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USGS2021

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↗

USGS2007

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in δ 65 Cu (− 1.41 to + 0.30‰), δ 56 Fe (− 0.56 to + 0.34‰), and δ 66 Zn (0.31 to 0.49‰) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Chemical Geology↗

USGS2010

River solute fluxes reflecting active hydrothermal chemical weathering of the Yellowstone Plateau Volcanic Field, USA

In the past few decades numerous studies have quantified the load of dissolved solids in large rivers to determine chemical weathering rates in orogenic belts and volcanic areas, mainly motivated by the notion that over timescales greater than ~100kyr, silicate hydrolysis may be the dominant sink for atmospheric CO2, thus creating a feedback between climate and weathering. Here, we report the results of a detailed study during water year 2007 (October 1, 2006 to September 30, 2007) in the major rivers of the Yellowstone Plateau Volcanic Field (YPVF) which hosts Earth's largest "restless" caldera and over 10,000 thermal features. The chemical compositions of rivers that drain thermal areas in the YPVF differ significantly from the compositions of rivers that drain non-thermal areas. There are large seasonal variations in river chemistry and solute flux, which increases with increasing water discharge. The river chemistry and discharge data collected periodically over an entire year allow us to constrain the annual solute fluxes and to distinguish between low-temperature weathering and hydrothermal flux components. The TDS flux from Yellowstone Caldera in water year 2007 was 93t/km2/year. Extensive magma degassing and hydrothermal interaction with rocks accounts for at least 82% of this TDS flux, 83% of the cation flux and 72% of the HCO3- flux. The low-temperature chemical weathering rate (17t/km2/year), calculated on the assumption that all the Cl- is of thermal origin, could include a component from low-temperature hydrolysis reactions induced by CO2 ascending from depth rather than by atmospheric CO2. Although this uncertainty remains, the calculated low-temperature weathering rate of the young rhyolitic rocks in the Yellowstone Caldera is comparable to the world average of large watersheds that drain also more soluble carbonates and evaporates but is slightly lower than calculated rates in other, less-silicic volcanic regions. Long-term average fluxes at Yellowstone are likely ~20% higher than those in the abnormally dry water year 2007, but the protocol used in this study can be easily adaptable to track future changes in low-temperature weathering and hydrothermal flux components, which could provide better monitoring of magmatic unrest. ?? 2010.

Chemical Geology↗

USGS2009

Effects of coal storage in air on physical and chemical properties of coal and on gas adsorption

This paper investigates changes in the high-volatile bituminous Lower Block Coal Member from Indiana owing to moisture availability and oxidation in air at ambient pressure and temperature over storage time. Specifically, it investigates changes in chemistry, in surface area, and pore structure, as well as changes in methane and carbon dioxide adsorption capacities. Our results document that the methane adsorption capacity increased by 40%, whereas CO 2 adsorption capacity increased by 18% during a 13-month time period. These changes in adsorption are accompanied by changes in chemistry and surface area of the coal. The observed changes in adsorption capacity indicate that special care must be taken when collecting samples and preserving coals until adsorption characteristics are measured in the laboratory. High-pressure isotherms from partially dried coal samples would likely cause overestimation of gas adsorption capacities, lead to a miscalculation of coal-bed methane prospects, and provide deceptively optimistic prognoses for recovery of coal-bed methane or capture of anthropogenic CO 2 . ?? 2009 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2008

Influence of flow-through and renewal exposures on the toxicity of copper to rainbow trout

We examined changes in water chemistry and copper (Cu) toxicity in three paired renewal and flow-through acute bioassays with rainbow trout (Oncorhynchus mykiss). Test exposure methodology influenced both exposure water chemistry and measured Cu toxicity. Ammonia and organic carbon concentrations were higher and the fraction of dissolved Cu lower in renewal tests than in paired flow-through tests. Cu toxicity was also lower in renewal tests; 96 h dissolved Cu LC50 values were 7-60% higher than LC50s from matching flow-through tests. LC50 values in both types of tests were related to dissolved organic carbon (DOC) concentrations in exposure tanks. Increases in organic carbon concentrations in renewal tests were associated with reduced Cu toxicity, likely as a result of the lower bioavailability of Cu-organic carbon complexes. The biotic ligand model of acute Cu toxicity tended to underpredict toxicity in the presence of DOC. Model fits between predicted and observed toxicity were improved by assuming that only 50% of the measured DOC was reactive, and that this reactive fraction was present as fulvic acid. ?? 2007 Elsevier Inc. All rights reserved.

Ecotoxicology and Environmental Safety↗

USGS2009

Impacts of acidification on macroinvertebrate communities in streams of the western Adirondack Mountains, New York, USA

Limited stream chemistry and macroinvertebrate data indicate that acidic deposition has adversely affected benthic macroinvertebrate assemblages in numerous headwater streams of the western Adirondack Mountains of New York. No studies, however, have quantified the effects that acidic deposition and acidification may have had on resident fish and macroinvertebrate communities in streams of the region. As part of the Western Adirondack Stream Survey, water chemistry from 200 streams was sampled five times and macroinvertebrate communities were surveyed once from a subset of 36 streams in the Oswegatchie and Black River Basins during 2003-2005 and evaluated to: (a) document the effects that chronic and episodic acidification have on macroinvertebrate communities across the region, (b) define the relations between acidification and the health of affected species assemblages, and (c) assess indicators and thresholds of biological effects. Concentrations of inorganic Al in 66% of the 200 streams periodically reached concentrations toxic to acid-tolerant biota. A new acid biological assessment profile (acidBAP) index for macroinvertebrates, derived from percent mayfly richness and percent acid-tolerant taxa, was strongly correlated (R2 values range from 0.58 to 0.76) with concentrations of inorganic Al, pH, ANC, and base cation surplus (BCS). The BCS and acidBAP index helped remove confounding influences of natural organic acidity and to redefine acidification-effect thresholds and biological-impact categories. AcidBAP scores indicated that macroinvertebrate communities were moderately or severely impacted by acidification in 44-56% of 36 study streams, however, additional data from randomly selected streams is needed to accurately estimate the true percentage of streams in which macroinvertebrate communities are adversely affected in this, or other, regions. As biologically relevant measures of impacts caused by acidification, both BCS and acidBAP may be useful indicators of ecosystem effects and potential recovery at the local and regional scale.

Ecological Indicators↗

USGS2012

Temporal changes in aquatic-invertebrate and fish assemblages in streams of the north-central and northeastern U.S.

Many management agencies seek to evaluate temporal changes in aquatic assemblages at monitoring sites, but few have sites with ecological time series that are long enough for this purpose. Trends in aquatic-invertebrate and fish assemblage composition were assessed at 27 long-term monitoring sites in the north-central and northeastern United States. Temporal changes were identified using serial trend analysis. Sites with significant serial trends were further evaluated by relating explanatory environmental variables (e.g., streamflow, habitat, and water chemistry) to changes in assemblage composition. Significant trends were found at 19 of 27 study sites; however, differences in the sensitivity of the aquatic fauna to environmental stressors were identified. For example, significant trends in fish assemblages were found at more sites (15 of 27) than for aquatic-invertebrate assemblages (10 of 27 sites). In addition, trends in the invertebrate assemblage were most often explained by changes in streamflow processes (e.g., duration and magnitude of low- and high-flows, streamflow variability, and annual rates of change), whereas trends in the fish assemblage were more related to changes in water chemistry. Results illustrate the value of long-term monitoring for the purpose of assessing temporal trends in aquatic assemblages. The ability to detect trends in assemblage composition and to attribute these changes to environmental factors is necessary to understand mechanistic pathways and to further our understanding of how incremental anthropogenic alterations modify aquatic assemblages over time. Finally, this study's approach to trends analysis can be used to better inform the design of monitoring programs as well as support the ongoing management needs of stakeholders, water-resource agencies, and policy makers.

Connecticut, Illinois, Indiana, Iowa, Massachusett↗

USGS2014

Evaluating the efficiency of environmental monitoring programs

Statistical uncertainty analyses can be used to improve the efficiency of environmental monitoring, allowing sampling designs to maximize information gained relative to resources required for data collection and analysis. In this paper, we illustrate four methods of data analysis appropriate to four types of environmental monitoring designs. To analyze a long-term record from a single site, we applied a general linear model to weekly stream chemistry data at Biscuit Brook, NY, to simulate the effects of reducing sampling effort and to evaluate statistical confidence in the detection of change over time. To illustrate a detectable difference analysis, we analyzed a one-time survey of mercury concentrations in loon tissues in lakes in the Adirondack Park, NY, demonstrating the effects of sampling intensity on statistical power and the selection of a resampling interval. To illustrate a bootstrapping method, we analyzed the plot-level sampling intensity of forest inventory at the Hubbard Brook Experimental Forest, NH, to quantify the sampling regime needed to achieve a desired confidence interval. Finally, to analyze time-series data from multiple sites, we assessed the number of lakes and the number of samples per year needed to monitor change over time in Adirondack lake chemistry using a repeated-measures mixed-effects model. Evaluations of time series and synoptic long-term monitoring data can help determine whether sampling should be re-allocated in space or time to optimize the use of financial and human resources.

Ecological Indicators↗

USGS2018

Contaminants of emerging concern presence and adverse effects in fish: A case study in the Laurentian Great Lakes

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of in vitro bioassays (focused on estrogenic activity) and in vivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total in vitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

Environmental Pollution↗

USGS2021

Growth and defense characteristics of whitebark pine (Pinus albicaulis) and lodgepole pine (Pinus contorta var latifolia) in a high-elevation, disturbance-prone mixed-conifer forest in northwestern Montana, USA

Recent, widespread tree mortality in the western U.S. resulting from changes in climate, pathogens, insect activity, and forest management practices has led to concerns for many ecologically and culturally important species. Within conifers, resin-based defenses have long been recognized as a primary defense mechanism against a variety of insects and pathogens. Oleoresin produced by trees contain complex mixtures of terpenoids that have numerous insecticidal and fungicidal properties. Research has also identified links between resin duct characteristics and increased probability of survival during bark beetle outbreaks. Whitebark pine ( Pinus albicaulis ) is a culturally significant high elevation species that provides numerous ecological services within subalpine and alpine ecosystems. Whitebark pine has co-evolved with a suite of biotic and abiotic disturbances. Individual trees allocate resources towards growth and resin-based defenses, making it a good candidate species to evaluate growth and defense relationships and tradeoffs. In this study we compared constitutive resin chemistry, tree growth and resin duct anatomy between similarly aged whitebark and lodgepole pine ( P. contorta var latifolia ) growing in proximity within a disturbance-prone, mixed-conifer forest in northwestern Montana. These two host species have varying degrees of historical exposure to mountain pine beetle. Our research yields four important findings. First, we did not find evidence of a tradeoff between tree growth and tree defenses (resin duct morphology and resin chemistry). This suggests that trees growing under favorable field conditions can experience high growth rates and still allocate ample resources towards defense. Second, we found that resin ducts and constitutive mono- and sesqui- terpenes were not correlated in lodgepole pine while duct production and area were positively related to constitutive monoterpenes, and duct size and area were positively related to constitutive sesquiterpenes, in whitebark pine. The lack of distinct, consistent relationships between these defensive features suggests that both whitebark and lodgepole pine trees present beetles with numerous, complex combinations of resin-based defenses. Third, based on constitutive terpene profiles, bark beetles are more likely to enter lodgepole pine but more likely to successfully elicit mass attacks in whitebark pine, which agrees with beetle attack and success patterns observed in the field. Fourth, overstory competition, particularly by Engelmann spruce ( Picea engelmannii ), can influence tree defenses, specifically by reducing constitutive terpene concentrations in lodgepole and whitebark pine. Competitive tree interactions could lead to altered bark beetle-conifer interactions as host and nonhost species migrate in response to changing climate. Our results suggest that strategies designed to support whitebark pine populations can benefit from better understanding interactions among growth, competition and physical and chemical defenses in response to multiple disturbance.

Montana↗

USGS2008

On the in situ aqueous alteration of soils on Mars

Early (>3 Gy) wetter climate conditions on Mars have been proposed, and it is thus likely that pedogenic processes have occurred there at some point in the past. Soil and rock chemistry of the Martian landing sites were evaluated to test the hypothesis that in situ aqueous alteration and downward movement of solutes have been among the processes that have transformed these portions of the Mars regolith. A geochemical mass balance shows that Martian soils at three landing sites have lost significant quantities of major rock-forming elements and have gained elements that are likely present as soluble ions. The loss of elements is interpreted to have occurred during an earlier stage(s) of weathering that may have been accompanied by the downward transport of weathering products, and the salts are interpreted to be emplaced later in a drier Mars history. Chemical differences exist among the sites, indicating regional differences in soil composition. Shallow soil profile excavations at Gusev crater are consistent with late stage downward migration of salts, implying the presence of small amounts of liquid water even in relatively recent Martian history. While the mechanisms for chemical weathering and salt additions on Mars remain unclear, the soil chemistry appears to record a decline in leaching efficiency. A deep sedimentary exposure at Endurance crater contains complex depth profiles of SO4, Cl, and Br, trends generally consistent with downward aqueous transport accompanied by drying. While no model for the origin of Martian soils can be fully constrained with the currently available data, a pedogenic origin is consistent with observed Martian geology and geochemistry, and provides a testable hypothesis that can be evaluated with present and future data from the Mars surface. ?? 2008 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2011

Geochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea

Processes controlling the composition of seafloor hydrothermal fluids in silicic back-arc or near-arc crustal settings remain poorly constrained despite growing evidence for extensive magmatic–hydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273–285 °C) and major element compositions, low dissolved CO 2 concentrations (4.4 mmol/kg) and high measured pH (4.2–4.9 at 25 °C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358 °C) fluid. All PACMANUS fluids are characterized by negative δ D H 2 O "> δDH 2 O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25 °C) values (∼2.6–2.7), high endmember CO 2 (up to 274 mmol/kg) and negative δ 34 S H 2 S "> δ 34 S H2 S values (down to −2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO 2 at PACMANUS is more enriched in 13 C (−4.1‰ to −2.3‰) than Vienna Woods (−5.2‰ to −5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater ingress into the upflow zone. Consistently high measured Mg concentrations as well as trends of increasingly non-conservative SO 4 behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (⩽80 °C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water–rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones.

Manus Basin↗

USGS2013

DOM composition in an agricultural watershed: assessing patterns and variability in the context of spatial scales

Willow Slough, a seasonally irrigated agricultural watershed in the Sacramento River valley, California, was sampled synoptically in order to investigate the extent to which dissolved organic carbon (DOC) concentrations and compositions from throughout the catchment are represented at the mouth. DOC concentrations ranged from 1.8 to 13.9 mg L −1 , with the lowest values in headwater 1st and 2nd order streams, and the highest values associated with flood irrigation. Carbon-normalized vanillyl phenols varied from 0.05 to 0.67 mg 100 mg OC −1 (0.37 mean), indicative of considerable contributions from vascular plants. DOC concentrations and compositions at the mouth appear to be primarily influenced by land use (agriculture) in the lower reaches, and therefore very little of the headwater chemistry (1st and 2nd order streams) can be discerned from the chemistry at or near the mouth (3rd and 4th order streams), indicating the need for synoptic sampling to capture the breadth of organic carbon cycling within a catchment. Field sampling during irrigation showed the large impact that flood irrigation can have on DOC concentrations and compositions, likely a primary cause of significantly elevated Willow Slough DOC concentrations during the summer irrigation season. Optical proxies exhibited varying degrees of correlation with chemical measurements, with strongest relationships to DOC and dissolved lignin ( r 2 = 0.95 and 0.73, respectively) and weaker relationships to carbon-normalized lignin yields and C:V ( r 2 from 0.31 to 0.42). Demonstrating the importance of matching scale to processes, we found no relationship between dissolved lignin concentrations and total suspended sediments (TSS) across all sites, in contrast to the strong relationship observed in weekly samples at the mouth. As DOC concentrations and compositions at the mouth of Willow Slough are closely tied to anthropogenic activities within the catchment, future changes in land-use driven by climate change, water availability, and economic pressures on crop types will also bring about changes in the overall biogeochemistry.

California↗

USGS2020

Biomarker similarities between the saline lacustrine Eocene Green River and the Paleoproterozoic Barney Creek Formations

The Paleoproterozoic Barney Creek Formation, which is currently interpreted as a restricted, deep marine paleoenvironment, plays a disproportionate role in our understanding of Proterozoic ocean chemistry and the rise of complex life. The Barney Creek Formation hosts several unusual biomarker features, specifically its methylhopane and carotenoid signatures. Herein, we demonstrate that the saline lacustrine Eocene Green River Formation shares a similar distribution of methylhopanes and carotenoids, which is characteristic of saline lacustrine organic matter more generally. These distinct methylhopane and carotenoid patterns are not observed together in marine organic matter of any geologic age. These results imply a saline lacustrine depositional environment for the Barney Creek Formation, which agrees with earlier but now abandoned depositional models of this formation. As a result, models of Proterozoic ocean chemistry and emergence of complex life that rely on a marine Barney Creek Formation should be re-examined. Alternatively, if Paleoproterozoic marine biomarker signatures resemble those of younger saline lacustrine systems, then this must be recognized to accurately interpret geologic biomarker and paleoenvironmental records.

Colorado, Utah↗

USGS2015

Long-term controls of soil organic carbon with depth and time: a case study from the Cowlitz River Chronosequence, WA USA

Over timescales of soil development (millennia), the capacity of soils to stabilize soil organic carbon (SOC) is linked to soil development through changes in soil mineralogy and other soil properties. In this study, an extensive dataset of soil profile chemistry and mineralogy is compiled from the Cowlitz River Chronosequence (CRC), WA USA. The CRC soils range in age from 0.25 to 1200 kyr, spanning a developmental gradient encompassing clear changes in soil mineralogy, chemistry, and surface area. Comparison of these and other metrics of soil development with SOC properties reveal several relationships that may be diagnostic of the long-term coupling of soil development and C cycling. Specifically, SOC content was significantly correlated with sodium pyrophosphate extractable metals emphasizing the relevance of organo-metal complexes in volcanic soils. The depth distributions of organo-metals and other secondary weathering products, including the kaolin and short-range order (SRO) minerals, support the so-called “binary composition” of volcanic soils. The formation of organo-metal complexes limits the accumulation of secondary minerals in shallow soils, whereas in deep soils with lower SOC content, secondary minerals accumulate. In the CRC soils, secondary minerals formed in deep soils (below 50 cm) including smectite, allophane, Fe-oxides and dominated by the kaolin mineral halloysite. The abundance of halloysite was significantly correlated with bulk soil surface area and 14 C content (a proxy for the mean age of SOC), implying enhanced stability of C in deep soils. Allophane, an SRO mineral commonly associated with SOC storage, was not correlated with SOC content or 14 C values in CRC soils. We propose conceptual framework to describe these observations based on a general understanding of pedogenesis in volcanic soils, where SOC cycling is coupled with soil development through the formation of and fate of organo-metal or other mobile weathering products. This framework highlights interactions between SOC and soil development, which may be applicable to other soils where organic inputs interact with the products of chemical weathering.

Washington↗

USGS2023

Soil and geomorphic patterns within relict charcoal hearths could represent unique ecosystem niches

Hearths used for 19th and 20th century charcoal manufacturing have been found to have unique plant communities or to produce unique growth characteristics for some species but not others. Given known differences in hearth morphology, within hearth physical and chemical differences may exist and result in unique ecologic niches. We examined soil stratigraphy across 8 relict charcoal hearths (RCH) and control soils on different landforms near a 19th century furnace complex (Greenwood Furnace, northcentral Appalachians USA). Soils were analyzed for particle size, total and trace elements, and fertility. Platform creation resulted in soils from upslope RCH positions mixed with subsurface materials on the downslope side to create a stabilized platform. The thin, uniform thickness of charcoal surface horizons (Ac) suggests that RCHs were not used more than once for charcoal manufacturing or that charcoal was always removed very efficiently. While rubification of soil or rock from high heat was seen in 6 of 8 sites sampled, it was not extensive across sampled areas of any one hearth, which suggests hearth use may not have frequent, hot enough, or spatially disparate. Soil fertility characteristics change within RCHs but also by landscape position. Downslope RCH positions are enriched in some parameters compared to control soils (total C, Mehlich 3 Mg, Ca, and Aquia Regia digestion Mn) and that enrichment often is from the surface downward. Downslope enrichment within RCH soils may have occurred from charcoal and released ions, slope erosion and accumulation, or transportation of constructed materials during RCH creation. Landscape position may accentuate or mute soil chemistry differences. Greenwood Furnace RCHs have unique patterns of chemistry, which could result in unique niches for flora and maybe fauna within RCH. Future research should more closely investigate whether hearths support unique species assemblages and how they may play a role in enhancing today’s forest biodiversity.

Pennsylvania↗

USGS2015

Targeting Cu–Au and Mo resources using multi-media exploration geochemistry: An example from Tyonek Quadrangle, Alaska Range, Alaska

Regional stream and pond sediment, panned concentrate, and water sampling at and around known mineral occurrences in the Tyonek quadrangle, Alaska Range, Alaska were undertaken to determine geochemical signatures in the different media. For sediment samples, two different size fractions (− 80 mesh and − 230 mesh) were analyzed. Elevated concentrations (mostly ~ 2 × median) of elements such as As, Au, Cd, Cu, Mo, Pb, and/or Zn were measured in both size fractions in streams draining known occurrences as well as from several other locations. Gold, molybdenite, arsenopyrite, and/or Cu minerals identified in panned concentrates explain some of these elevated values. Water samples from most stream, pond and seep sediment sample sites were analyzed by high-resolution ICP-MS methodology. Relative high concentrations of constituents (including Mo, Re, As, Tl, and/or Cu and/or SO 4 ) were commonly measured in waters where high metal concentrations were also measured in corresponding sediments and/or heavy mineral concentrates. However, water chemistry yielded higher contrast of upper quartile and anomalous groups relative to median values than observed in sediments. Elevated As, Mo and/or Re probably relate both to deposit mineralogy and the higher solubility of these metals (compared to that of Cu, Pb, Zn) under the predominantly oxidized and near-neutral pH conditions. Our pilot study indicates that, despite large input of snowmelt and very low absolute concentrations (μg/L), water chemistry can be useful for delineating sulfide-bearing mineral occurrences in this region.

Alaska↗

USGS2018

The isometric log-ratio (ilr)-ion plot: A proposed alternative to the Piper diagram

The Piper diagram has been a staple for the analysis of water chemistry data since its introduction in 1944. It was conceived to be a method for water classification, determination of potential water mixing between end-members, and to aid in the identification of chemical reactions controlling a sample set. This study uses the information gleaned over the years since the release of the Piper diagram and proposes an alternative to it, capturing the strengths of the original diagram while adding new ideas to increase its robustness. The new method uses compositional data analysis to create 4 isometric log-ratio coordinates for the 6 major chemical species analyzed in the Piper diagram and transforms the data to a 4-field bi-plot, the ilr-ion plot. This ilr-ion plot conveys all of the information in the Piper diagram (water mixing, water types, and chemical reactions) while also visualizing additional data, the ability to examine Ca 2+ /Mg 2+ versus Cl-/SO 4 2− . The Piper and the ilr-ion plot were also compared using multiple synthetic and real datasets in order to illustrate the caveats and the advantages of using either diagram to analyze water chemistry data. Although there are challenges with using the ilr-ion plot (e.g., missing or zero values zeros in the dataset must be imputed by positive real numbers), it appears that the use of compositional data analysis coupled with the ilr-ion plot provides a more in-depth and complete analysis of water quality data compared to the original Piper diagram.

Journal of Geochemical Exploration↗