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The mineral chemistry networks of tin and tungsten reflect metallogenic eras of the Mesozoic

Continental remobilization is a crucial driver of metallogenesis and the formation of ore deposits. Some of the world’s largest mineral deposits of the economically valuable elements tin (Sn), tungsten (W), gold (Au), copper (Cu), lead (Pb), and zinc (Zn) formed during the Mesozoic Era. Additionally, the chemistry and distribution of the elements Sn and W have been investigated in previous studies to understand planetary formation and differentiation processes. These two elements are largely co-located during certain South China Mesozoic metallogenic events but are not co-located during other time periods in the same regions. Here, we investigated the mineral chemistry network similarities and dissimilarities of Sn and W to understand their mineral formation and distribution during the Mesozoic Era and throughout Earth history. Mineral chemistry network community detection analysis and electronegativity associations among mineral constituent elements of Sn minerals and W minerals indicate that the elements have similar chemistry among their oxide minerals. However, Sn forms a much wider range of minerals that also contain S compared to W, which occurs in a limited number of S-containing minerals. The divergent constituent element interactions among S-containing Sn minerals and W minerals reflect the redox sensitivity and importance of oxygen (O) fugacity in Sn mineral formation. Conversely, extensive W mineral deposits are known to form at both high and low O fugacities. The similarities and differences between the mineral chemistry networks of Sn and W reflect the mineral distribution of the two elements in the Sn-W mineralization event from 160 to 139 Ma vs. the Sn–uranium (U) mineralization event from 125 to 98 million years ago (Ma). The mineral chemistry and distribution of Mesozoic Sn and W deposits illustrate the contrasting importance of redox and O fugacity on the mineral formation of different elements, and the dynamic crustal evolution that took place during this period of Earth history.

Geosciences↗

Carbon dioxide toxicity to zebra mussels (Dreissena polymorpha) is dependent on water chemistry

Carbon dioxide (CO 2 ) is gaining interest as a tool to combat aquatic invasive species, including zebra mussels ( Dreissena polymorpha ). However, the effects of water chemistry on CO 2 efficacy are not well described. We conducted five trials in which we exposed adult zebra mussels to a range of CO 2 in water with adjusted total hardness and specific conductance. We compared dose–responses and found differences in lethal concentration to 50% of organisms (LC50) estimates ranging from 108.3 to 179.3 mg/L CO 2 and lethal concentration to 90% of organisms (LC90) estimates ranging from 163.7 to 216.6 mg/L CO 2 . We modeled LC50 and LC90 estimates with measured water chemistry variables from the trials. We found sodium (Na + ) concentration to have the strongest correlation to changes in the LC50 and specific conductance to have the strongest correlation to changes in the LC90. Our results identify water chemistry as an important factor in considering efficacious CO 2 concentrations for zebra mussel control. Additional research into the physiological responses of zebra mussels exposed to CO 2 may be warranted to further explain mode of action and reported selectivity. Further study could likely develop a robust and relevant model to refine CO 2 applications for a wider range of water chemistries. Environ Toxicol Chem 2024;00:1–8. Published 2024. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Environmental Toxicology and Chemistry↗

Evaluation of stream chemistry trends in US Geological Survey reference watersheds, 1970-2010

The Hydrologic Benchmark Network (HBN) is a long-term monitoring program established by the US Geological Survey in the 1960s to track changes in the streamflow and stream chemistry in undeveloped watersheds across the USA. Trends in stream chemistry were tested at 15 HBN stations over two periods (1970–2010 and 1990–2010) using the parametric Load Estimator (LOADEST) model and the nonparametric seasonal Kendall test. Trends in annual streamflow and precipitation chemistry also were tested to help identify likely drivers of changes in stream chemistry. At stations in the northeastern USA, there were significant declines in stream sulfate, which were consistent with declines in sulfate deposition resulting from the reductions in SO 2 emissions mandated under the Clean Air Act Amendments. Sulfate declines in stream water were smaller than declines in deposition suggesting sulfate may be accumulating in watershed soils and thereby delaying the stream response to improvements in deposition. Trends in stream chemistry at stations in other part of the country generally were attributed to climate variability or land disturbance. Despite declines in sulfate deposition, increasing stream sulfate was observed at several stations and appeared to be linked to periods of drought or declining streamflow. Falling water tables might have enhanced oxidation of organic matter in wetlands or pyrite in mineralized bedrock thereby increasing sulfate export in surface water. Increasing sulfate and nitrate at a station in the western USA were attributed to release of soluble salts and nutrients from soils following a large wildfire in the watershed.

Environmental Monitoring and Assessment↗

Changes in stream chemistry and biology in response to reduced levels of acid deposition during 1987-2003 in the Neversink River Basin, Catskill Mountains

Atmospheric acid deposition has decreased in the northeastern United States since the 1970s, resulting in modest increases in pH, acid-neutralizing capacity (ANC), and decreases in inorganic monomeric aluminum (AlIM) concentrations since stream chemistry monitoring began in the 1980s in the acid-sensitive upper Neversink River basin in the Catskill Mountains of New York. Stream pH has increased by 0.01 units/year during 1987-2003 at three sites in the Neversink basin as determined by Seasonal Kendall trend analysis. In light of this observed decrease in stream acidity, we sampled 12 stream sites within the Neversink River watershed for water chemistry, macroinvertebrates, fish, and periphytic diatoms in 2003 to compare with a similar data set collected in 1987. Metrics and indices that reflect sensitivity to stream acidity were developed with these biological data to determine whether changes in stream biota over the intervening 16 years parallel those of stream chemistry. Statistical comparisons of data on stream chemistry and an acid biological assessment profile (Acid BAP) derived from invertebrate data showed no significant differences between the two years. For pH and ANC, however, values in 2003 were generally lower than those in 1987; this difference likely resulted from higher streamflow in summer 2003. Despite these likely flow-induced changes in summer 2003, an ordination and cluster analysis of macroinvertebrate taxa based on the Acid BAP indicated that the most acidic sites in the upstream half of the East Branch Neversink River form a statistically significant separate cluster consistent with less acidic stream conditions. This analysis is consistent with limited recovery of invertebrate species in the most acidic reaches of the river, but will require additional improvement in stream chemistry before a stronger conclusion can be drawn. Data on the fish and periphytic diatom communities in 2003 indicate that slimy sculpin had not extended their habitat to upstream reaches that previously were devoid of this acid-intolerant species in 1987; a diatom acid-tolerance index indicates continued high-acid impact throughout most of the East Branch and headwaters of the West Branch Neversink River. ?? 2007 Elsevier Ltd. All rights reserved.

Ecological Indicators↗

Modeling aluminum-silicon chemistries and application to Australian acidic playa lakes as analogues for Mars

Recent Mars missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major relevant findings are the presence in Meridiani Planum sediments of the mineral jarosite (a ferric sulfate salt) and related minerals that require formation from an acid-salt brine and oxidizing environment. Similar mineralogies have been observed in acidic saline lake sediments in Western Australia (WA), and these lakes have been proposed as analogues for acidic sedimentary environments on Mars. The prior version of the equilibrium chemical thermodynamic FREZCHEM model lacked Al and Si chemistries that are needed to appropriately model acidic aqueous geochemistries on Earth and Mars. The objectives of this work were to (1) add Al and Si chemistries to the FREZCHEM model, (2) extend these chemistries to low temperatures (<0 ??C), if possible, and (3) use the reformulated model to investigate parallels in the mineral precipitation behavior of acidic Australian lakes and hypothetical Martian brines. FREZCHEM is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <-70 to 25 ??C and the pressure range from 1 to 1000 bars. Aluminum chloride and sulfate mineral parameterizations were based on experimental data. Aluminum hydroxide and silicon mineral parameterizations were based on Gibbs free energy and enthalpy data. New aluminum and silicon parameterizations added 12 new aluminum/silicon minerals to this Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO 4 -NO 3 -OH-HCO 3 -CO 3 -CO 2 -O 2 -CH 4 -Si-H 2 O system that now contain 95 solid phases. There were similarities, differences, and uncertainties between Australian acidic, saline playa lakes and waters that likely led to the Burns formation salt accumulations on Mars. Both systems are similar in that they are dominated by (1) acidic, saline ground waters and sediments, (2) Ca and/or Mg sulfates, and (3) iron precipitates such as jarosite and hematite. Differences include: (1) the dominance of NaCl in many WA lakes, versus the dominance of Fe-Mg-Ca-SO 4 in Meridiani Planum, (2) excessively low K + concentrations in Meridiani Planum due to jarosite precipitation, (3) higher acid production in the presence of high iron concentrations in Meridiani Planum, and probably lower rates of acid neutralization and hence, higher acidities on Mars owing to colder temperatures, and (4) lateral salt patterns in WA lakes. The WA playa lakes display significant lateral variations in mineralogy and water chemistry over short distances, reflecting the interaction of acid ground waters with neutral to alkaline lake waters derived from ponded surface runoff. Meridiani Planum observations indicate that such lateral variations are much less pronounced, pointing to the dominant influence of ground water chemistry, vertical ground water movements, and aeolian processes on the Martian surface mineralogy. ?? 2009 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

Characterizing sulfur redox state and geochemical implications in deep-time using mineral chemistry network analysis

Sulfur (S) is a central element in global biogeochemical cycling and Earth’s redox evolution. Minerals that contain S are an important record of local environmental conditions at the time of their formation based on chemical speciation and redox. However, the oxidation state of S for hundreds of different S-containing minerals and thousands of S-containing mineral localities is unknown, largely sulfides and sulfosalts, and the redox state alone does not fully capture mineral chemistry diversity, thus limiting understanding of S redox evolution. Here, we use mineral chemistry network analysis and the weighted Mineral Element Electronegativity Coefficient of Variation (wMEE CV ) metric to investigate the element interactions and localities of S-containing minerals from the Mineral Evolution Database (MED) to infer the redox state of S in minerals where the redox state is unknown (S U ). Louvain community detection of the S mineral chemistry redox network reveals that there are three main network communities that are separated by redox state. The S 6+ community includes minerals that contain the S 6+ redox state and a small number of S 4+ and S 2+ minerals, the S 2− community includes S 2− -containing minerals, and the S U community includes minerals in which the redox state of S is unknown. The wMEE CV values of the S U community closely overlap with the wMEE CV values of the S 2− community, and do not overlap with the wMEE CV values of the S 6+ community, indicating the S U community minerals contain predominately reduced S. Assuming that S U community minerals contain reduced S, as supported by their network chemical associations and wMEE CV values, then reduced S-containing minerals make up approximately 81 % of S-containing mineral localities in the S mineral chemistry network, even though the majority of all mineral localities (S-containing and non-S-containing) are oxygen (O)-containing minerals. Additionally, reduced S-containing minerals make up the majority (∼75 %) of all non-O containing mineral localities in the MED, representing the importance of reduced S as an electron source and substrate in the evolution of microbial metabolic networks. The range wMEE CV values of S 6+ community minerals expands through time due primarily to formation of chemically diverse sulfate minerals, coinciding with crustal oxidation from the late Proterozoic to Phanerozoic and the expansion of the marine sulfate reservoir. The intersection of shared constituent elements among reduced and oxidized S in the mineral chemistry network represents redox convergence of weathered S in the geosphere that was crucial in the formation of natural resource deposits and the evolution of biogeochemical cycles.

Geochimica et Cosmochimica Acta↗

Chemistry of rock-forming minerals of the Cretaceous-Paleocene batholith in southwestern Japan and implications for magma genesis

Petrographic descriptions and electron microprobe analyses of minerals are presented for 35 specimens from seven suites chosen to examine the transition from magnetite series to ilmenite series granitoids along two transects across the Cretaceous-Paleocene Inner Zone batholith of southwestern Japan. Regularities in chemical compositions of amphiboles, biotites, and feldspars suggest that fundamentally similar processes produced the magmas that formed the two series. Constant or decreasing Fe/(Fe+Mg) for biotites and amphiboles with increasing host rock silica content, coupled with the absence of early formed magnetite and sphene, suggest that magnetite series rocks may have become oxidized during crystallization near the level of intrusion, through the processes of second boiling and differential loss of hydrogen. For the Daito-Yokota, magnetite series suite, Fe/(Fe+Mg) for biotites decreased from 0.48 to 0.37 as SiO 2 content of the host rock increased from 55.3 to 75.5 wt %; for an ilmenite series suite from the Takanawa Peninsula, Fe/(Fe+Mg) for biotites increased from 0.51 to 0.77 with an increase in host rock SiO 2 from 53.4 to 75.5. Detailed consideration of amphibole chemistry shows predominance of edenitic and tschermakitic substitution schemes as well as coupling between substitutions of Ti in octahedral sites and Al IV . Interrelations between amphibole and biotite chemistry show that Fe/(Fe+Mg) and Mn contents can be interpreted in terms of equilibration, whereas Ti content cannot. The chemistry of chlorites correlates well with that of biotites; primary and secondary muscovites are distinct in composition. Plagioclase in all studied suites shows igneous zoning appropriate to host rock composition; perthitic alkali feldspars in all samples have lost albite component, and temperatures based on the two-feldspar geothermometer are low. The biotite-apatite geothermometer is also inoperative for this group of samples because fully fluorinated apatites typically occur in biotites of modest F content. Whereas magnetites have reequilibrated, analyses of ilmenites for the representative Daito-Yokota and Takanawa suites corroborate biotite compositional data and suggest that f O2 probably differed by 2 to 3 orders of magnitude during crystallization of silica-rich magnetite and ilmenite series granites. Whole-rock chemistry supports mineral chemistry in suggesting that the studied granitoids have crystallized from magmas generated in a lower crustal environment in which mantle-derived magmas partially melted source materials with igneous characteristics.

Journal of Geophysical Research Solid Earth↗

Soil chemistry, and not short-term (1–2 year) deer exclusion, explains understory plant occupancy in forests affected by acid deposition

The loss of species diversity and plant community structure throughout the temperate deciduous forests of North America have often been attributed to overbrowsing by white-tailed deer ( Odocoileus virginanus ). Slow species recovery following removal from browsing, or reduction in deer density, has been termed a legacy effect of past deer herbivory. However, vegetation legacy effects have also coincided with changes to soil chemistry throughout the north-eastern USA. In this paper, we assess the viability of soil chemistry (i.e. pH, extractable nutrients and extractable metals) and other factors (topography, light, overstory basal area and location) as alternative explanations for a lack of vegetation recovery. We compared the relative effects of soil chemistry, site conditions and short-term (1–2 year) deer exclusion on single-species occupancy probabilities of 10 plant taxa common to oak-hickory forests in central Pennsylvania. We found detection for all modelled species was constant and high ( ⁠ p ^ "> p ^ p^ > 0.65), and occupancy probability of most taxa was best explained by at least one soil chemistry parameter. Specifically, ericaceous competing vegetation was more likely to occupy acidic (pH < 3.5), base cation-poor (K < 0.20 cmol c kg −1 ) sites, while deer-preferred plants were less likely to occur when soil manganese exceeded 0.1 cmol c kg −1 . Short-term deer exclusion did not explain occupancy of any plant taxon, and site conditions were of nominal importance. This study demonstrates the importance of soil chemistry in shaping plant community composition in the north-central Appalachians, and suggests soil as an alternative, or additional, explanation for deer vegetation legacy effects. We suggest that the reliance on phyto-indicators of deer browsing effects may overestimate the effects of browsing if those species are also limited by unfavourable soil conditions. Future research should consider study designs that address the complexity of deer forest interactions, especially in areas with complex site-vegetation histories.

Pennsylvania↗

Rock-Bound Arsenic Influences Ground Water and Sediment Chemistry Throughout New England

The information in this report was presented at the Northeastern Region Geological Society of America meeting held March 11-14, 2007, in Durham, New Hampshire. In the New England crystalline bedrock aquifer, concentrations of arsenic that exceed the drinking water standard of 10 ?g/L occur most frequently in ground water from wells sited in specific metamorphic and igneous rock units. Geochemical investigations indicate that these geologic units typically have moderately elevated whole-rock concentrations of arsenic compared to other rocks in the region. The distribution of ground water wells with As > 5 ?g/L has a strong spatial correlation with specific bedrock units where average whole-rock concentrations of arsenic exceed 1.1 mg/kg and where geologic and geochemical factors produce high pH ground water. Arsenic concentrations in stream sediments collected from small drainages reflect the regional distribution of this natural arsenic source and have a strong correlation with both rock chemistry and the distribution of bedrock units with elevated arsenic chemistry. The distribution of ground water wells with As > 5 ?g/L has a strong spatial correlation with the distribution of stream sediments where concentrations of arsenic exceed 6 mg/kg. Stream sediment chemistry also has a weak correlation with the distribution of agricultural lands where arsenical pesticides were used on apple, blueberry, and potato crops. Elevated arsenic concentrations in bedrock wells, however, do not correlate with agricultural areas where arsenical pesticides were used. These results indicate that both stream sediment chemistry and the solubility and mobility of arsenic in ground water in bedrock are influenced by host-rock arsenic concentrations. Stream sediment chemistry and the distribution of geologic units have been found to be useful parameters to predict the areas of greatest concern for elevated arsenic in ground water and to estimate the likely levels of human exposure to elevated arsenic in drinking water in New England. However, the extreme local variability of arsenic concentrations in ground water from these rock sources indicate that arsenic concentrations in ground water are affected by other factors in addition to arsenic concentrations in rock.

Open-File Report↗

Vertical gradients in water chemistry and age in the Northern High Plains Aquifer, Nebraska, 2003

The northern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of Colorado, Kansas, Nebraska, South Dakota, and Wyoming. Despite the aquifer’s importance to the regional economy, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey’s National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the northern High Plains aquifer were analyzed for major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, dissolved gases, and other parameters to evaluate vertical gradients in water chemistry and age in the aquifer. Chemical data and tritium and radiocarbon ages show that water in the aquifer was chemically and temporally stratified in the study area, with a relatively thin zone of recently recharged water (less than 50 years) near the water table overlying a thicker zone of older water (1,800 to 15,600 radiocarbon years). In areas where irrigated agriculture was an important land use, the recently recharged ground water was characterized by elevated concentrations of major ions and nitrate and the detection of pesticide compounds. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions. The concentration increases were accounted for primarily by dissolved calcium, sodium, bicarbonate, sulfate, and silica. In general, the chemistry of ground water throughout the aquifer was of high quality. None of the approximately 90 chemical constituents analyzed in each sample exceeded primary drinking-water standards. Mass-balance models indicate that changes in groundwater chemistry along flow paths in the aquifer can be accounted for by small amounts of feldspar and calcite dissolution; goethite and clay-mineral precipitation; organic-carbon and pyrite oxidation; oxygen reduction and denitrification; and cation exchange. Mixing with surface water affected the chemistry of ground water in alluvial sediments of the Platte River Valley. Radiocarbon ages in the aquifer, adjusted for carbon mass transfers, ranged from 1,800 to 15,600 14C years before present. These results have important implications with respect to development of ground-water resources in the Sand Hills. Most of the water in the aquifer predates modern anthropogenic activity so excessive removal of water by pumping is not likely to be replenished by natural recharge in a meaningful timeframe. Vertical gradients in ground-water age were used to estimate long-term average recharge rates in the aquifer. In most areas, the recharge rates ranged from 0.02 to 0.05 foot per year. The recharge rate was 0.2 foot per year in one part of the aquifer characterized by large downward hydraulic gradients. Nitrite plus nitrate concentrations at the water table were 0.13 to 3.13 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer. Dissolved-gas and nitrogen-isotope data indicate that denitrification in the aquifer removed 0 to 97 percent (average = 50 percent) of the nitrate originally present in recharge. The average amount of nitrate removed by denitrification in the aquifer north of the Platte River (Sand Hills) was substantially greater than the amount removed south of the river (66 as opposed to 0 percent), and the extent of nitrate removal appears to be related to the presence of thick deposits of sediment on top of the Ogallala Group in the Sand Hills that contained electron donors, such as organic carbon and pyrite, to support denitrification. Apparent rates of dissolved-oxygen reduction and denitrification were estimated on the basis of decreases in dissolved-oxygen concentrations and increases in concentrations of excess nitrogen gas and ground-water ages along flow paths from the water table to deeper wells. Median rates of dissolved-oxygen reduction and denitrification south of the Platte River were at least 10 times smaller than the median rates north of the river in the Sand Hills. The relatively large denitrification rates in the Sand Hills indicate that the aquifer in that area may have a greater capacity to attenuate nitrate contamination than the aquifer south of the river, depending on rates of ground-water movement in the two areas. Small denitrification rates south of the river indicate that nitrate contamination in that part of the aquifer would likely persist for a longer period of time.

Nebraska↗

Discharge, sediment, and water chemistry in Clear Creek, western Nevada, water years 2013–16

Clear Creek is a small stream that drains the eastern Carson Range near Lake Tahoe, flows roughly parallel to the Highway 50 corridor, and discharges to the Carson River near Carson City, Nevada. Historical and ongoing development in the drainage basin is thought to be affecting Clear Creek and its sediment-transport characteristics. Previous studies from water years (WYs) 2004 to 2007 and from 2010 to 2012 evaluated discharge, selected water-quality parameters, and suspended-sediment concentrations, loads, and yields at three Clear Creek sampling sites. This report serves as a continuation of the data collection and analyses of the Clear Creek discharge regime and associated water-chemistry and sediment concentrations and loads during WYs 2013–16. Total annual sediment loads ranged from 870 to 5,300 tons during WYs 2004–07, from 320 to 1,770 tons during WYs 2010–12, and from 50 to 200 tons during WYs 2013–16. Ranges in annual loads during the three study periods were not significantly different; however, total loads were greater during 2004–07 than they were during 2013–16. Annual suspended-sediment loads in WYs 2013–16 showed no significant change since WYs 2010–12 at sites 1 (U.S. Geological Survey reference site 10310485; Clear Creek above Highway 50, near Spooner Summit, Nevada) or 2 (U.S. Geological Survey streamgage 10310500; Clear Creek above Highway 50, near Spooner Summit, Nevada), but significantly lower loads at site 3 (U.S. Geological Survey site 10310518; Clear Creek at Fuji Park, at Carson City, Nevada), supporting the theory of sediment deposition between sites 2 and 3 where the stream gradient becomes more gradual. Currently, a threshold discharge of about 3.3 cubic feet per second is required to mobilize streambed sediment (bedload) from site 2 in Clear Creek. Mean daily discharge was significantly lower in 2010–12 than in 2004–07 and also significantly lower in 2013–16 than in 2010–12. During this study, lower bedload, and therefore lower total sediment load in Clear Creek was primarily due to significantly lower discharge and cannot be directly attributed to sediment mitigation work in the basin. Water chemistry in Clear Creek shows that the general water type of the creek under base-flow conditions in autumn is a dilute calcium bicarbonate. During winter and spring, the chemistry shifts toward a slightly more sodium and chloride character. Though the chemical characteristics show seasonal change, the water chemistries examined as part of this investigation remain within ecological criteria as adopted by the Nevada Division of Environmental Protection. There was no evidence of aqueous polynuclear aromatic hydrocarbons (PAHs) present in Clear Creek water during this study. Concentrations of PAHs, as determined in one bed-sediment sample and multiple semi-permeable membrane device extracts, were either less than quantifiable limits of analysis or were found at similar concentrations as blank samples. In July 2014, a 250–300-acre fire burned in the Clear Creek drainage basin. One day after the fire was extinguished, a thunderstorm washed sediment into the creek. A water chemistry sample collected as part of the post-fire storm event showed that the stormwater entering the creek had increased the concentrations of ammonium and organic nitrogen, phosphorus, manganese, and potassium; a similar finding of many other studies evaluating the effects of fires in small drainage basins. Subsequent chemical analyses of Clear Creek water in August 2014 (one month later) showed that these constituents had returned to pre-fire concentrations.

Nevada↗

Groundwater chemistry and water-level elevations in bedrock aquifers of the Piceance and Yellow Creek watersheds, Rio Blanco County, Colorado, 2013–16

The Piceance and Yellow Creek watersheds in Rio Blanco County, Colorado, are known to contain important energy resources (oil shale and natural gas) and mineral resources (nahcolite). The primary sources of fresh groundwater in the Piceance and Yellow Creek watersheds are bedrock aquifers in the Uinta and Green River Formations. The aquifers are divided into an upper and lower aquifer separated by a regionally extensive semiconfining layer. These aquifers provide water to streams and springs in the watersheds and are an important resource to people living and working in the area. Development of energy and mineral resources has the potential to affect the quality of groundwater in several ways. The Bureau of Land Management and the U.S. Geological Survey began groundwater monitoring in 2010 to characterize the groundwater quality and water-level elevations of shallow bedrock aquifers in the Piceance and Yellow Creek watersheds. The purpose of this report is to present ground-water chemistry and water-level elevations collected during 2013–16. Comparisons are made to data that were collected from the bedrock aquifers from 2010 to 2012 to identify the potential for changes in water quality and water-level elevations. Appreciable changes in water-level elevations and hydraulic gradient were observed in early April 2015 in two wells completed in the upper and lower aquifers. The hydraulic gradient between the two wells was consistently downward from the upper aquifer to the lower aquifer during 2010–15; however, in early April 2015, the gradient changed from downward to upward between the two aquifers. Overall, water-level elevations declined by about 14 and 11 feet in the upper and lower aquifers, respectively, from 2013 to 2016. Previously published data estimated groundwater ages at 1,200 years old in the upper aquifer and 9,600 years old in the lower aquifer. These groundwater ages indicate that ground-water was recharged over thousands of years. With such long periods of time for aquifer recharge, declines in water-level elevation over short time steps (a few months) have important implications for sustainable management of this resource. Solution mining activities or drilling for oil and natural gas in the area could be related to the changes observed in water-level elevations in these wells; however, further investigation would be needed to evaluate causation. Changes in major-ion chemistry were evaluated in the bedrock aquifer using time series plots of select major-ion data from 2010 to 2016. Major-ion chemistry was variable for a single well from 2010 to 2016 where alkalinity and sulfate were the most variable constituents. One possible explanation for the observed changes in major-ion chemistry may be that the sample depth for that well no longer represents the most appreciable flow in the borehole. On a larger scale, potential changes in flow within the borehole may indicate changes in the regional flow system. Methane and volatile organic compound concentrations were evaluated using a similar approach to that of major ions and had similar findings. Methane concentrations in wells sampled from 2010 to 2016 were generally constant. The only exception was observed at a single well where the range of methane concentrations was from 57.4 (2010) to 4.02 milligrams per liter (2013). This is the same well where changes in water-level elevation, hydraulic gradient, and major-ion chemistry were observed, providing multiple lines of evidence to indicate change in the bedrock aquifers. Sampling of a well located in an area with little energy development but where faults or fractures could provide a path for the migration of fluids indicate mixing of groundwater between the upper and lower aquifers.

Colorado↗

Hydrogeologic characteristics of Hourglass and New Years Cave Lakes at Jewel Cave National Monument, South Dakota, from water-level and water-chemistry data, 2015–21

Jewel Cave National Monument is in the western Black Hills of South Dakota and contains an extensive cave network, including various subterranean water bodies (cave lakes) that are believed to represent the regionally important Madison aquifer. Recent investigations have sought to improve understanding of hydrogeologic characteristics of cave lakes in Jewel Cave. The U.S. Geological Survey, in cooperation with the National Park Service, collected water-level and water-chemistry data within and near Jewel Cave to better understand groundwater interactions in Jewel Cave and to evaluate recharge characteristics of cave lakes. Continuous water-level data were collected at two cave lakes (Hourglass and New Years Lakes) from 2018 to 2021, and discrete measurements were collected by National Park Service staff from 2015 to 2021. Water samples were collected from one stream, one rain collector, three springs, and two cave lakes. The approach for this study included comparing water-level data collected from two cave lakes to historical climate data and using multivariate statistical analyses to evaluate water samples collected during this study and from previous investigations. This study builds on interpretations from previous investigations that collected similar datasets and performed similar analyses. Hydrographs of Hourglass and News Years Lakes from 2015 to 2021 demonstrated the variability of groundwater levels in Jewel Cave in response to dry and wet climate conditions. Hourglass Lake displayed small (up to 4.8 feet), gradual water-level changes, whereas New Years Lake displayed relatively large (up to at least 27.5 feet) and rapid water-level changes. Hourglass and New Years Lakes are about 0.4 mile apart at the land surface, and the water-level elevation between the lakes varied from 61 to 93.5 feet from 2016 to 2021. The proximity and relatively small elevation difference of Hourglass and New Years Lakes indicated different recharge sources and (or) mechanisms were responsible for hydrograph dissimilarities. Water-level changes at Hourglass Lake were similar to water-level changes at a well completed in the Madison aquifer about 9 miles south of Jewel Cave National Monument, which indicated Hourglass Lake may be recharged similar to the regional Madison aquifer along outcrops north of Jewel Cave. New Years Lake displayed almost no similarities to the well completed in the Madison aquifer—indicating a more direct connection to local recharge rather than solely from outcrops recharging the regional Madison aquifer. Results from multivariate statistical analyses of water-chemistry data were used to evaluate recharge observations from water-level data. The water chemistry of Hourglass Lake indicated its water was chemically more similar to precipitation than other groundwater sites sampled. A conceptual karst recharge model indicated that the dominant recharge source to Hourglass Lake was diffuse allogenic recharge from vertical movement of infiltrated precipitation through vertical or near-vertical fractures that extend through the Minnelusa Formation and unsaturated zone of the Madison Limestone. The water chemistry of New Years Lake was chemically similar to Hell Canyon Creek about 0.2 mile from New Years Lake at the land surface. Streamflow loss zones (concentrated allogenic recharge) along Hell Canyon Creek have not been mapped, but their presence in the Jewel Cave area has been speculated by previous investigations. A fault observed in the cave ceiling above New Years Lake by National Park Service staff could provide a natural conduit for direct recharge from Hell Canyon Creek to New Years Lake if the fault is extensive. Additional water-chemistry and water-level data, as well as streamflow data upstream and downstream of the potential streamflow loss zone along Hell Canyon Creek, are needed to prove the presence of this loss zone and discern further correlations between streamflow and water levels in New Years Lake. Observations from previous investigations and this study indicated recharge to Jewel Cave is complex and occurs on various timescales that are affected temporally by precipitation patterns and spatially by hydrologic connection with the overlying Minnelusa aquifer of the Minnelusa Formation.

South Dakota↗

Soil and soil solution chemistry under red spruce stands across the northeastern united states

Red spruce ecosystems in the northeastern United States are of interest because this species is undergoing regional decline. Their underlying soils have been examined closely at only a few sites, and information available on red spruce soils throughout this region is limited.This study was conducted to examine soil and soil solution chemistry at red spruce sites in the northeastern US that encompass the range of soil conditions in which red spruce grow. Soils and soil solutions from Oa and B horizons were obtained over a 2-year period from 12 undisturbed red spruce forests (elevations of 80-975 m) in New York, Vermont, New Hampshire, and Maine. All sites had extremely acid Spodosols (Oa soil pH range 2.56 to 3.11 in 0.01 M CaCl2), with generally low concentrations of base cations and high concentrations of Al on soil exchange sites. There was considerable range in exchange chemistry across the sites, however, with exchangeable Ca in Oa horizons ranging from 2.1 to 21.6 cmolckg-1 and exchangeable Al from 3.6 to 18.3 cmolckg-1. Solution chemistry had high concentrations of DOC in the Oa horizons (1160-15200 ??mol L-1), with higher concentrations in the fall than in the spring, which was probably a reflection of fresh litter inputs. Despite high concentrations of DOC in all solutions, inorganic Al was found in some Oa solutions at concentrations as high as 26 ??mol L-1. Ratios of Ca2+ to inorganic Al concentraturns were less than 1.0 in the Oa horizon of one site, and were well below 1.0 in B horizons of all sites. That soil chemistry was related to soil solution chemistry was demonstrated by solution Al concentrations in the forest floor having significant relationships with pyrophosphate extractable Al, although it was not related in the B horizon. Soil exchangeable Ca/Al ratios in the Oa horizon explained 75% of the variation in solution Ca2+/inorganic Al ratios when mean values were used for each site. Our studies have expanded the range of soil chemical conditions measured for red spruce soils. By characterizing the regional variability, these results will enable site intensive process studies to be better applied to regional problems such as spruce decline.

Soil Science↗

The association of water chemistry variables and fish condition in streams of Shenandoah National Park (USA)

As part of the “Shenandoah National Park: Fish in Sensitive Habitats” (SNP:FISH) project, the blacknose dace ( Rhinichthys atratulus ) was utilized as an indicator species to assess the susceptibility of the ichthyofaunal community of Shenandoah National Park (USA) to acidification. Water chemistry (ANC, conductivity, pH, and concentrations of Ca 2+ , Mg 2+ , Na + , K + , Cl − , NO 3 − , SO 4 2− , and SiO 2 ) was sampled every three months over the course of 3 1/4 years which represents the probable maximum lifetime of R atratulus. Condition factors (K=[g/mm 3 ] * 10 6 ) were calculated for samples of fish (age class 2+ yr; n=370) from nine montane, second/third order streams representing a range of ANCs. A principle components regression was performed on factor scores from a principle components analysis of the water chemistry variables and fish condition factor. Two factors, one associated with stream water ANC and ion concentrations, and another associated with SO 4 2− concentration, collectively explained 84% of the variance in condition factor. The influence of variables other than water chemistry upon R atratulus K is addressed. The results show that environmental chemistry is highly associated with the K of R atratulus.

Shenandoah National Park↗

Soil chemistry in lithologically diverse datasets: the quartz dilution effect

National- and continental-scale soil geochemical datasets are likely to move our understanding of broad soil geochemistry patterns forward significantly. Patterns of chemistry and mineralogy delineated from these datasets are strongly influenced by the composition of the soil parent material, which itself is largely a function of lithology and particle size sorting. Such controls present a challenge by obscuring subtler patterns arising from subsequent pedogenic processes. Here the effect of quartz concentration is examined in moist-climate soils from a pilot dataset of the North American Soil Geochemical Landscapes Project. Due to variable and high quartz contents (6.2&ndash;81.7 wt.%), and its residual and inert nature in soil, quartz is demonstrated to influence broad patterns in soil chemistry. A dilution effect is observed whereby concentrations of various elements are significantly and strongly negatively correlated with quartz. Quartz content drives artificial positive correlations between concentrations of some elements and obscures negative correlations between others. Unadjusted soil data show the highly mobile base cations Ca, Mg, and Na to be often strongly positively correlated with intermediately mobile Al or Fe, and generally uncorrelated with the relatively immobile high-field-strength elements (HFS) Ti and Nb. Both patterns are contrary to broad expectations for soils being weathered and leached. After transforming bulk soil chemistry to a quartz-free basis, the base cations are generally uncorrelated with Al and Fe, and negative correlations generally emerge with the HFS elements. Quartz-free element data may be a useful tool for elucidating patterns of weathering or parent-material chemistry in large soil datasets.

Applied Geochemistry↗

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↗

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13 C and 18 O isotopes bound to each other within carbonate minerals in 13 C 18 O 16 O 2 2- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13 C- 18 O bond ordering (Δ 47 ) and δ 18 O of CO 3 2- and HCO 3 - molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13 C- 18 O bond abundances and δ 18 O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ 47 and δ 18 O compositions of CO 3 2- and HCO 3- ions are significantly different from each other. Experiments constrain the Δ 47- δ 18 O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ 47- δ 18 O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ 47 and δ 18 O are intermediate between HCO 3 − and CO 3 2− . We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ 47 and δ 18 O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ 18 O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO 3 − ) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO 3 - dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Geochimica et Cosmochimica Acta↗