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USGS2009

The potential of mid- and near-infrared diffuse reflectance spectroscopy for determining major- and trace-element concentrations in soils from a geochemical survey of North America

In 2004, soils were collected at 220 sites along two transects across the USA and Canada as a pilot study for a planned soil geochemical survey of North America (North American Soil Geochemical Landscapes Project). The objective of the current study was to examine the potential of diffuse reflectance (DR) Fourier Transform (FT) mid-infrared (mid-IR) and near-infrared (NIRS) spectroscopy to reduce the need for conventional analysis for the determination of major and trace elements in such continental-scale surveys. Soil samples (n = 720) were collected from two transects (east-west across the USA, and north-south from Manitoba, Canada to El Paso, Texas (USA), n = 453 and 267, respectively). The samples came from 19 USA states and the province of Manitoba in Canada. They represented 31 types of land use (e.g., national forest, rangeland, etc.), and 123 different land covers (e.g., soybeans, oak forest, etc.). The samples represented a combination of depth-based sampling (0-5 cm) and horizon-based sampling (O, A and C horizons) with 123 different depths identified. The set was very diverse with few samples similar in land use, land cover, etc. All samples were analyzed by conventional means for the near-total concentration of 49 analytes (C total , C carbonate and C organic , and 46 major and trace elements). Spectra were obtained using dried, ground samples using a Digilab FTS-7000 FT spectrometer in the mid- (4000-400 cm -1 ) and near-infrared (10,000-4000 cm -1 ) at 4 cm -1 resolution (64 co-added scans per spectrum) using a Pike AutoDIFF DR autosampler. Partial least squares calibrations were develop using: (1) all samples as a calibration set; (2) samples evenly divided into calibration and validation sets based on spectral diversity; and (3) samples divided to have matching analyte concentrations in calibration and validation sets. In general, results supported the conclusion that neither mid-IR nor NIRS would be particularly useful in reducing the need for conventional analysis of soils from this continental-scale geochemical survey. The extreme sample diversity, likely caused by the widely varied parent material, land use at the site of collection (e.g., grazing, recreation, agriculture, etc.), and climate resulted in poor calibrations even for C total , C organic and C carbonate . The results indicated potential for mid-IR and NIRS to differentiate soils containing high concentrations (>100 mg/kg) of some metals (e.g., Co, Cr, Ni) from low-level samples (<50 mg/kg). However, because of the small number of high-level samples, it is possible that differentiation was based on factors other than metal concentration. Results for Mg and Sr were good, but results for other metals examined were fair to poor, at best. In essence, it appears that the great variation in chemical and physical properties seen in soils from this continental-scale survey resulted in each sample being virtually unique. Thus, suitable spectroscopic calibrations were generally not possible.

Applied Geochemistry↗

USGS2015

Comparing activated alumina with indigenous laterite and bauxite as potential sorbents for removing fluoride from drinking water in Ghana

Fluoride is considered beneficial to teeth and bones when consumed in low concentrations, but at elevated concentrations it can cause dental and skeletal fluorosis. Most fluoride-related health problems occur in poor, rural communities of the developing world where groundwater fluoride concentrations are high and the primary sources of drinking water are from community hand-pump borehole drilled wells. One solution to drinking high fluoride water is to attach a simple de-fluoridation filter to the hand-pump; and indigenous materials have been recommended as low-cost sorbents for use in these filters. In an effort to develop an effective, inexpensive, and low-maintenance de-fluoridation filter for a high fluoride region in rural northern Ghana, this study conducted batch fluoride adsorption experiments and potentiometric titrations to investigate the effectiveness of indigenous laterite and bauxite as sorbents for fluoride removal. It also determined the physical and chemical properties of each sorbent. Their properties and the experimental results, including fluoride adsorption capacity, were then compared to those of activated alumina, which has been identified as a good sorbent for removing fluoride from drinking water. The results indicate that, of the three sorbents, bauxite has the highest fluoride adsorption capacity per unit area, but is limited by a low specific surface area. When considering fluoride adsorption per unit weight, activated alumina has the highest fluoride adsorption capacity because of its high specific surface area. Activated alumina also adsorbs fluoride well in a wider pH range than bauxite, and particularly laterite. The differences in adsorption capacity are largely due to surface area, pore size, and mineralogy of the sorbent.

Applied Geochemistry↗

USGS2020

Natural attenuation can lead to environmental resilience in mine environment

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and “green rust”), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants ( Phragmites australis and Juncus acutus ) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate) The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favoring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions.

Sardinia↗

USGS2016

Soil microbial community profiles and functional diversity in limestone cedar glades

Rock outcrop ecosystems, such as limestone cedar glades (LCGs), are known for their rare and endemic plant species adapted to high levels of abiotic stress. Soils in LCGs are thin (< 25 cm), soil-moisture conditions fluctuate seasonally between xeric and saturated, and summer soil temperatures commonly exceed 48 °C. The effects of these stressors on soil microbial communities (SMC) remain largely unstudied, despite the importance of SMC-plant interactions in regulating the structure and function of terrestrial ecosystems. SMC profiles and functional diversity were characterized in LCGs using community level physiological profiling (CLPP) and plate-dilution frequency assays (PDFA). Most-probable number (MPN) estimates and microbial substrate-utilization diversity (H) were positively related to soil thickness, soil organic matter (OM), soil water content, and vegetation density, and were diminished in alkaline soil relative to circumneutral soil. Soil nitrate showed no relationship to SMCs, suggesting lack of N-limitation. Canonical correlation analysis indicated strong correlations between microbial CLPP patterns and several physical and chemical properties of soil, primarily temperature at the ground surface and at 4-cm depth, and secondarily soil-water content, enabling differentiation by season. Thus, it was demonstrated that several well-described abiotic determinants of plant community structure in this ecosystem are also reflected in SMC profiles.

Tennessee↗

USGS2014

Carbon and geochemical properties of cryosols on the North Slope of Alaska

Cryosols contain roughly 1700 Gt of Soil organic carbon (SOC) roughly double the carbon content of the atmosphere. As global temperature rises and permafrost thaws, this carbon reservoir becomes vulnerable to microbial decomposition, resulting in greenhouse gas emissions that will amplify anthropogenic warming. Improving our understanding of carbon dynamics in thawing permafrost requires more data on carbon and nitrogen content, soil physical and chemical properties and substrate quality in cryosols. We analyzed five permafrost cores obtained from the North Slope of Alaska during the summer of 2009. The relationship between SOC and soil bulk density can be adequately represented by a logarithmic function. Gas fluxes at − 5 °C and 5 °C were measured to calculate the temperature response quotient (Q 10 ). Q 10 and the respiration per unit soil C were higher in permafrost-affected soils than that in the active layer, suggesting that decomposition and heterotrophic respiration in cryosols may contribute more to global warming.

Alaska↗

USGS2004

Mars chronology: Assessing techniques for quantifying surficial processes

Currently, the absolute chronology of Martian rocks, deposits and events is based mainly on crater counting and remains highly imprecise with epoch boundary uncertainties in excess of 2 billion years. Answers to key questions concerning the comparative origin and evolution of Mars and Earth will not be forthcoming without a rigid Martian chronology, enabling the construction of a time scale comparable to Earth's. Priorities for exploration include calibration of the cratering rate, dating major volcanic and fluvial events and establishing chronology of the polar layered deposits. If extinct and/or extant life is discovered, the chronology of the biosphere will be of paramount importance. Many radiometric and cosmogenic techniques applicable on Earth and the Moon will apply to Mars after certain baselines (e.g. composition of the atmosphere, trace species, chemical and physical characteristics of Martian dust) are established. The high radiation regime may pose a problem for dosimetry-based techniques (e.g. luminescence). The unique isotopic composition of nitrogen in the Martian atmosphere may permit a Mars-specific chronometer for tracing the time-evolution of the atmosphere and of lithic phases with trapped atmospheric gases. Other Mars-specific chronometers include measurement of gas fluxes and accumulation of platinum group elements (PGE) in the regolith. Putting collected samples into geologic context is deemed essential, as is using multiple techniques on multiple samples. If in situ measurements are restricted to a single technique it must be shown to give consistent results on multiple samples, but in all cases, using two or more techniques (e.g. on the same lander) will reduce error. While there is no question that returned samples will yield the best ages, in situ techniques have the potential to be flown on multiple missions providing a larger data set and broader context in which to place the more accurate dates. ?? 2004 Elsevier B.V. All rights reserved.

Earth-Science Reviews↗

USGS2014

Wildland fire ash: Production, composition and eco-hydro-geomorphic effects

Fire transforms fuels (i.e. biomass, necromass, soil organic matter) into materials with different chemical and physical properties. One of these materials is ash, which is the particulate residue remaining or deposited on the ground that consists of mineral materials and charred organic components. The quantity and characteristics of ash produced during a wildland fire depend mainly on (1) the total burned fuel (i.e. fuel load), (2) fuel type and (3) its combustion completeness. For a given fuel load and type, a higher combustion completeness will reduce the ash organic carbon content, increasing the relative mineral content, and hence reducing total mass of ash produced. The homogeneity and thickness of the ash layer can vary substantially in space and time and reported average thicknesses range from close to 0 to 50 mm. Ash is a highly mobile material that, after its deposition, may be incorporated into the soil profile, redistributed or removed from a burned site within days or weeks by wind and water erosion to surface depressions, footslopes, streams, lakes, reservoirs and, potentially, into marine deposits. Research on the composition, properties and effects of ash on the burned ecosystem has been conducted on material collected in the field after wildland and prescribed fires as well as on material produced in the laboratory. At low combustion completeness (typically T < 450 °C), ash is organic-rich, with organic carbon as the main component. At high combustion completeness (T > 450 °C), most organic carbon is volatized and the remaining mineral ash has elevated pH when in solution. It is composed mainly of calcium, magnesium, sodium, potassium, silicon and phosphorous in the form of inorganic carbonates, whereas at T > 580 °C the most common forms are oxides. Ash produced under lower combustion completeness is usually darker, coarser, and less dense and has a higher saturated hydraulic conductivity than ash with higher combustion completeness, although physical reactions with CO 2 and when moistened produce further changes in ash characteristics. As a new material present after a wildland fire, ash can have profound effects on ecosystems. It affects biogeochemical cycles, including the C cycle, not only within the burned area, but also globally. Ash incorporated into the soil increases temporarily soil pH and nutrient pools and changes physical properties such as albedo, soil texture and hydraulic properties including water repellency. Ash modifies soil hydrologic behavior by creating a two-layer system: the soil and the ash layer, which can function in different ways depending on (1) ash depth and type, (2) soil type and (3) rainfall characteristics. Key parameters are the ash's water holding capacity, hydraulic conductivity and its potential to clog soil pores. Runoff from burned areas carries soluble nutrients contained in ash, which can lead to problems for potable water supplies. Ash deposition also stimulates soil microbial activity and vegetation growth. Further work is needed to (1) standardize methods for investigating ash and its effects on the ecosystem, (2) characterize ash properties for specific ecosystems and wildland fire types, (3) determine the effects of ash on human and ecosystem health, especially when transported by wind or water, (4) investigate ash's controls on water and soil losses at slope and catchment scales, (5) examine its role in the C cycle, and (6) study its redistribution and fate in the environment.

Earth-Science Reviews↗

USGS2022

Divergent successional trajectories of soil seed bank and post-fire vegetation in a semiarid oak forest: Implications for post-fire ecological restoration

Wildfires are a major disturbance in forest ecosystems around the world and may lead to changes in vegetation succession trajectories. This study examined the impact of time since wildfires on the successional gradients of the degraded Zagros semi-arid oak forest in Iran. Here, we investigated the role of soil seed bank in postfire understory vegetation successional trajectories after wildfires and how time-since-fire influenced plant recovery of this disturbed site. Three adjacent high severity burned areas with different fire histories and the same physiographic conditions were considered. In sampling, we surveyed both aboveground understory vegetation and soil seed bank in all the 96 plots taken along the transects of each area. Soil samples were also collected from each plot and physicochemical properties were analysed in the laboratory. Species composition in the seed bank showed divergent successional trajectories compared to the aboveground vegetation after wildfire. The diversity of soil seed banks followed a gradual decrease, while aboveground understory plants revealed an increasing trend of diversity over time. In addition, the physical and chemical composition of soils was significantly altered by fire. This study presents important insights into soil seed bank dynamics compared to the corresponding aboveground vegetation during postfire succession. The observed changes in diversity and vegetation composition after wildfire can give important insights to management strategies involving prescribed fire in the restoration efforts of highly disturbed semiarid oak forest.

Ecological Engineering↗

USGS2010

Development of a macrophyte-based index of biotic integrity for Minnesota lakes

Traditional approaches for managing aquatic resources have often failed to account for effects of anthropogenic disturbances on biota that are not directly reflected by chemical and physical proxies of environmental condition. The index of biotic integrity (IBI) is a potentially effective assessment method to integrate ecological, functional, and structural aspects of aquatic systems. A macrophyte-based IBI was developed for Minnesota lakes to assess the ability of aquatic plant communities to indicate environmental condition. The index was developed using quantitative point intercept vegetation surveys for 97 lakes that represent a range of limnological and watershed characteristics. We followed an approach similar to that used in Wisconsin to develop the aquatic macrophyte community index (AMCI). Regional adaptation of the AMCI required the identification of species representative of macrophyte communities in Minnesota. Metrics and scaling methods were also substantially modified to produce a more empirically robust index. Regression analyses indicated that IBI scores reflected statewide differences in lake trophic state (R2 = 0.57, F = 130.3, df = 1, 95, p < 0.005), agricultural (R2 = 0.51, F = 83.0, df = 1, 79, p < 0.005), urban (R2 = 0.22, F = 23.0, df = 1, 79, p < 0.005), and forested land uses (R2 = 0.51, F = 84.7, df = 1, 79, p < 0.005), and county population density (R2 = 0.14, F = 16.6, df = 1, 95, p < 0.005). Variance partitioning analyses using multiple regression models indicated a unique response of the IBI to human-induced stress separate from a response to natural lake characteristics. The IBI was minimally affected by differences in sample point density as indicated by Monte Carlo analyses of reduced sampling effort. Our analysis indicates that a macrophyte IBI calibrated for Minnesota lakes could be useful for identifying differences in environmental condition attributed to human-induced stress gradients. ?? 2010 Elsevier Ltd.

Ecological Indicators↗

USGS2019

Slough evolution and legacy mercury remobilization induced by wetland restoration in South San Francisco Bay

Coastal wetlands have a long history of degradation and destruction due to human development. Now recognized as one of the most productive ecosystems in the world, substantial efforts are being made to restore this critical habitat. While wetland restoration efforts are generally viewed as beneficial in terms of providing wildlife habitat and flood control, they are often accompanied by dramatic physical and chemical changes that may result in unintended consequences, which are rarely studied. Alviso Slough, a tidal slough in South San Francisco Bay, California, is the site of an ongoing effort to restore former salt-production ponds to intertidal marsh habitat. Restoration is complicated by the fact that (1) the ponds undergoing restoration are severely subsided and (2) subsurface sediments within the slough and surrounding ponds are contaminated with legacy mercury deposits. Due to concerns regarding mercury remobilization, restoration has proceeded in a cautious, methodical manner. To assess the amount of legacy mercury remobilized since restoration began, we developed a technique of combining high-resolution, biannual measurements of bathymetric scour with mercury concentration measurements from sediment cores. We estimate that 52 kg (±3) of mercury was remobilized in the 6 years since restoration began. Net bathymetric change analyses revealed seasonal trends of peak erosion during the winter months and little to no net change during summer months. Our analyses provide crucial insight on the spatial and temporal scales of geomorphic evolution within a tidal slough resulting from both natural (seasonal) variability and restoration actions. The technique presented here could be applied to other study sites and various sediment-associated contaminants of concern to aid in the design and management of restoration projects aiming to minimize negative impacts from legacy contaminants.

California↗

USGS2019

Assessment of the potential for in-plume sulphur dioxide gas-ash interactions to influence the respiratory toxicity of volcanic ash

Background Volcanic plumes are complex environments composed of gases and ash particles, where chemical and physical processes occur at different temperature and compositional regimes. Commonly, soluble sulphate- and chloride-bearing salts are formed on ash as gases interact with ash surfaces. Exposure to respirable volcanic ash following an eruption is potentially a significant health concern. The impact of such gas-ash interactions on ash toxicity is wholly un-investigated. Here, we study, for the first time, whether the interaction of volcanic particles with sulphur dioxide (SO 2 ) gas, and the resulting presence of sulphate salt deposits on particle surfaces, influences toxicity to the respiratory system, using an advanced in vitro approach. Methods To emplace surface sulphate salts on particles, via replication of the physicochemical reactions that occur between pristine ash surfaces and volcanic gas, analogue substrates (powdered synthetic volcanic glass and natural pumice) were exposed to SO 2 at 500 °C, in a novel Advanced Gas-Ash Reactor, resulting in salt-laden particles. The solubility of surface salt deposits was then assessed by leaching in water and geochemical modelling. A human multicellular lung model was exposed to aerosolised salt-laden and pristine (salt-free) particles, and incubated for 24 h. Cell cultures were subsequently assessed for biological endpoints, including cytotoxicity (lactate dehydrogenase release), oxidative stress (oxidative stress-related gene expression; heme oxygenase 1 and NAD(P)H dehydrogenase [quinone] 1) and its (pro-)inflammatory response (tumour necrosis factor α, interleukin 8 and interleukin 1β at gene and protein levels). Results In the lung cell model no significant effects were observed between the pristine and SO 2 -exposed particles, indicating that the surface salt deposits, and the underlying alterations to the substrate, do not cause acute adverse effects in vitro . Based on the leachate data, the majority of the sulphate salts from the ash surfaces are likely to dissolve in the lungs prior to cellular uptake. Conclusions The findings of this study indicate that interaction of volcanic ash with SO 2 during ash generation and transport does not significantly affect the respiratory toxicity of volcanic ash in vitro . Therefore, sulphate salts are unlikely a dominant factor controlling variability in in vitro toxicity assessments observed during previous eruption response efforts.

Environmental Research↗

USGS2024

Design and calibration of a nitrate decision support tool for groundwater wells in Wisconsin, USA

This paper describes development of a nitrate decision support tool for groundwater wells (GW-NDST) that combines nitrate leaching and groundwater lag-times to compute well concentrations. The GW-NDST uses output from support models that simulate leached nitrate, groundwater age distributions, and nitrate reduction rates. The support models are linked through convolution to simulate nitrate transport to wells. Spatially distributed parameters were adjusted through calibration to 34,255 nitrate sample targets. Prediction uncertainty is illustrated via Monte Carlo realizations informed during calibration. Over 78% of target concentrations were within the simulated range of results from 450 realizations. An example forecasting scenario illustrates that a range of feasible outcomes exist and should be considered when interpreting forecasts for decision making. Uncertainty in forecasting is unavoidable; the intent of characterizing uncertainty in the GW-NDST is to facilitate decision making by increasing insight into the response of nitrate contamination to physical and chemical processes.

Wisconsin↗

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↗

USGS2004

Massive sulfide deposition and trace element remobilization in the Middle Valley sediment-hosted hydrothermal system, northern Juan de Fuca Rdge

The Bent Hill massive sulfide deposit and ODP Mound deposit in Middle Valley at the northernmost end of the Juan de Fuca Ridge are two of the largest modern seafloor hydrothermal deposits yet explored. Trace metal concentrations of sulfide minerals, determined by laser-ablation ICP-MS, were used in conjunction with mineral paragenetic studies and thermodynamic calculations to deduce the history of fluid-mineral reactions during sulfide deposition. Detailed analyses of the distribution of metals in sulfides indicate significant shifts in the physical and chemical conditions responsible for the trace element variability observed in these sulfide deposits. Trace elements (Mn, Co, Ni, As, Se, Ag, Cd, Sb, Pb, and Bi) analyzed in a representative suite of 10 thin sections from these deposits suggest differences in conditions and processes of hydrothermal alteration resulting in mass transfer of metals from the center of the deposits to the margins. Enrichments of some trace metals (Pb, Sb, Cd, Ag) in sphalerite at the margins of the deposits are best explained by dissolution/reprecipitation processes consistent with secondary remineralization. Results of reaction-path models clarify mechanisms of mass transfer during remineralization of sulfide deposits due to mixing of hydrothermal fluids with seawater. Model results are consistent with patterns of observed mineral paragenesis and help to identify conditions (pH, redox, temperature) that may be responsible for variations in trace metal concentrations in primary and secondary minerals. Differences in trace metal distributions throughout a single deposit and between nearby deposits at Middle Valley can be linked to the history of metal mobilization within this active hydrothermal system that may have broad implications for sulfide ore formation in other sedimented and unsedimented ridge systems. ?? 2004 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2014

Modeling the influence of organic acids on soil weathering

Biological inputs and organic matter cycling have long been regarded as important factors in the physical and chemical development of soils. In particular, the extent to which low molecular weight organic acids, such as oxalate, influence geochemical reactions has been widely studied. Although the effects of organic acids are diverse, there is strong evidence that organic acids accelerate the dissolution of some minerals. However, the influence of organic acids at the field-scale and over the timescales of soil development has not been evaluated in detail. In this study, a reactive-transport model of soil chemical weathering and pedogenic development was used to quantify the extent to which organic acid cycling controls mineral dissolution rates and long-term patterns of chemical weathering. Specifically, oxalic acid was added to simulations of soil development to investigate a well-studied chronosequence of soils near Santa Cruz, CA. The model formulation includes organic acid input, transport, decomposition, organic-metal aqueous complexation and mineral surface complexation in various combinations. Results suggest that although organic acid reactions accelerate mineral dissolution rates near the soil surface, the net response is an overall decrease in chemical weathering. Model results demonstrate the importance of organic acid input concentrations, fluid flow, decomposition and secondary mineral precipitation rates on the evolution of mineral weathering fronts. In particular, model soil profile evolution is sensitive to kaolinite precipitation and oxalate decomposition rates. The soil profile-scale modeling presented here provides insights into the influence of organic carbon cycling on soil weathering and pedogenesis and supports the need for further field-scale measurements of the flux and speciation of reactive organic compounds.

California↗

USGS2017

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

e of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (lXAS) approach is developed and applied to rotosonic drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s lXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity observed in the distribution of elevated-As wells.

Geochimica et Cosmochimica Acta↗

USGS2022

Small anthropogenic landforms from past charcoal production control moisture dynamics and chemistry in northcentral Appalachian soils

Throughout the northeastern United States (U.S.) and Europe, relict charcoal hearths (RCHs) are regularly being discovered in proximity to furnaces once used for the extraction of metal from ore or quick-lime production; charcoal produced in hearths was used as a furnace fuel. Given previous research has shown that topographic and subsurface disturbance can be great when a hearth is constructed, we hypothesize that hearth construction alters surface hydrology and soil chemistry in environments in and near hearths. We used a landscape classification process to identify 6,758 hearths near furnaces at Greenwood and Pine Grove Furnace State Park, central and southcentral Pennsylvania, U.S. Two types of digital elevation model wetness indexes were used to quantify surface hydrology effects in and around hearths. Modeled wetness conditions were compared to field soil volumetric water content in RCHs near Greenwood Furnace State Park. Modeled wetness indexes indicate that RCH interiors are significantly wetter than RCH rim areas; RCHs are acting as a landscape moisture sink. Results also indicate that RCHs on slopes result in downslope drier conditions below RCHs. Field measured volumetric water content indicates that as distance from the center of the hearth increases, soil moisture significantly decreases. Geomorphic position was found to not be related to RCH wetness. Soil from RCHs, compared to nearby native soils, has significantly higher total C, a lower Mehlich 3 extractable acidity, higher Ca and P. No trend was evident with RCH soil chemistry and geomorphic position. The high frequency of RCH occurrence, in proximity to the furnace’s RCHs supported, suggests that RCHs today could locally be an important niche for understory flora and fauna. Further research could explore how RCHs might be affecting surrounding plant populations and how within RCH patterns, especially on hillslopes, might represent a distinctly different scale of physical and chemical variability.

Pennsylvania↗

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↗