Transport and speciation of uranium in groundwater-surface water systems impacted by legacy milling operations.

Growing worldwide concern over uranium contamination of groundwater resources has placed an emphasis on understanding uranium transport dynamics and potential toxicity in groundwater-surface water systems. In this study, we utilized novel in-situ sampling methods to establish the location and magnitude of contaminated groundwater entry into a receiving surface water environment, and to investigate the speciation and potential bioavailability of uranium in groundwater and surface water. Streambed temperature mapping successfully identified the location of groundwater entry to the Little Wind River, downgradient from the former Riverton uranium mill site, Wyoming, USA. Diffusive equilibrium in thin-film (DET) samplers further constrained the groundwater plume and established sediment pore water solute concentrations and patterns. In this system, evidence is presented for attenuation of uranium-rich groundwater in the shallow sediments where surface water and groundwater interaction occurs. Surface water grab and DET sampling successfully detected an increase in river uranium concentrations where the groundwater plume enters the Little Wind River; however, concentrations remained below environmental guideline levels. Uranium speciation was investigated using diffusive gradients in thin-film (DGT) samplers and geochemical speciation modelling. Together, these investigations indicate uranium may have limited bioavailability to organisms in the Little Wind River and, possibly, in other similar sites in the western U.S.A. This could be due to ion competition effects or the presence of non- or partially labile uranium complexes. Development of methods to establish the location of contaminated (uranium) groundwater entry to surface water environments, and the potential effects on ecosystems, is crucial to develop both site-specific and general conceptual models of uranium behavior and potential toxicity in affected ground and surface water environments.

Natural and anthropogenic processes affecting radon releases during mining and early stage reclamation activities, Pinenut uranium mine, Arizona, USA.

Radon (Rnair) was monitored in open air in publicly accessible areas surrounding the Pinenut uranium (U) mine during mining and reclamation activities in 2015-16 to address concerns about mining related effects to areas surrounding Grand Canyon National Park (GCNP) in Arizona, USA. During July 2015, Rnair concentrations associated with the ore storage pile monitoring site were larger than those at the mine vent monitoring site and likely resulted from the relatively large amount of ore stored on site during this period. Higher wind velocities at the ore pile monitoring site generally resulted in lower Rnair concentrations; however, wind velocity did not appear to be an important factor in controlling Rnair concentrations at the mine vent monitoring site. Physical disturbances of the ore pile by heavy equipment did not coincide with elevated Rnair concentrations at the ore storage pile or mine vent monitoring sites. The relative size of the ore storage pile showed a positive trend with the daily mean Rnair concentration measured at the ore pile monitoring site. Principal component analysis (PCA) was applied to the ore pile and mine vent multivariate data sets for simultaneous comparison of all measured variables during 230 days of the study period. A significant positive coefficient for Rnair was associated with a significant negative coefficient for wind speed for principal component (PC) 2ore pile. Significant, positive PC2mine vent coefficients included Rnair, wind direction, and relative ore pile size indicating that Rnair variations at the mine vent monitoring site may be affected by Rn sourced from the ore pile. The ore pile is located about 200 m south of the mine vent Rn monitor with the prevalent wind direction coming from the south. All data generated during the field study and laboratory verification tests were published by Naftz et al. (2018) and are available online at: https://doi.org/10.5066/F79Z946T.

Improved enrichment factor calculations through principal component analysis: Examples from soils near breccia pipe uranium mines, Arizona, USA.

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.

Effect of salinity on mercury methylating benthic microbes and their activities in Great Salt Lake, Utah.

Surface water and biota from Great Salt Lake (GSL) contain some of the highest documented concentrations of total mercury (THg) and methylmercury (MeHg) in the United States. In order to identify potential biological sources of MeHg and controls on its production in this ecosystem, THg and MeHg concentrations, rates of Hg(II)-methylation and MeHg degradation, and abundances and compositions of archaeal and bacterial 16 rRNA gene transcripts were determined in sediment along a salinity gradient in GSL. Rates of Hg(II)-methylation were inversely correlated with salinity and were at or below the limits of detection in sediment sampled from areas with hypersaline surface water. The highest rates of Hg(II)-methylation were measured in sediment with low porewater salinity, suggesting that benthic microbial communities inhabiting less saline environments are supplying the majority of MeHg in the GSL ecosystem. The abundance of 16S rRNA gene transcripts affiliated with the sulfate reducer Desulfobacterium sp. was positively correlated with MeHg concentrations and Hg(II)-methylation rates in sediment, indicating a potential role for this taxon in Hg(II)-methylation in low salinity areas of GSL. Reactive inorganic Hg(II) (a proxy used for Hg(II) available for methylation) and MeHg concentrations were inversely correlated with salinity. Thus, constraints imposed by salinity on Hg(II)-methylating populations and the availability of Hg(II) for methylation are inferred to result in higher MeHg production potentials in lower salinity environments. Benthic microbial MeHg degradation was also most active in lower salinity environments. Collectively, these results suggest an important role for sediment anoxia and microbial sulfate reducers in the production of MeHg in low salinity GSL sub-habitats and may indicate a role for salinity in constraining Hg(II)-methylation and MeHg degradation activities by influencing the availability of Hg(II) for methylation.

A 50-year record of NOx and SO2 sources in precipitation in the Northern Rocky Mountains, USA.

Ice-core samples from Upper Fremont Glacier (UFG), Wyoming, were used as proxy records for the chemical composition of atmospheric deposition. Results of analysis of the ice-core samples for stable isotopes of nitrogen (δ15N, ) and sulfur (δ34S, ), as well as and deposition rates from the late-1940s thru the early-1990s, were used to enhance and extend existing National Atmospheric Deposition Program/National Trends Network (NADP/NTN) data in western Wyoming. The most enriched δ34S value in the UFG ice-core samples coincided with snow deposited during the 1980 eruption of Mt. St. Helens, Washington. The remaining δ34S values were similar to the isotopic composition of coal from southern Wyoming. The δ15N values in ice-core samples representing a similar period of snow deposition were negative, ranging from -5.9 to -3.2 ‰ and all fall within the δ15N values expected from vehicle emissions. Ice-core nitrate and sulfate deposition data reflect the sharply increasing U.S. emissions data from 1950 to the mid-1970s.

Selenium and trace element mobility affected by periodic displacement of stratification in the Great Salt Lake, Utah.

The Great Salt Lake (GSL) is a unique ecosystem in which trace element activity cannot be characterized by standard geochemical parameters due to the high salinity. Movement of selenium and other trace elements present in the lake bed sediments of GSL may occur due to periodic stratification displacement events or lake bed exposure. The water column of GSL is complicated by the presence of a chemocline persistent over annual to decadal time scales. The water below the chemocline is referred to as the deep brine layer (DBL), has a high salinity (16.5 to 22.9%) and is anoxic. The upper brine layer (UBL) resides above the chemocline, has lower salinity (12.6 to 14.7%) and is oxic. Displacement of the DBL may involve trace element movement within the water column due to changes in redox potential. Evidence of stratification displacement in the water column has been observed at two fixed stations on the lake by monitoring vertical water temperature profiles with horizontal and vertical velocity profiles. Stratification displacement events occur over periods of 12 to 24h and are associated with strong wind events that can produce seiches within the water column. In addition to displacement events, the DBL shrinks and expands in response to changes in the lake surface area over a period of months. Laboratory tests simulating the observed sediment re-suspension were conducted over daily, weekly and monthly time scales to understand the effect of placing anoxic bottom sediments in contact with oxic water, and the associated effect of trace element desorption and (or) dissolution. Results from the laboratory simulations indicate that a small percentage (1%) of selenium associated with anoxic bottom sediments is periodically solubilized into the UBL where it potentially can be incorporated into the biota utilizing the oxic part of GSL.

Volatile selenium flux from the Great Salt Lake, Utah.

The removal mechanisms that govern Se concentrations in the Great Salt Lake are unknown despite this terminal lake being an avian habitat of hemispheric importance. However, the volatilization flux of Se from the Great Salt Lake has not been previously measured due to challenges of analysis in this hypersaline environment This paper presents results from recent field studies examining the spatial distribution of dissolved volatile Se (areally and with depth) in the south arm (main body) of the Great Salt Lake. The analyses involved collection of dissolved volatile Se in a cryofocusing trap system via sparging with helium. The cryotrapped volatile Se was digested with nitric acid and analyzed by inductively coupled plasma mass spectrometry(ICP-MS). Results show concentrations of dissolved volatile Se that increase with depth in the shallow brine, suggesting that phytoplankton in the open waters and bioherms in shallow sites (<4 m in depth) may be responsible for volatile Se production. Volatile Se flux to the atmosphere was determined using mass transport models corrected to simulate the highly saline environment of the south arm of the Great Salt Lake. The estimated annual flux of volatile Se was 1455 kg/year within a range from 560 to 3780 kg Se/year for the 95% confidence interval and from 970 to 2180 kg Se/year within the 68% confidence interval.

Selenium mass balance in the Great Salt Lake, Utah.

A mass balance for Se in the south arm of the Great Salt Lake was developed for September 2006 to August 2007 of monitoring for Se loads and removal flows. The combined removal flows (sedimentation and volatilization) totaled to a geometric mean value of 2079 kg Se/yr, with the estimated low value being 1255 kg Se/yr, and an estimated high value of 3143 kg Se/yr at the 68% confidence level. The total (particulates+dissolved) loads (via runoff) were about 1560 kg Se/yr, for which the error is expected to be +/-15% for the measured loads. Comparison of volatilization to sedimentation flux demonstrates that volatilization rather than sedimentation is likely the major mechanism of selenium removal from the Great Salt Lake. The measured loss flows balance (within the range of uncertainties), and possibly surpass, the measured annual loads. Concentration histories were modeled using a simple mass balance, which indicated that no significant change in Se concentration was expected during the period of study. Surprisingly, the measured total Se concentration increased during the period of the study, indicating that the removal processes operate at their low estimated rates, and/or there are unmeasured selenium loads entering the lake. The selenium concentration trajectories were compared to those of other trace metals to assess the significance of selenium concentration trends.

Utilizing geochemical, hydrologic, and boron isotopic data to assess the success of a salinity and selenium remediation project, Upper Colorado River Basin, Utah.

Stream discharge and geochemical data were collected at two sites along lower Ashley Creek, Utah, from 1999 to 2003, to assess the success of a site specific salinity and Se remediation project. The remediation project involved the replacement of a leaking sewage lagoon system that was interacting with Mancos Shale and increasing the dissolved salinity and Se load in Ashley Creek. Regression modeling successfully simulated the mean daily dissolved salinity and Se loads (R(2) values ranging from 0.82 to 0.97) at both the upstream (AC1) and downstream (AC2/AC2A) sites during the study period. Prior to lagoon closure, net gain in dissolved-salinity load exceeded 2177 metric tons/month and decreased after remediation to less than 590 metric tons/month. The net gain in dissolved Se load during the same pre-closure period exceeded 120 kg/month and decreased to less than 18 kg/month. Sen's slope estimator verified the statistical significance of the modeled reduction in monthly salinity and Se loads. Measured gain in dissolved constituent loads during seepage tests conducted during September and November 2003 ranged from 0.334 to 0.362 kg/day for dissolved Se and 16.9 to 26.1 metric tons/day for dissolved salinity. Stream discharge and changes in the isotopic values of delta boron-11 (delta(11)B) were used in a mixing model to differentiate between constituent loadings contributed by residual sewage effluent and naturally occurring ground-water seepage entering Ashley Creek. The majority of the modeled delta(11)B values of ground-water seepage were positive, indicative of minimal seepage contributions from sewage effluent. The stream reach between sites S3 and AC2A contained a modeled ground-water seepage delta(11)B value of -2.4 per thousand, indicative of ground-water seepage composed of remnant water still draining from the abandoned sewage lagoons.

Atmospherc mercury deposition during the last 270 years: a glacial ice core record of natural and anthropogenic sources.

Mercury (Hg) contamination of aquatic ecosystems and subsequent methylmercury bioaccumulation are significant environmental problems of global extent. At regional to global scales, the primary mechanism of Hg contamination is atmospheric Hg transport. Thus, a better understanding of the long-term history of atmospheric Hg cycling and quantification of the sources is critical for assessing the regional and global impact of anthropogenic Hg emissions. Ice cores collected from the Upper Fremont Glacier (UFG), Wyoming, contain a high-resolution record of total atmospheric Hg deposition (ca. 1720-1993). Total Hg in 97 ice-core samples was determined with trace-metal clean handling methods and low-level analytical procedures to reconstruct the first and most comprehensive atmospheric Hg deposition record of its kind yet available from North America. The record indicates major atmospheric releases of both natural and anthropogenic Hg from regional and global sources. Integrated over the past 270-year ice-core history, anthropogenic inputs contributed 52%, volcanic events 6%, and background sources 42%. More significantly, during the last 100 years, anthropogenic sources contributed 70% of the total Hg input. Unlike the 2-7-fold increase observed from preindustrial times (before 1840) to the mid-1980s in sediment-core records, the UFG record indicates a 20-fold increase for the same period. The sediment-core records, however, are in agreement with the last 10 years of this ice-core record, indicating declines in atmospheric Hg deposition.