Climate change and a related increase in temperature, particularly in alpine areas, force both flora and fauna to adapt to the new conditions. These changes should in turn affect soil formation processes. The aim of this study was to identify possible consequences for soils in a dry-alpine region with respect to weathering of primary minerals and leaching of elements under expected vegetation and climate changes. To achieve this, a field empirical approach investigating an attitudinal sequence was used in combination with laboratory weathering experiments simulating several scenarios. The study sites are located in Sinks Canyon and Stough Basin of the Wind River Range, Wyoming, USA. The following sites (from moist to dry with increasing temperature along the sequence) were investigated: 10 soil profiles (Typic Haplocryoll) in a tundra ecotone, 10 soil profiles (Ustic Haplocryoll) in a pine-fir forest and 20 soil profiles (Ustic Argicryoll) in sagebrush. All soils developed on granitoid moraines. Soil mineralogy was analysed using cathodoluminescence and X-ray diffraction. This revealed that biotite and plagioclase were both weathered to smectite while plagioclase also weathered to kaolinite. Cooler, wetter, altitude-dependent conditions promoted weathering of primary minerals. Furthermore, the soils of the tundra and forest zone exhibited a higher acidity and more organic carbon.In a series of wet laboratory batch experiments, materials from topsoils (A horizons) and subsoils (B horizons) in each ecotone were examined alone or in combination with other samples. In a first step, aqueous extracts of the topsoil samples were generated in batch reactors and analysed for the main ions. In a second and a third step the topsoil extracts were reacted with the subsoil samples of the same ecotone, and with the subsoil samples of the ecotones at higher altitude. The total duration of these batch experiments was 1800 h, and the solutes were measured using ICP-OES and ion chromatography. Dissolved Ca, Mg and K were mainly controlled by the chemical weathering of oligoclase, K-feldspar and biotite. With increasing altitude the total concentrations of Ca, Mg and K in the aqueous extracts decreased, the relative ionic contribution from K decreased, while the ionic contribution from Ca increased.Climate change (warming, changed precipitation) potentially will reduce weathering intensity, soil acidity and the content of organic carbon. An attitudinal shift in vegetation due to climate change seems to affect the ionic composition of the soil solution. In the case of a shift from forest to sagebrush and tundra to forest or sagebrush, the relative contribution from K would increase at the expense of Ca. We hypothesise that K will play an important role in future biogeochemical cycles under the assumptions of climate warming and subsequent vegetation shifts to higher altitudes. (C) 2015 Elsevier B.V. All rights reserved.

Exotic earthworms are invading forests in North America where native earthworms have been absent since the last glaciation. These earthworms bioturbate soils and may enhance physical interactions between minerals and organic matter (OM), thus affecting mineral sorption of carbon (C) which may affect C cycling. We quantitatively show how OM-mineral sorption and soil C inventories respond to exotic earthworms along an earthworm invasion chronosequence in a sugar maple forest in northern Minnesota. We hypothesized that mineral surface area in A horizons would increase as burrowing earthworms incorporated clay minerals from the B horizons and that enhanced contacts between OM and minerals would increase the OM sorption on mineral surfaces and mineral-associated C inventories in A horizons. Contrary to our hypotheses, mineral surface areas within A horizons were lowered because earthworm burrows only extended into the silt-rich loess that separated the A and clay-rich B horizons. Furthermore, where endogeic earthworms were present, a smaller fraction of mineral surface area was covered with OM. OM sorption on minerals in the A horizons shifted from a limitation of mineral surface availability to a limitation of OM availability within a decade after the arrival of endogeic earthworms. C-mineral sorption depends on earthworm consumption of OM as well as the composition and vertical distribution of minerals. This finding may thus explain the contradictory results reported in earlier investigations. Our results highlight the rapid and drastic effects of exotic earthworms on key ecosystem processes in deciduous forests in post-glacial settings.

Hardwood forests of the Great Lakes Region have evolved without earthworms since the Last Glacial Maximum, but are now being invaded by exotic earthworms introduced through agriculture, fishing, and logging. These exotic earthworms are known to increase soil mixing, affect soil carbon storage, and dramatically alter soil morphology. Here we show, using an active earthworm invasion chronosequence in a hardwood forest in northern Minnesota, that such disturbances by exotic earthworms profoundly affect inorganic nutrient cycles in soils. Soil nutrient elemental concentrations (Ca, Mg, K, and P) were normalized to biogeochemically inert Zr to quantify their losses and gains. This geochemical normalization revealed that elements were highly enriched in the A horizon of pre-invasion soils, suggesting tight biological recycling of the nutrients. In the early stage of invasion, epi-endogeic earthworm species appeared to have been responsible for further enriching the elements in the A horizon possibly by incorporating leaf organic matter (OM). The arrival of geophagous soil mixing endogeic earthworms, however, was associated with near complete losses of these enrichments, which was related to the loss of OM in soils. Our study highlights that elemental concentrations may not be sufficient to quantify biogeochemical effects of earthworms. The geochemical normalization approach, which has been widely used to study soil formation, may help when determining how invasive soil organisms affect soil elemental cycles. More generally, this approach has potential for much wider use in studies of belowground nutrient dynamics. The results support the existing ecological literature demonstrating that invasive earthworms may ultimately reduce productivity in formerly glaciated forests under climate change.

Release of arsenic (As) from sedimentary rocks has resulted in contamination of groundwater in aquifers of the New Jersey Piedmont Physiographic Province, USA; the contamination also may affect the quality of the region's streamwater to which groundwater discharges. Biogeochemical mechanisms involved in the release process were investigated in the streambeds of Six Mile Run and Pike Run, tributaries to the Millstone River in the Piedmont. At Six Mile Run, streambed pore water and shallow groundwater were low or depleted in oxygen, and contained As at concentrations greater than 20 mu g/L. At Pike Run, oxidizing conditions were present in the streambed, and the As concentration in pore water was 2.1 mu g/L. The 16S rRNA gene and the As(V) respiratory reductase gene, arrA, were amplified from DNA extracted from streambed pore water at both sites and analyzed, revealing that distinct bacterial communities that corresponded to the redox conditions were present at each site. Anaerobic enrichment cultures were inoculated with pore water from gaining reaches of the streams with acetate and As(V). As(V) was reduced by microbes to As(III) in enrichments with Six Mile Run pore water and groundwater, whereas no reduction occurred in enrichments with Pike Run pore water. Cloning and sequencing of the arrA gene indicated 8 unique operational taxonomic units (OTUs) at Six Mile Run and 11 unique OTUs at Pike Run, which may be representative of the arsenite oxidase gene arxA. Low-oxygen conditions at Six Mile Run have favored microbial As reduction and release, whereas release was inhibited by oxidizing conditions at Pike Run. Published by Elsevier B.V.

(1) Department of Earth Sciences, Natural History Museum, Cromwell Road, London SW7 5BD, U.K., (2) Institute of Biogeochemistry and Pollutant Dynamics (IBP), ETH Zurich, CH-8092, Switzerland, (3) Department of Geography, University of Northern Iowa, Cedar Falls, USA, (4) INSTAAR and Dept. of Geography UCB-450, University of Colorado, Boulder, CO 80309, USA, (5) US Geological Survey, 3215 Marine Street, Boulder, CO 80303, USA, (6) Department of Mineralogy, TU Bergakademie Freiberg, D-09596 Freiberg, Germany , (7) ABR, Inc. Environmental Research and Services, Anchorage, AK, 99518 , (8) Department of Geography, University of Zurich, CH-8057, Switzerland

Dating of gravel‐capped strath terraces in basins adjacent to western U.S. Laramide Ranges is one approach to document the history of late Cenozoic fluvial exhumation. We use in situ 10Be measurements to date the broad surfaces adjacent to the eastern edge of the Rocky Mountains in Colorado, and compare these calculated ages with results from meteoric 10Be measurements. We analyze three sites near Boulder, Colorado (Gunbarrel Hill, Table Mountain, and Pioneer) that have been mapped as the oldest terrace surfaces with suggested ages ranging from 640 ka to the Plio‐Pleistocene transition. Our in situ 10Be results reveal abandonment ages of 95 ± 129 ka at Table Mountain, 175 ± 27 ka at Pioneer, and ages of 251 ± 10 ka and 307 ± 15 ka at Gunbarrel Hill. All are far younger than previously thought. Inventories of meteoric 10Be support this interpretation, yielding ages that are comparable to Table Mountain and ∼20% lower than Pioneer in situ ages. We argue that lateral beveling by rivers dominated during protracted times of even moderate glacial climate, and that vertical incision rates of several mm/yr likely occurred during times of very low sediment supply during the few interglacials that were characterized by particularly warm climate conditions. In contrast to the traditional age chronology in the area, our ages suggest that the deep exhumation of the western edge the High Plains occurred relatively recently and at an unsteady pace.

Analyses of organic-rich mudstones from wells that penetrated the Upper Jurassic Kimmeridge Clay Formation, offshore United Kingdom, were performed to evaluate the nature of both organic and inorganic rock constituents and their relation to porosity in this world-class source rock. The formation is at varying levels of thermal maturity, ranging from immature in the shallowest core samples to mature in the deepest core samples. The intent of this study was to evaluate porosity as a function of both organic macerals and thermal maturity.At least four distinct types of organic macerals were observed in petrographic and SEM analyses and they all were present across the study area. The macerals include, in decreasing abundance: 1) bituminite admixed with clays; 2) elongate lamellar masses (alginite or bituminite) with small quartz, feldspar, and clay entrained within it; 3) terrestrial (vitrinite, fusinite, semifusinite) grains; and 4) Tasmanites microfossils. Although pores in all maceral types were observed on ion-milled surfaces of all samples, the pores (largely nanopores with some micropores) vary as a function of maceral type. Importantly, pores in the macerals do not vary systematically as a function of thermal maturity, insofar as organic pores are of similar size and shape in both the immature and mature Kimmeridge rocks. If any organic pores developed during the generation of hydrocarbons, they were apparently not preserved, possibly because of the highly ductile nature of much of the rock constituents of Kimmeridge mudstones (clays and organic material).Inorganic pores (largely micropores with some nanopores) have been observed in all Kimmeridge mudstones. These pores, particularly interparticle (i.e., between clay platelets), and intraparticle (i.e., in framboidal pyrite, in partially dissolved detrital K-feldspar, and in both detrital and authigenic dolomite) are noteworthy because they compose much of the observable porosity in the shales in both immature and mature samples.The absence of a systematic increase in organic porosity as a function of either maceral type or thermal maturity indicates that such porosity was probably unrelated to hydrocarbon generation. Instead, much of the porosity within mudstones of the Kimmeridge appears to be largely intraparticle and interparticle (adjacent to inorganic constituents), so the petroleum storage potential in these organic-rich mudstones largely resides in inorganic pores.

The architecture of the Critical Zone, including mobile regolith thickness and depth to the weathering front, is first order controlled by advance of a weathering front at depth and transport of sediment at the surface. Differences in conditions imposed by slope aspect in the Gordon Gulch catchment of the Boulder Creek Critical Zone Observatory present a natural experiment to explore these interactions. The weathering front is deeper and saprolite more decayed on north-facing than on south-facing slopes. Simple numerical models of weathering front advance, mobile regolith production, and regolith transport are used to test how weathering and erosion rates interact in the evolution of weathered profiles. As the processes which attempt are being made to mimic are directly tied to climate variables such as mean annual temperature, the role of Quaternary climate variation in governing the evolution of Critical Zone architecture can be explored with greater confidence. (C) 2011 Elsevier Ltd. All rights reserved.

In the paper ‘Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance’ from Clays and Clay Minerals, vol. 52, 2004, 589–602, equation 3 should read:

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ∼0.99 mg/m2, which corresponds to ∼0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (∼725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Glauconite-bearing deposits are found worldwide, but As levels have been determined for relatively few. The As content of glauconites in sediments of the Inner Coastal Plain of New Jersey can exceed 100 mg/kg, and total As concentrations (up to 5.95 mu g/L) found historically and recently in streamwaters exceed the State standard. In a major watershed of the Inner Coastal Plain, chemical "fingerprints" were developed for streambed sediments and groundwater to identify contributions of As to the watershed from geologic and anthropogenic sources. The fingerprint for streambed sediments, which included Be, Cr, Fe and V, indicated that As was predominantly of geologic origin. High concentrations of dissolved organic C, nutrients (and Cl(-)) in shallow groundwater indicated anthropogenic inputs that provided an environment where microbial activity released As from minerals to groundwater discharging to the stream. Particulates in streamwater during high flow constituted most of the As load; the chemical patterns for these particulates resembled the geologic fingerprint of the streambed sediments. The As/Cr ratio of these suspended particles likely indicates they derived not only from runoff, but from groundwater inputs, because As contributed by groundwater is sequestered on streambed sediments. Agricultural inputs of As were not clearly identified, although chemical characteristics of some sediments indicated vehicle-related inputs of metals. Sediment sampling during dry and wet years showed that, under differing hydrologic conditions, local anthropogenic fingerprints could be obscured but the geologic fingerprint, indicating glauconitic sediments as an As source, was robust. Published by Elsevier Ltd.

The illite layer content of mixed-layer illite/smectite (I/S) in a 2.5 m thick, zoned, metabentonite bed from Montana decreases regularly from the edges to the center of the bed. Traditional X-ray diffraction (XRD) pattern modeling using Markovian statistics indicated that this zonation results from a mixing in different proportions of smectite-rich R0 I/S and illite-rich R1 I/S, with each phase having a relatively constant illite layer content. However, a new method for modeling XRD patterns of US indicates that R0 and R1 I/S in these samples are not separate phases (in the mineralogical sense of the word), but that the samples are composed of illite crystals that have continuous distributions of crystal thicknesses, and of 1 nm thick smectite crystals. The shapes of these distributions indicate that the crystals were formed by simultaneous nucleation and growth. XRD patterns for R0 and R1 I/S arise by interparticle diffraction from a random stacking of the crystals, with swelling interlayers formed at interfaces between crystals from water or glycol that is sorbed on crystal surfaces. It is the thickness distributions of smectite and illite crystals (also termed fundamental particles, or Nadeau particles), rather than XRD patterns for mixed-layer I/S, that are the more reliable indicators of geologic history, because such distributions are composed of well-defined crystals that are not affected by differences in surface sorption and particle arrangements, and because their thickness distribution shapes conform to the predictions of crystal growth theory, which describes their genesis.

Millions of pounds of mercury (Hg) were deposited in the river and stream channels of the Sierra Nevada from placer and hard-rock mining operations in the late 1800s and early 1900s. The resulting contaminated sediments are relatively harmless when buried and isolated from the overlying aquatic environment. The entrained Hg in the sediment constitutes a potential risk to human and ecosystem health should it be reintroduced to the actively cycling portion of the aquatic system, where it can become methylated and subsequently bioaccumulated in the food web. Each year, sediment is mobilized within these fluvial systems during high stormflows, transporting hundreds of tons of Hg-laden sediment downstream. The State of California and resource-management agencies, including the Bureau of Land Management (BLM) and the U.S. Forest Service, are concerned about additional disturbances, such as from suction gold dredging activities, which have the potential to mobilize Hg associated with buried sediment layers elevated in Hg that are otherwise likely to remain buried under normal storm conditions.The BLM initiated a study looking at the feasibility of removing Hg-contaminated sediment at the confluence of the South Yuba River and Humbug Creek in the northern Sierra Nevada of California by using standard suction-dredge technology. Additionally, the California State Water Resources Control Board (SWRCB) supported a comprehensive characterization of the intended dredge site. Together, the BLM and SWRCB supported a comprehensive characterization of Hg contamination at the site and the potential effects of sediment disturbance at locations with historical hydraulic mining debris on downstream environments. The comprehensive study consisted of two primary components: field studies and laboratory experiments. The field component, described in this report, had several study elements: 1) a preliminary, smallscale, in-stream dredge test; 2) comprehensive characterization of grain size distribution, Hg speciation, and mineralogy of bed and suspended sediment; 3) a determination of the past and current sources of sediment in the study area; 4) an assessment of Hg bioaccumulation in the local invertebrate population; and 5) a comparison of potential Hg transport caused by natural storm disturbances with potential Hg mobilization caused by suction dredging as a method of Hg removal at the study site. The laboratory component of the study assessed the potential influence of the disturbance of Hg-contaminated sediment through experiments designed to simulate in-stream transport, deposition, and potential methylation of Hg, described in a companion report (see Marvin-DiPasquale and others, 2011).Results of the field studies indicate that the fine-grained fraction (silt-clay, less than 0.063 millimeters) contains the greatest concentration of Hg in contaminated sediment. Because the fine-grained fraction is the most susceptible to longrange fluvial transport, disturbance of Hg-contaminated sediment is likely to increase the concentration and load of Hg in downstream waters. The preliminary, small-scale dredge test showed an increase in the concentration of fine particles and Hg in the water column caused by the dredge activity, despite relatively low concentrations of fine particles and Hg (about 300 nanograms per gram) at the dredge site. Characterization of sediment from two test pits and other sites in the vicinity of the confluence of the South Yuba River and Humbug Creek revealed a highly variable distribution of fine- and coarse-grained sediment. The highest levels of Hg contamination (up to 11,100 ng/g) were associated with the fine-grained fraction of sediment from the bedrock contact zone of Pit 2, a horizon which also yielded grains of gold and gold-Hg amalgam.A closed-circuit tank experiment with a venturi dredge at the base of Pit 1, in a gravel bar within the South Yuba River, resulted in fine-grained suspended sediment remaining in suspension more than 40 hours following the disturbance simulation. Although the volumetric concentration of Hg declined over time as particles settled out, the concentration of Hg on the suspended particles increased over time as the suspended material became finer grained, because Hg is preferentially adsorbed on to clay-sized particles. Mineralogical and chemical analyses indicated that the buried fine-grained material with the greatest Hg contamination was derived from hydraulic mining debris, which consist primarily of Eocene gravels mined in the Malakoff Diggins, North Bloomfield, and Lake City areas within the South Yuba River watershed. Coarse material and more recently deposited sediment were derived primarily from upstream sources on the South Yuba River.The biota assessment indicated that invertebrate taxa collected from all sites on the South Yuba River in 2007, including lower Humbug Creek, had elevated concentrations of total mercury (THg) and methylmercury (MeHg) compared to a reference site on the Bear River, upstream of mining effects. Differences with the reference site were less pronounced in 2008 when a significant reduction in MeHg concentrations was observed in biota across all taxa from concentrations in 2007. It is possible that the inter-annual variation was related to the fact that suction dredging was active in the South Yuba River in 2007 but not in 2008 when a local moratorium was imposed by the BLM. There were significant variations among taxa for both THg and MeHg concentrations, with the water striders (Gerridae) having the highest concentrations of both THg and MeHg; variation among sites was not as strong as between years or among taxa. These results suggest that additional monitoring would be helpful to investigate the possible linkage between variations in MeHg bioaccumulation and levels of suction dredge activity in areas of historical gold mining.Results from the field studies indicate that disturbance of the finegrained Hg-contaminated sediment would likely lead to enhanced mobilization of Hg to downstream environments; therefore, the use of suction dredging to remove Hg at the South Yuba River and Humbug Creek confluence area would likely result in enhanced Hg transport downstream relative to natural conditions.

Minnesota forested soils have evolved without the presence of earthworms since the last glacial retreat. When exotic earthworms arrive, enhanced soil bioturbation often results in dramatic morphological and chemical changes in soils with negative implications for the forests’ sustainability. However, the impacts of earthworm invasion on geochemical processes in soils are not well understood. This study attempts to quantify the role of earthworm invasion in mineral chemical weathering and nutrient dynamics along an earthworm invasion chronosequence in a sugar maple forest in Northern Minnesota. Depth and rates of soil mixing can be tracked with atmospherically derived short lived radioisotopes 210Pb and 137Cs. Their radioactivities increase in the lower A horizon at the expense of the peak activities near the soil surface, which indicate that soil mixing rate and its depth reach have been enhanced by earthworms. Enhanced soil mixing by earthworms is consistent with the ways that the vertical profiles of elemental and mineralogical compositions were affected by earthworm invasion. Biologically cycled Ca and P have peak concentrations near the soil surface prior to earthworm invasion. However, these peak abundances significantly declined in the earthworm invaded soils presumably due to enhanced soil mixing. It is clear that enhanced soil mixing due to earthworms also profoundly altered the vertical distribution of most mineral species within A horizons. Though the mechanisms are not clear yet, earthworm invasion appears to have contributed to net losses of clay mineral species and opal from the A horizons. As much as earthworms vertically relocated minerals and elements, they also intensify the contacts between organic matter and cations as shown in the increased amount of Ca and Fe in organically complexed and in exchangeable pools. With future studies on soil mixing rates and elemental leaching, this study will quantitatively and mechanically address the role of earthworms in geochemical evolution of soils and forests’ nutrient dynamics.