is not needed, since the mixing patterns are derived from the end-member analysis.

Journal of Hydrology↗

USGS1990

Modelling streamwater chemistry as a mixture of soilwater end-members - An application to the Panola Mountain catchment, Georgia, U.S.A.

Streamwater chemistry at Panola Mountain research catchment, Georgia, U.S.A., is explained as a mixture of representative soilwater solutions that are considered to be temporally invariant to a first approximation. The selection of three end-members from all sampled soil waters is evaluated by comparing the observed and predicted streamwater concentration of six solutes (alkalinity, sulfate, sodium, magnesium, calcium and dissolved silica), which are assumed to mix conservatively, and by assessing the consistency of the implied hydrograph separation with the hydrological mechanisms that are believed to be operating in this catchment. The percentage of variation in the streamwater solute concentrations explained by the end-member mixing analysis (EMMA) ranges from 82 to >97%, and the hydrograph separation is, intuitively, physically reasonable. If the correct end-members have been identified, the streamwater chemical response to different levels of acidic deposition can be predicted by examining the change in each end-member under different loads; no hydrological model is required. If a traditional hydrochemical model, which is driven by rainfall quantity and quality, is desired, this analysis provides an indication of the model structure that would be necessary to reproduce both streamwater and soilwater chemistry.

Georgia↗

USGS1990

Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HCl HF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C "> HC ratios, X-ray diffraction (XRD), 13 C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C "> HC ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp 2 -hybridized and 20% is sp 3 -hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300°C shows that the materials examined have not previously been subjected to temperatures as high as 300°C.

Witwatersrand goldfields↗

USGS1990

Influence of climate and eolian dust on the major-element chemistry and clay mineralogy of soils in the northern Bighorn basin, U.S.A.

Soil chronosequences in the northern Bighorn basin permit the study of chronologic changes in the major-element chemistry and clay mineralogy of soils formed in different climates. Two chronosequences along Rock Creek in south-central Montana formed on granitic alluvium in humid and semiarid climates over the past two million years. A chronosequence at the Kane fans in north-central Wyoming formed on calcareous alluvium in an arid climate over the past 600,000 years. Detailed analyses of elemental chemistry indicate that the soils in all three areas gradually incorporated eolian dust that contained less zirconium, considered to be chemically immobile during weathering, than did the alluvium. B and C horizons of soils in the wettest of the chronosequences developed mainly at logarithmic rates, suggesting that leaching, initially rapid but decelerating, dominated the dust additions. In contrast, soils in the most arid of the chronosequences developed at linear rates that reflect progressive dust additions that were little affected by leaching. Both weathering and erosion may cause changes with time to appear logarithmic in A horizons of soils under the moist and semiarid climatic regimes. Clay minerals form with time in the basal B and C horizons and reflect climatic differences in the three areas. Vermiculite, mixed-layer illite-smectite, and smectite form in the soils of the moist-climate chronosequence; smectite forms in the semiarid-climate chronosequence; and smectite and palygorskite form in the arid-climate chronosequence. ?? 1990.

Catena↗

USGS1992

Ground water chemistry and geochemical modeling of water-rock interactions at the Osamu Utsumi mine and the Morro do Ferro analogue study sites, Poços de Caldas, Minas Gerais, Brazil

Surface and ground waters, collected over a period of three years from the Osamu Utsumi uranium mine and the Morro do Ferro thorium/rare-earth element (Th/REE) deposits, were analyzed and interpreted to identify the major hydrogeochemical processes. These results provided information on the current geochemical evolution of ground waters for two study sites within the Poços de Caldas Natural Analogue Project. The ground waters are a K–Fe–SO 4 –F type, a highly unusual composition related to intense weathering of a hydrothermally altered and mineralized complex of phonolites. Tritium and stable isotope data indicate that ground waters are of meteoric origin and are not affected significantly by evaporation or water–rock interactions. Recharging ground waters at both study sites demonstrate water of less than about 35 years in age, whereas deeper, more evolved ground waters are below 1 TU but still contain in most cases detectable tritium. These deeper ground waters may be interpreted as being of 35 to 60 or more years in age, resulting mainly from an admixture of younger with older ground waters and/or indicating the influence of subsurface produced tritium. Geochemical processes involving water–rock–gas interactions have been modeled using ground water compositions, mineralogic data, ion plots and computations of speciation, non-thermodynamic mass balance and thermodynamic mass transfer. The geochemical reaction models can reproduce the water chemistry and mineral occurrences and they were validated by comparing the results of thermodynamic mass transfer calculations (using the PHREEQE program, Parkhurst et al., 1980). The results from the geochemical reaction models reveal that the dominant processes are production of CO 2 in the soil zone through aerobic decay of organic matter, dissolution of fluorite, calcite, K-feldspar, albite, chlorite and manganese oxides, oxidation of pyrite and sphalerite, and precipitation of ferric oxides, silica and kaolinite. Gibbsite precipitation can be modeled for the shallow (recharge) water chemistry at Morro do Ferro, consistent with known mineralogy. Recharge waters are undersaturated with respect to barite and discharging waters and deeper ground waters are saturated to supersaturated with respect to barite demonstrating a strong solubility control. Strontium isotope data demonstrate that sources other than calcium-bearing minerals are required to account for the dissolved strontium in the ground waters. These may include K-feldspar, smectite–chlorite mixed-layer clays and goyazite [SrAl 3 (PO 4 ) 2 (OH) 5 • H 2 O]. 1992.

Journal of Geochemical Exploration↗

USGS2016

Increasing aeolian dust deposition to snowpacks in the Rocky Mountains inferred from snowpack, wet deposition, and aerosol chemistry

Mountain snowpacks are a vital natural resource for ∼1.5 billion people in the northern Hemisphere, helping to meet human and ecological demand for water in excess of that provided by summer rain. Springtime warming and aeolian dust deposition accelerate snowmelt, increasing the risk of water shortages during late summer, when demand is greatest. While climate networks provide data that can be used to evaluate the effect of warming on snowpack resources, there are no established regional networks for monitoring aeolian dust deposition to snow. In this study, we test the hypothesis that chemistry of snow, wet deposition, and aerosols can be used as a surrogate for dust deposition to snow. We then analyze spatial patterns and temporal trends in inferred springtime dust deposition to snow across the Rocky Mountains, USA, for 1993–2014. Geochemical evidence, including strong correlations (r 2 ≥ 0.94) between Ca 2+ , alkalinity, and dust concentrations in snow deposited during dust events, indicate that carbonate minerals in dust impart a strong chemical signature that can be used to track dust deposition to snow. Spatial patterns in chemistry of snow, wet deposition, and aerosols indicate that dust deposition increases from north to south in the Rocky Mountains, and temporal trends indicate that winter/spring dust deposition increased by 81% in the southern Rockies during 1993–2014. Using a multivariate modeling approach, we determined that increases in dust deposition and decreases in springtime snowfall combined to accelerate snowmelt timing in the southern Rockies by approximately 7–18 days between 1993 and 2014. Previous studies have shown that aeolian dust emissions may have doubled globally during the 20th century, possibly due to drought and land-use change. Climate projections for increased aridity in the southwestern U.S., northern Africa, and other mid-latitude regions of the northern Hemisphere suggest that aeolian dust emissions may continue to increase, compounding the risk that climate warming poses to snowpack water resources in arid/semi-arid regions of the world.

Atmospheric Environment↗

USGS2009

Changes in optical properties, chemistry, and micropore and mesopore characteristics of bituminous coal at the contact with dikes in the Illinois Basin

Changes in high-volatile bituminous coal (Pennsylvanian) near contacts with two volcanic intrusions in Illinois were investigated with respect to optical properties, coal chemistry, and coal pore structure. Vitrinite reflectance (Ro) increases from 0.62% to 5.03% within a distance of 5.5??m from the larger dike, and from 0.63% to 3.71% within 3.3??m from the small dike. Elemental chemistry of the coal shows distinct reductions in hydrogen and nitrogen content close to the intrusions. No trend was observed for total sulfur content, but decreases in sulfate content towards the dikes indicate thermochemical sulfate reduction (TSR). Contact-metamorphism has a dramatic effect on coal porosity, and microporosity in particular. Around the large dike, the micropore volume, after a slight initial increase, progressively decreases from 0.0417??cm3/g in coal situated 4.7??m from the intrusive contact to 0.0126??cm3/g at the contact. Strongly decreasing mesopore and micropore volumes in the altered zone, together with frequent cleat and fracture filling by calcite, indicate deteriorating conditions for both coalbed gas sorption and gas transmissibility. ?? 2008 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2018

Relationships between indicators of acid-base chemistry and fish assemblages in streams of the Great Smoky Mountains National Park

The acidity of many streams in the Great Smoky Mountains National Park (GRSM) has increased significantly since pre-industrial (∼1850) times due to the effects of highly acidic atmospheric deposition in poorly buffered watersheds. Extensive stream-monitoring programs since 1993 have shown that fish and macroinvertebrate assemblages have been adversely affected in many streams across the GRSM. Matching chemistry and fishery information collected from 389 surveys performed at 52 stream sites over a 22-year period were assessed using logistic regression analysis to help inform the U.S. Environmental Protection Agency’s assessment of the environmental impacts of emissions of oxides of nitrogen (NO x ) and sulfur (SO x ). Numerous logistic equations and associated curves were derived that defined the relations between acid neutralizing capacity (ANC) or pH and different levels of community richness, density, and biomass; and density and biomass of brook trout, rainbow trout, and small prey (minnow) populations in streams of the GRSM. The equations and curves describe the status of fish assemblages in the GRSM under contemporary emission levels and deposition loads of nitrogen (N) and sulfur (S) and provide a means to estimate how newly proposed (and various alternative) target deposition loads, which strongly influence stream ANC, might affect key ecological indicators. Several examples using ANC, community richness, and brook trout density are presented to illustrate the steps needed to predict how future changes in stream chemistry (resulting from different target deposition loads of N and S) will affect the probabilities of observing specific levels of selected biological indicators in GRSM streams. The implications of this study to the regulation of NO x and SO x emissions, water quality, and fisheries management in streams of the GRSM are discussed, but also qualified by the fact that specific examples provided need to be further explored before recommendations concerning their use as ecological indicators could be proposed.

North Carolina, Tennessee↗

USGS2021

A reactive transport approach to modeling cave seepage water chemistry II: Elemental signatures

Karst systems are useful for examining spatial and temporal variability in Critical Zone processes because they provide a window into the subsurface where waters have interacted with vegetation, soils, regolith, and bedrock across a range of length and timescales. These hydrologic pathways frequently include the precipitation of speleothems, which provide long-term archives of climate and environmental change. Trace element ratios in speleothems (Mg/Ca, Sr/Ca, Ba/Ca) have the potential to provide information about past changes in rainfall and infiltration, but controls on them can be complex and their interpretation must be based on an understanding of the modern cave system. Here we integrate observations of surface conditions, bedrock, soil, and drip water chemistry of Blue Spring Cave in Tennessee, USA with the reactive transport model CrunchTope, which we have calibrated for karst systems to investigate the primary controls on trace element variations in cave seepage waters. We find that measured drip water Mg/Ca and Sr/Ca are captured within the model through variable amounts of limestone dissolution followed by precipitation of secondary calcite that happens within the cave rather than the host limestone. However, strong spatial controls on drip water Mg/Ca and Sr/Ca likely reflect seepage water interactions with variable amounts of diagenetic phases in the host rock. In contrast, Ba/Ca values are consistent across the cave and vary with effective rainfall, suggesting that this parameter may be the most consistent metric for limestone dissolution and prior calcite precipitation and can act as a proxy for rainfall and infiltration in this cave system. Our findings emphasize the importance of evaluating spatial heterogeneity in cave drip waters and outline a novel modeling approach for determining the dominant controls on drip water chemistry in support of the interpretations of paleoclimate records.

Geochimica et Cosmochimica Acta↗