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Studies of co-produced waters from hydrocarbon extraction across multiple energy-producing basins have generally focused on major ions or a few select tracers, and studies that examine trace elements and involve laboratory experiments have generally been basin specific. Here, new perspective is sought through a broad analysis of concentration data for 26 elements from three hydrocarbon well types using the U.S. Geological Survey National Produced Waters Geochemical Database (v2.3). Those data are compared to leachates (water, hydrochloric acid, and artificial brine) from 12 energy-resource related shales from across the United States. Both lower pH and higher ionic strength were associated with greater concentrations of many trace elements in produced waters. However, individual effects were difficult to distinguish because higher ionic strengths drive decreases in pH. Water–rock interactions in the leaching experiments generally replicated produced water concentrations for trace elements including Al, As, Cd, Co, Cu, Mo, Ni, Pb, Sb, Si, and Zn. Enhanced middle rare earth element (REE) mobilization relative to shale REE content occurred with low pH leachates. Produced water concentrations of Li, Sr, and Ba were not replicated by the leaching experiments. Patterns of high Li, Sr, and Ba concentrations and ratios relative to other elements across produced waters types indicate controls on these elements in many settings related to pore space pools of salts, brines, and ion-exchange sites affected by diagenetic processes. The size of those pools is diluted and masked by other water–rock interaction processes at the water–rock ratios necessitated by laboratory experiments. The results broadly link water–rock interaction processes and environmental patterns across a wide variety of produced waters and host formations and thus provide context for trace element data from other environmental and laboratory studies of such waters.

Water quality and quantity can be influenced by transit through and storage in reservoirs. Assessing such effects can be challenging, however, because of mixing and residence times, and inter-annual net storage and release from both the reservoir itself and surrounding porosity. Here, different methodologies were used to assess the effect of John Martin Reservoir (JMR), located on the Arkansas River, on water volumes and the problematic constituents salinity (total dissolved solids, TDS), selenium (Se), and uranium (U). Methodologies addressed short-term (16 months) and long-term (31 years) effects depending upon data availability. Evaporation was assessed by using isotopes of water to determine 12% short-term evaporation, and by pan evaporation and changes in storage to determine 11% long-term evaporation. Salinity, Se, and U mass balance were assessed by using chloride (Cl−) as an index by which to measure short-term gains or losses between inflows and outflows in the short term. Chloride gain from ungaged inflows skewed those results to overestimate retention. Continuous monitoring of discharge and specific conductance for inflows and outflows, along with discrete sampling for dissolved constituents were used to compute long-term, load-based mass balance. Mild gains of TDS (34,000 ± 15,000 Mg/yr) and U (0.1 ± 0.5 Mg/yr) in JMR were detected. Although the additions are small relative to uncertainty, they indicate little to no retention of TDS and U and likely additions from ungaged inflows. In contrast, an average of 0.6 ± 0.2 Mg/yr or 23% of gaged inflow Se was removed in JMR. The study illustrates the benefit of long-term records for assessing the influence of reservoirs for which net storage and release keep them from approaching steady-state conditions. Keywords: Selenium, Uranium, Evaporation, Sulfate isotopes, Water isotopes

Losses of small mineral particles can be a significant physical process that affects the elemental composition of soils derived from sedimentary rocks. Shales, in particular, contain abundant clay-sized minerals that can be mobilized by simple disaggregation, and solutional weathering is limited because the parent rock is composed primarily of recalcitrant minerals previously subjected to continental weathering. Here, the dual-phase mass balance model is employed to quantify losses of small mineral particles as water dispersible colloids (WDCs) from three previously studied soil profiles along a hill slope at the Susquehanna Shale Hills Critical Zone Observatory (SSHO). WDCs were isolated from soil in the laboratory to determine their mineralogical and elemental compositions. Clay minerals dominated WDCs, including illite, vermiculite, and chlorite inherited from the parent shale, along with neoformed kaolinite. Quartz present in bulk soil was generally excluded from WDCs. Elements of low solubility and/or bound in recalcitrant forms, like Rb in illite, were employed in tracer ratios in the dual-phase model. Aluminum, Ga, and Rb were enriched in WDCs, and Zr and Hf were partially excluded. Six different combinations of elements into tracer ratios (Al/Zr, Ga/Zr, Rb/Zr, Al/Hf, Ga/Hf, Rb/Hf) each yielded similar model results. Mass losses of WDCs were large, ranging from − 68 ± 7% to − 15 ± 5% relative to soil parent material in different parts of the profiles. Mass losses via solution were smaller, ranging from − 7 ± 2% to a gain of 6 ± 1% in part of one profile. Losses of WDCs account for > 90% of total mass loss, surpassing chemical dissolution, and therefore dominate the weathering portion of denudation at SSHO. Zirconium concentrations were 97–158 ppm in the generally ≤ 1 μm WDCs, suggesting colloidal, Zr-bearing phases. Model-quantified losses of Zr via WDCs were large, with a median loss of 41% relative to parent material. Such losses indicate systematic underestimates of weathering by traditional mass balance that uses Zr as an index element. Losses of Ca, Mg, and K via WDCs exceeded losses via solution, countering assumptions of base cation losses primarily via mineral dissolution. The results illustrate a geochemical fingerprint of physical weathering and the ability of the dual-phase model to quantify that weathering process.

Ion-adsorbed rare earth element (REE) deposits supply the majority of world heavy REE production and substantial light REE production, but relatively little is known of their occurrence outside Southeast Asia. We examined the distribution and forms of REEs on a North American pluton located in the highly weathered and slowly eroding South Carolina Piedmont. The Hercynian Liberty Hill pluton experiences a modern climate that includes ~ 1500 mm annual rainfall and a mean annual temperature of 17 °C. The pluton is medium- to coarse-grained biotite-amphibole granite with minor biotite granite facies. REE-bearing phases are diverse and include monazite, zircon, titanite, allanite, apatite and bastnasite. Weathered profiles were sampled up to 7 m-deep across the ~ 400 km 2 pluton. In one profile, ion-adsorbed REEs plus yttrium (REE + Y) ranged up to 581 mg/kg and accounted for up to 77% of total REE + Y in saprolite. In other profiles, ion-adsorbed REE + Y ranged 12–194 mg/kg and only accounted for 3–37% of totals. The profile most enriched in ion-adsorbed REEs was located along the mapped boundary of two granite facies and contained trioctahedral smectite in the saprolite, evidence suggestive of hydrothermal alteration of biotite at that location. Post-emplacement deuteric alteration can generate easily weathered REE phases, particularly fluorocarbonates. In the case of Liberty Hill, hydrothermal alteration may have converted less soluble to more soluble REE minerals. Additionally, regolith P content was inversely correlated with the fraction ion-adsorbed REEs, and weathering related secondary REE-phosphates were found in some regolith profiles. Both patterns illustrate how low P content aids in the accumulation of ion-adsorbed REEs. The localized occurrence at Liberty Hill sheds light on conditions and processes that generate ion-adsorbed REEs.

Rare earth element (REE) resources are currently of great interest because of their importance as raw materials for high-technology manufacturing. The REE-phosphates monazite (light REE enriched) and xenotime (heavy REE enriched) resist weathering and can accumulate in placer deposits as part of the heavy mineral assemblage. The Atlantic and Gulf coastal plains of the southeastern United States are known to host heavy mineral deposits with economic concentrations of zircon, ilmenite and rutile. This study provides a perspective on the distribution and composition of REE phosphate minerals in the region. The elemental chemistry and mineralogy of sands and associated heavy-mineral assemblages from new and archived sediment samples across the coastal plains are examined, along with phase-specific compositions of monazite, xenotime and zircon. Both monazite and xenotime are present across the coastal plains. The phase-specific compositions allow monazite content to be estimated using La as a geochemical proxy. Similarly, both Y and Yb are geochemical proxies for xenotime, but their additional presence in zircon and monazite require a correction to prevent overestimation of xenotime content. Applying this correction, maps of monazite and xenotime content across the coastal plains were generated using sample coverage from the National Geochemical Database (NGS) and National Uranium Resource Evaluation (NURE). The NGS and NURE approach of sampling stream sediments in small watersheds links samples to nearby lithologies. The results show an approximately 40 km-wide band of primarily Cretaceous, marine sediments bordering the Piedmont province from North Carolina to Alabama in which monazite and xenotime content are relatively high (up to 4.4 wt. % in

Nontuberculous mycobacteria (NTM) are environmental bacteria that may cause chronic lung disease. Environmental factors that favor NTM growth likely increase the risk of NTM exposure within specific environments. We aimed to identify water-quality constituents (Al, As, Cd, Ca, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Se, Na, Zn, and pH) associated with NTM disease across Colorado watersheds. We conducted a geospatial, ecological study, associating data from patients with NTM disease treated at National Jewish Health and water-quality data from the Water Quality Portal. Water-quality constituents associated with disease risk were identified using generalized linear models with Poisson-distributed discrete responses. We observed a highly robust association between molybdenum (Mo) in the source water and disease risk. For every 1- unit increase in the log concentration of molybdenum in the source water, disease risk increased by 17.0%. We also observed a statistically significant association between calcium (Ca) in the source water and disease risk. The risk of NTM varied by watershed and was associated with watershed-specific water-quality constituents. These findings may inform mitigation strategies to decrease the overall risk of exposure.

The enrichment factor (EF) is a widely used metric for determining how much the presence of an element in a sampling media has increased relative to average natural abundance because of human activity. Calculation of an EF requires the selection of both a background composition and a reference element, choices that can strongly influence the result of the calculation. Here, it is shown how carefully applied, classical principal component analysis (PCA) examined via biplots can guide the selections of background compositions and reference elements. Elemental data were treated using the centered log ratio (CLR) transformation, and multiple subsets of major and trace elements were examined to gain different perspectives. The methodology was applied to a dataset of elemental soil concentrations from around breccia pipe uranium mines in Arizona, U.S.A., with most samples collected via incremental sampling methodology. Storage of ore at the surface creates the potential for wind dispersal of ore-derived material. Uranium was found to be the best individual tracer of dispersal of ore-derived material to nearby soils, with EF values up to 75. Sulfur, As, Mo, and Cu were also enriched but to lesser degrees. The results demonstrate several practical benefits of a PCA in these situations: (1) the ability to identify one or more elements best suited to distinguish a specific source of enrichment from background composition; (2) understanding how background compositions vary within and between sites; (3) identification of samples containing enriched or anthropogenic materials based upon their integrated, multi-element composition. Calculating the most representative EF values is useful for numerical assessment of enrichment, whether anthropogenic or natural. As shown here, however, the PCA and biplot method provide a visual approach that integrates information from all elements for a given subset of data in a manner that yields geochemical insights beyond the power of the EF.

Organic matter–mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40–70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9–47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had TTs averaging 190 ± 190 years in surface horizons. Summed over the bulk soil profile, we found that smectite content correlated with the mean TT of bulk soil C across varied lithologies. The SRO mineral content in KNP soils was generally very low, except for the soils developed on gabbros under more humid climate that also had very high Fe and C contents with a surprisingly short, mean C TTs. In younger landscapes, SRO minerals are metastable and sequester C for long timescales. We hypothesize that in the KNP, SRO minerals represent a transient stage of mineral evolution and therefore lock up C for a shorter time. Overall, we found crystalline Fe-oxyhydroxides (determined as the difference between Fe in dithionate citrate and oxalate extractions) to be the strongest predictor for soil C content, while the mean TT of soil C was best predicted from the amount of smectite, which was also related to more easily measured bulk properties such as cation exchange capacity or pH. Combined with previous research on C turnover times in 2 : 1 vs. 1 : 1 clays, our results hold promise for predicting C inventory and persistence based on intrinsic timescales of specific carbon–mineral interactions.

Summary Salinization is a global threat to the quality of streams and rivers, but it can have many causes. Oil and gas development were investigated as one of several potential causes of changes in the salinity of Muddy Creek, which drains 2470 km 2 of mostly public land in Wyoming, U.S.A. Stream discharge and salinity vary with seasonal snowmelt and define a primary salinity–discharge relationship. Salinity, measured by specific conductance, increased substantially in 2009 and was 53–71% higher at low discharge and 33–34% higher at high discharge for the years 2009–2012 compared to 2005–2008. Short-term processes (e.g., flushing of efflorescent salts) cause within-year deviations from the primary relation but do not obscure the overall increase in salinity. Dissolved elements associated with increased salinity include calcium, magnesium, and sulfate, a composition that points to native soil salts derived from marine shales as a likely source. Potential causes of the salinity increase were evaluated for consistency by using measured patterns in stream chemistry, slope of the salinity–discharge relationship, and inter-annual timing of the salinity increase. Potential causes that were inconsistent with one or more of those criteria included effects from precipitation, evapotranspiration, reservoirs, grazing, irrigation return flow, groundwater discharge, discharge of energy co-produced waters, and stream habitat restoration. In contrast, surface disturbance of naturally salt-rich soil by oil and gas development activities, such as pipeline, road, and well pad construction, is a reasonable candidate for explaining the salinity increase. As development continues to expand in semiarid lands worldwide, the potential for soil disturbance to increase stream salinity should be considered, particularly where soils host substantial quantities of native salts.

It has been shown that EPA Method 3060A does not adequately extract Cr(VI) from chromium ore processing residue (COPR). We modified various parameters of EPA 3060A toward understanding the transformation of COPR minerals in the alkaline extraction and improving extraction of Cr(VI) from NIST SRM 2701, a standard COPR-contaminated soil. Aluminum and Si were the major elements dissolved from NIST 2701, and their concentrations in solution were correlated with Cr(VI). The extraction fluid leached additional Al and Si from the method-prescribed borosilicate glass vessels which appeared to suppress the release of Cr(VI). Use of polytetrafluoroethylene vessels and intensive grinding of NIST 2701 increased the amount of Cr(VI) extracted. These modifications, combined with an increased extraction fluid to sample ratio of ≥900 mL g–1 and 48-h extraction time resulted in a maximum release of 1274 ± 7 mg kg–1 Cr(VI). This is greater than the NIST 2701 certified value of 551 ± 35 mg kg–1 but less than 3050 mg kg–1 Cr...

Colloids can be important vectors for the transport of contaminants in the environment, but little is known about colloid mobilization at the watershed scale. We present colloid concentration, composition, and flux data over a large range of hydrologic conditions from a small watershed (Gordon Gulch) in the foothills of the Colorado Front Range. Colloids, consisting predominantly of Si, Fe, and Al, were present in most stream samples but were not detected in groundwater samples. Mineralogical and morphological analysis indicated that the colloids were composed of kaolinite and illite clays with lesser amounts of amorphous Fe-hydroxides. Although colloid composition remained relatively constant over the sampled flow conditions, colloid concentrations varied considerably and increased as ionic strength of stream water decreased. The highest concentrations occurred during precipitation events after extended dry periods. These observations are consistent with laboratory studies that have shown colloids can be mobilized by decreases in pore-water ionic strength, which likely occurs during precipitation events. Colloidal particles constituted 30 to 35% of the Si mass flux and 93 to 97% of the Fe and Al mass fluxes in the

Disposal of produced waters, pumped to the surface as part of coalbed methane (CBM) development, is a significant environmental issue in the Wyoming portion of the Powder River Basin, USA. High sodium adsorption ratios (SAR) of the waters could degrade agricultural land, especially if directly applied to the soil surface. One method of disposing of CBM water, while deriving beneficial use, is subsurface drip irrigation (SDI), where acidified CBM waters are applied to alfalfa fields year-round via tubing buried 0.92 m deep. Effects of the method were studied on an alluvial terrace with a relatively shallow depth to water table (∼3 m). Excess irrigation water caused the water table to rise, even temporarily reaching the depth of drip tubing. The rise corresponded to increased salinity in some monitoring wells. Three factors appeared to drive increased groundwater salinity: (1) CBM solutes, concentrated by evapotranspiration; (2) gypsum dissolution, apparently enhanced by cation exchange; and (3) dissolution of native Na–Mg–SO4 salts more soluble than gypsum. Irrigation with high SAR (∼24) water has increased soil saturated paste SAR up to 15 near the drip tubing. Importantly though, little change in SAR has occurred at the surface.

A catena is a series of distinct but co-evolving soils arrayed along a slope. On low-slope, slowly eroding catenas the redistribution of mass occurs predominantly as plasma, the dissolved and suspended constituents in soil water. We applied mass balance methods to track how redistribution via plasma contributed to physical and geochemical differentiation of nine slowly eroding (~ 5 mm ky − 1 ) granitic catenas. The catenas were arrayed in a 3 × 3 climate by relief matrix and located in Kruger National Park, South Africa. Most of the catenas contained at least one illuviated soil profile that had undergone more volumetric expansion and less mass loss, and these soils were located in the lower halves of the slopes. By comparison, the majority of slope positions were eluviated. Soils from the wetter climates (550 and 730 mm precipitation yr − 1 ) generally had undergone greater collapse and lost more mass, while soils in the drier climate (470 mm yr − 1 ) had undergone expansion and lost less mass. Effects of differences in catena relief were less clear. Within each climate zone, soil horizon mass loss and strain were correlated, as were losses of most major elements, illustrating the predominant influence of primary mineral weathering. Nevertheless, mass loss and volumetric collapse did not become extreme because of the skeleton of resistant primary mineral grains inherited from the granite. Colloidal clay redistribution, as traced by the ratio of Ti to Zr in soil, suggested clay losses via suspension from catena eluvial zones. Thus illuviation of colloidal clays into downslope soils may be crucial to catena development by restricting subsurface flow there. Our analysis provides quantitative support for the conceptual understanding of catenas in cratonic landscapes and provides an endmember reference point in understanding the development of slowly eroding soil landscapes.

Waters with low salinity and high sodium adsorption ratios (SARs) present a challenge to irrigation because they degrade soil structure and infiltration capacity. In the Powder River Basin of Wyoming, such low salinity (electrical conductivity, EC 2.1 mS cm−1) and high-SAR (54) waters are co-produced with coal-bed methane and some are used for subsurface drip irrigation (SDI). The SDI system studied mixes sulfuric acid with irrigation water and applies water year-round via drip tubing buried 92 cm deep. After six years of irrigation, SAR values between 0 and 30 cm depth (0.5–1.2) are only slightly increased over non-irrigated soils (0.1–0.5). Only 8–15% of added Na has accumulated above the drip tubing. Sodicity has increased in soil surrounding the drip tubing, and geochemical simulations show that two pathways can generate sodic conditions. In soil between 45-cm depth and the drip tubing, Na from the irrigation water accumulates as evapotranspiration concentrates solutes. SAR values >12, measured by 1:1 water–soil extracts, are caused by concentration of solutes by factors up to 13. Low-EC ( 14 and decreasing EC in soil water to 3.2 mS cm−1. Increased sodicity in the subsurface, rather than the surface, indicates that deep SDI can be a viable means of irrigating with sodic waters.

Water co-produced with coal-bed methane (CBM) in the semi-arid Powder River Basin of Wyoming and Montana commonly has relatively low salinity and high sodium adsorption ratios that can degrade soil permeability where used for irrigation. Nevertheless, a desire to derive beneficial use from the water and a need to dispose of large volumes of it have motivated the design of a deep subsurface drip irrigation (SDI) system capable of utilizing that water. Drip tubing is buried 92 cm deep and irrigates at a relatively constant rate year-round, while evapotranspiration by the alfalfa and grass crops grown is seasonal. We use field data from two sites and computer simulations of unsaturated flow to understand water and solute movements in the SDI fields. Combined irrigation and precipitation exceed potential evapotranspiration by 300–480 mm annually. Initially, excess water contributes to increased storage in the unsaturated zone, and then drainage causes cyclical rises in the water table beneath the fields. Native chloride and nitrate below 200 cm depth are leached by the drainage. Some CBM water moves upward from the drip tubing, drawn by drier conditions above. Chloride from CBM water accumulates there as root uptake removes the water. Year over year accumulations indicated by computer simulations illustrate that infiltration of precipitation water from the surface only partially leaches such accumulations away. Field data show that 7% and 27% of added chloride has accumulated above the drip tubing in an alfalfa and grass field, respectively, following 6 years of irrigation. Maximum chloride concentrations in the alfalfa field are around 45 cm depth but reach the surface in parts of the grass field, illustrating differences driven by crop physiology. Deep SDI offers a means of utilizing marginal quality irrigation waters and managing the accumulation of their associated solutes in the crop rooting zone.

Organic matter-mineral associations stabilize much of the carbon stored globally in soils. Metastable shortrange-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in soil. However, ancient and highly weathered soils that cover a large fraction of land area lack SRO minerals. Here we evaluate the role of different minerals on the amount and turnover time (TT) of carbon in a field setting designed to 15 minimize the role of SRO by taking advantage of multiple lithologies in Kruger National Park, South Africa. Density separation demonstrated that most of the C was associated with minerals, even in surface soils. A parallel separation of claysized material demonstrated that 9-47% of the organic C in these soils was stabilized by clays. Organic C associated with clay-sized material had average TT of 1020 ± 460 years in surface soils. The mean TT of this clay-associated C increased with depth and with fraction of total clay that was smectite. Because the C associated with smectite clay was so old, the 20 amount of smectite (2:1 clays) controlled the age of bulk soil C across Kruger landscapes. The TT of the majority of soil C – not stabilized by clays was much shorter, 190±190 years in surface horizons. We suggest that this faster component reflects timescales of weaker C stabilization by crystalline Fe and Al oxyhydr)oxides and kaolinite (1:1) clays, as well as LF fractions not associated with minerals. Thus, bulk or HF carbon integrates C stabilized by mechanisms with inherently different TT, something that is often inferred from radiocarbon measurements. While SRO mineral concentrations were 25 very low in these soils, the soils with most SRO had very high C content but also very young C. In other environments, SRO can be very stable and sorb C on very long timescales. We hypothesize that the seasonal wetting and drying in the KNP may reduce the age of SRO minerals as well as the C associated with them. Across the varying lithologies and a precipitation gradient found in the KNP, we found mineralogy to be the most important explanatory factor for C content (related to crystalline Fe) and turnover time (related to the amount of smectite). 30 SOIL Discuss., doi:10.5194/soil-2016-31, 2016 Manuscript under review for journal SOIL Published: 26 April 2016 c © Author(s) 2016. CC-BY 3.0 License.

One method to beneficially use water produced from coalbed methane (CBM) extraction is subsurface drip irrigation (SDI) of croplands. In SDI systems, treated CBM water (injectate) is supplied to the soil at depth, with the purpose of preventing the buildup of detrimental salts near the surface. The technology is expanding within the Powder River Basin, but little research has been published on its environmental impacts. This article reports on initial results from tracking water and solutes from the injected CBM-produced waters at an SDI system in Johnson County, Wyoming. In the first year of SDI operation, soil moisture significantly increased in the SDI areas, but well water levels increased only modestly, suggesting that most of the water added was stored in the vadose zone or lost to evapotranspiration. The injectate has lower concentrations of most inorganic constituents relative to ambient groundwater at the site but exhibits a high sodium adsorption ratio. Changes in groundwater chemistry during the same period of SDI operation were small; the increase in groundwater-specific conductance relative to pre-SDI conditions was observed in a single well. Conversely, groundwater samples collected beneath another SDI field showed decreased concentrations of several constituents since the SDI operation. Groundwater-specific conductance at the 12 other wells showed no significant changes. Major controls on and compositional variability of groundwater, surface water, and soil water chemistry are discussed in detail. Findings from this research provide an understanding of water and salt dynamics associated with SDI systems using CBM-produced water.

Studies of weathering and pedogenesis have long used calculations based upon low solubility index elements to determine mass gains and losses in open systems. One of the questions currently unanswered in these settings is the degree to which mass is transferred in solution (solutes) versus suspension (colloids). Here we show that differential mobility of the low solubility, high field strength (HFS) elements Ti and Zr can trace colloidal redistribution, and we present a model for distinguishing between mass transfer in suspension and solution. The model is tested on a well-differentiated granitic catena located in Kruger National Park, South Africa. Ti and Zr ratios from parent material, soil and colloidal material are substituted into a mixing equation to quantify colloidal movement. The results show zones of both colloid removal and augmentation along the catena. Colloidal losses of 110 kg m −2 (− 5% relative to parent material) are calculated for one eluviated soil profile. A downslope illuviated profile has gained 169 kg m −2 (10%) colloidal material. Elemental losses by mobilization in true solution are ubiquitous across the catena, even in zones of colloidal accumulation, and range from 1418 kg m −2 (− 46%) for an eluviated profile to 195 kg m −2 (− 23%) at the bottom of the catena. Quantification of simultaneous mass transfers in solution and suspension provide greater specificity on processes within soils and across hillslopes. Additionally, because colloids include both HFS and other elements, the ability to quantify their redistribution has implications for standard calculations of soil mass balances using such index elements.

Silicon isotope ratios (δ30Si) of bulk mineral materials in soil integrate effects from both silicon sources and processing. Here we report δ30Si values from a climate gradient of Hawaiian soils developed on 170 ka basalt and relate them to patterns of soil chemistry and mineralogy. The results demonstrate informative relationships between the mass fraction of soil Si depletion and δ30Si. In upper ( 1 m deep) soil horizons generally correlate with the isotope fractionation predicted by a study of dissolved Si in basalt-watershed rivers and driven by preferential 28Si removal from the dissolved phase during precipitation. In contrast, after correcting for the influence of dust, secondary mineral Si depletion and δ30Si values in shallow (

Strontium isotope ratios assist ecosystem scientists in constraining the sources of alkaline earth elements, but their interpretation can be difficult because of complexities in mineral weathering and in the geographical and environmental controls on elemental additions and losses. Hawaii is a “natural laboratory” where a number of important biogeochemical variables have either limited ranges or vary in systematic ways, providing a unique opportunity to understand the impact of time, climate, and atmospheric inputs on the evolution of base cation sources to ecosystems. There are three major sources of strontium (Sr) to these ecosystems, each with distinct isotopic compositions: basalt lava, Asian dust, and rainfall. We present Sr isotope and concentration data on both bulk soil digests and NH4Ac extracts from soil profiles covering a wide range of environments and substrate ages. Bulk soil material from dry climates and/or young substrate ages with > 80 µg g− 1 Sr retain basalt-like Sr isotopic signatures, whereas those with Sr concentrations 40% by mass. At elevated dust levels, lava-derived Sr is low and dust-derived Sr is the dominant control of 87Sr/86Sr in bulk soils; however, 87Sr/86Sr of NH4Ac-extractable Sr largely reflects atmospheric deposition of marine aerosol in these situations. Overall, whole-soil Sr isotope values are controlled by complex interactions between Sr provided by lava weathering but partially lost by leaching, and Sr provided by dust but held in more resistant minerals. The isotopic composition of NH4Ac-extractable Sr and of the biota is controlled by lava weathering and rainfall contribution of Sr with only minor contributions from radiogenic dust sources.

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

Knowledge of diet–tissue stable isotope discrimination is required to properly interpret stable isotope values and to identify possible diet shifts, such as might be expected from nursing through weaning. This study compared δ13C and δ15Ν οf paired serum and vibrissal roots with those of ingested milk (n = 52) from free-ranging Steller sea lion ( Eumetopias jubatus (Schreber, 1776)) pups (1–11 months) and juveniles (14–27 months) to estimate diet–tissue discrimination. Mean 15N enrichment from ingested milk to serum was 2.1‰ ± 0.6‰ and δ15Ν at the root of the vibrissae (representing current growth) were not significantly different from serum values. Milk was enriched for mean 13C by 5.0‰ ± 1.0‰ and 7.3‰ ± 1.2‰ relative to serum and vibrissal roots, respectively, which was due to the presence of 13C-depleted lipids in milk. This was confirmed by lipid extraction from a subset of milk and serum samples, resulting in a 5.8‰ ± 1.0‰ change only in milk. This study established that vibrissal roots and serum are reflective of a milk diet with approximately 2.0‰ 15N enrichment, and vibrissal roots reflect serum and lipid-extracted milk values with approximately 2.0‰ 13C enrichment. These discrimination factors are important to establish for stable isotope studies assessing diet shifts.

Weathering and leaching can progressively deplete the pools of soluble, rock-derived elements in soils and ecosystems over millennial time-scales, such that productivity increasingly relies on inputs from atmospheric deposition. This transition has been explored using strontium isotopes, which have been widely assumed to be a proxy for the provenance of other rock-derived elements. We compared rock versus atmospheric proportions of strontium to those for sulfur, a plant macronutrient, at several tropical forest sites in Hawaii and Costa Rica. Isotopic analyses reveal that sulfur is often decoupled from strontium in the transition to atmospheric dependence. Decoupling is likely the result of differences in chemical factors such as atmospheric input rates, mobility in the soil environment, and mineral weathering susceptibility. Strontium and sulfur decoupling appears to be accentuated by the physical process of erosion. Erosion rates are presumed to be high on the Osa Peninsula of Costa Rica, where the recent onset of rapid tectonic uplift has placed the landscape in a transient state. Decoupling is strong there, as erosion has rejuvenated the supply of rock-derived strontium but not sulfur. The landscape response to changes in tectonic uplift on the Osa Peninsula has produced decoupling at the landscape scale. Decoupling is more variable along a Hawaiian catena, presumably due to smaller scale variations in erosion rates and their influence on rejuvenation of rock-strontium inputs. These results illustrate how chemical and physical processes can interact to produce contrasting origins for different nutrient elements in soils and the ecosystems they support.

© 2014. Mass balance models have become standard tools for characterizing element gains and losses and volumetric change during weathering and soil development. However, they rely on the assumption of complete immobility for an index element such as Ti or Zr. Here we describe a dual-phase mass balance model that eliminates the need for an assumption of immobility and in the process quantifies the contribution of aqueous versus colloidal element transfer. In the model, the high field strength elements Ti and Zr are assumed to be mobile only as suspended solids (colloids) and can therefore be used to distinguish elemental redistribution via colloids from redistribution via dissolved aqueous solutes. Calculations are based upon element concentrations in soil, parent material, and colloids dispersed from soil in the laboratory. We illustrate the utility of this model using a catena in South Africa. Traditional mass balance models systematically distort elemental gains and losses and changes in soil volume in this catena due to significant redistribution of Zr-bearing colloids. Applying the dual-phase model accounts for this colloidal redistribution and we find that the process accounts for a substantial portion of the major element (e.g., Al, Fe and Si) loss from eluvial soil. In addition, we find that in illuvial soils along this catena, gains of colloidal material significantly offset aqueous elemental loss. In other settings, processes such as accumulation of exogenous dust can mimic the geochemical effects of colloid redistribution and we suggest strategies for distinguishing between the two. The movement of clays and colloidal material is a major process in weathering and pedogenesis; the mass balance model presented here is a tool for quantifying effects of that process over time scales of soil development.

Controls over nutrient supply are key to understanding the structure and functioning of terrestrial ecosystems. Conceptual models once held that in situ mineral weathering was the primary long-term control over the availability of many plant nutrients, including the base cations calcium (Ca), magnesium (Mg), and potassium (K). Recent evidence has shown that atmospheric sources of these “rock-derived” nutrients can dominate actively cycling ecosystem pools, especially in systems on highly weathered soils. Such studies have relied heavily on the use of strontium isotopes as a proxy for base-cation cycling. Here we show that vegetation and soil-exchangeable pools of strontium in a tropical rainforest on highly weathered soils are still dominated by local rock sources. This pattern exists despite substantial atmospheric inputs of Sr, Ca, K, and Mg, and despite nearly 100% depletion of these elements from the top 1 m of soil. We present a model demonstrating that modest weathering inputs, resulting from tectonically driven erosion, could maintain parent-material dominance of actively cycling Sr. The majority of tropical forests are on highly weathered soils, but our results suggest that these forests may still show considerable variation in their primary sources of essential nutrients.

We combined geophysical, geochemical, mineralogical, and geological data to evaluate the regional presence of rare earth element (REE)−bearing minerals in heavy mineral sand deposits of the southeastern U.S. Coastal Plain. We also analyzed regional differences in these data to determine probable sedimentary provenance. Analyses of heavy mineral separates covering the region show strong correlations between thorium, monazite, and xenotime, suggesting that radiometric equivalent thorium (eTh) can be used as a geophysical proxy for those REE-bearing minerals. Airborne radiometric data collected during the National Uranium Resource Evaluation (NURE) program cover the southeastern United States with line spacing varying from ∼2 to 10 km. These data show eTh highs over Cretaceous and Tertiary Coastal Plain sediments from the Cape Fear arch in North Carolina to eastern Alabama; these highs decrease with distance from the Piedmont. Quaternary sediments along the modern coasts show weaker eTh anomalies, except near coast-parallel ridges from South Carolina to northern Florida. Prominent eTh anomalies are also observed over large riverbeds and their floodplains, even north of the Cape Fear arch where surrounding areas are relatively low. These variations were verified using ground geophysical measurements and sample analyses, indicating that radiometric methods are a useful exploration tool at varying scales. Further analyses of heavy mineral separates showed regional differences, not only in concentrations of monazite, but also of rutile and staurolite, and in magnetic susceptibility. The combined properties suggest the presence of subregions where heavy mineral sediments are primarily sourced from high-grade metamorphic, low-grade metamorphic, or igneous terrains, or where they represent a mixing of these sources. Comparisons between interpreted sources of heavy mineral sands near the Fall Line and igneous and metamorphic Piedmont and Blue Ridge units showed a strong correspondence with rocks closest to the Fall Line and poor correspondence with rocks farther inland. This strongly suggests that the primary source of those heavy minerals, especially monazite, is the rocks that formed the rocky coast that was present during opening of the Atlantic Ocean, which in turn indicates the importance of coastal processes in forming heavy mineral sand concentrations. Furthermore, narrow radiometric eTh and K anomalies are associated with major rivers, indicating limited spatial influence of fluvial processes. Later coastal plain sediment deposition appears to have involved reworking of sediments, providing an “inheritance” of the rocky coast composition that persists for some distance from the Fall Line. However, this inheritance is reduced with distance, and sediments within ∼100 km of the coast in Georgia and Florida exhibit properties indicative of mixing from multiple sources.

Evidence shows that high field strength (HFS) elements commonly used to index chemical weathering are variably mobile. This mobility may be linked to redistribution of suspended solids. A mass-balance model is presented that can quantify such redistribution without assuming immobility for any single element. Two tropical weathering profiles on quartz diorite and basalt are examined and redistribution of the HFS elements Zr and Ti is documented, along with potential corrections for the resulting changes in measured concentrations.

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ(34)S VCDT) of -0.8‰. Bulk deposition on the island of Maui had a δ(34)S VCDT that varied temporally, spanned a range from +8.2 to +19.7‰, and reflected isotopic mixing from three sources: sea-salt (+21.1‰), marine biogenic emissions (+15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to +2.7‰) to relatively high (+17.8 to +19.3‰) soil δ(34)S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from +8.1 to +20.3‰ and generally decreased with increasing elevation (0-2000 m), distance from the coast (0-12 km), and annual rainfall (180-5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over ecosystem sulfur biogeochemistry across relatively small spatial scales.

[1] Sulfur is one of the macronutrient elements whose sources to terrestrial ecosystems should shift from dominance by rock-weathering to atmospheric deposition as soils and underlying substrate undergo progressive weathering and leaching. However, the nature and timing of this transition is not well known. We investigated sources of sulfur to tropical rain forests growing on basalt-derived soils in the Osa Peninsula region of Costa Rica. Sulfur sources were examined using stable isotope ratios (δ34S) and compared to chemical indices of soil development. The most weathered soils, and the forests they supported, are dominated by atmospheric sulfur, while a less weathered soil type contains both rock-derived and atmospheric sulfur. Patterns of increasing δ34S with increasing soil sulfur concentration across the landscape suggest atmospheric sulfur is accumulating, and little rock-derived sulfur has been retained. Soil sulfur, minus adsorbed sulfate, is correlated with carbon and nitrogen, implying that sulfur accumulation occurs as plants and microbes incorporate sulfur into organic matter. Only the lower depth increments of the more weathered soils contained significant adsorbed sulfate. The evidence suggests a pattern of soil development in which sulfur-bearing minerals in rock, such as sulfides, weather early relative to other minerals, and the released sulfate is leached away. Sulfur added via atmospheric deposition is retained as organic matter accumulates in the soil profile. Adsorbed sulfate accumulates later, driven by changes in soil chemistry and mineralogy. These aspects of sulfur behavior during pedogenesis in this environment may hasten the transition to dominance by atmospheric sources.

We evaluated the potential use of stable isotopes to establish linkages between the wintering grounds and the breeding grounds of the Pectoral Sandpiper (Calidris melanotos), the White-rumped Sandpiper (Calidris fuscicollis), the Baird's Sandpiper (Calidris bairdii), and other Neotropical migratory shorebird species (e.g., Tringa spp.). These species molt their flight feathers on the wintering grounds and hence their flight feathers carry chemical signatures that are characteristic of their winter habitat. The objective of our pilot study was to assess the feasibility of identifying the winter origin of individual birds by: (1) collecting shorebird flight feathers from several widely separated Argentine sites and analyzing these for a suite of stable isotopes; and 2) analyzing the deuterium and 18O isotope data that were available from precipitation measurement stations in Argentina. Isotopic ratios (delta13C, delta15N and delta34S) of flight feathers were significantly different among three widely separated sites in Argentina during January 2001. In terms of relative importance in separating the sites, delta34S was most important, followed by delta15N, and then delta13C. In the complete discriminant analysis, the classification function correctly predicted group membership in 85% of the cases (jackknifed classification matrix). In a stepwise analysis delta13C was dropped from the solution, and site membership was correctly predicted in 92% of cases (jackknifed matrix). Analysis of precipitation data showed that both deltaD and delta18O were significantly related to both latitude and longitude on a countrywide scale (p0.001). Other variables, month, altitude, explained little additional variation in these isotope ratios. Several issues were identified that will likely constrain the degree of accuracy one can expect in predicting the geographic origin of birds from Argentina. There was unexplained variation in isotope ratios within and among the different wing feathers from individual birds. Such variation may indicate that birds are not faithful to a local site during their winter stay in Argentina. There was significant interannual variation in the deltaD and delta18O of precipitation. Hence, specific locations may not have a constant signature for some isotopes. Moreover, the fractionation that occurs in wetlands due to evaporation significantly skews local deltaD and delta18O values, which may undermine the strong large-scale gradients seen in the precipitation data. We are continuing the research with universities in Argentina with a focus on expanding the breadth of feather collection and attempting to resolve the identified issues.

White-tailed kite (Elanus leucurus) populations in the 1930s were close to extirpation in the United States. But by the 1940s, an upward trend towards recovery was apparent and continued to their current stable population levels. These dramatic fluctuations in kite numbers may have been related to changes in rodent prey populations due to the conversion of native habitats to agriculture. To address this question, we evaluated the use of stable isotope analysis in determining if a shift in diet could be isotopically differentiated in current and historic kite populations. We first compared delta13C, delta15N, and delta34S values from present-day kite flight feathers and prey fur samples from four locations in California. The total ranges of isotope values for kite and their rodent prey were similar within each site. Carbon isotope values ranged from -27.1 to -22.2 per thousand in Arcata, -26.1 to -16.9 per thousand in Davis, -27.0 to -15.0 per thousand in Cosumnes, and -28.2 to -11.6 per thousand in Santa Barbara. Nitrogen isotope values ranged from 3.2 to 15.7 per thousand in Arcata, 2.8 to 12.7 per thousand in Davis, 4.0 to 15.7 per thousand in Cosumnes, and 1.7 to 20.0 per thousand in Santa Barbara. Sulfur isotope values ranged from -7.8 to 12.4 per thousand in Arcata, -1.1 to 9.2 per thousand in Davis, 0.7 to 10.9 per thousand in Cosumnes, and -8.6 to 15.6 per thousand in Santa Barbara. Carbon, nitrogen, and sulfur isotope values at each site reflect typical trophic enrichments due to physiological processes. At each site, delta13C and delta15N values reflected the influence of a predominantly C3 or a mixed C3/C4 plant community. Sulfur isotope values reflect the influence of predominant marine or terrestrial sulfur sources at each site. However, variability in isotope values may limit the usefulness of such analyses for addressing prey utilization and population dynamics.