Zinc isotopic signatures in eight lake sediment cores from across the United States.

Zinc is an important trace element pollutant in urban environments; however, the extent of Zn contamination and the sources of urban Zn pollution are often unclear. We measured Zn concentrations and isotopes in sediment cores collected from eight lakes or reservoirs across the United States. We paired these data with historical records of land use within each watershed to calculate a mean Zn concentration and δ(66)Zn for natural (less than 5% urban land use; 123 ± 21.7 mg/kg; +0.33 ± 0.08‰, n = 6 lakes) and urban (greater than 70% urban land use; 389 ± 200 mg/kg; +0.14 ± 0.07‰, n = 3 lakes) lake sediments. The relation between Zn concentration data and Zn isotope data allows us to create a mixing model between two end members: natural and urban. The δ(66)Zn of the urban end-member is consistent with Zn pollution from vehicle-related sources (tire wear and emissions). Application of this model to samples collected from lakes recording periods ranging from 5 to 70% urban land use in their surrounding watersheds indicates that the lakes and reservoirs were affected by large amounts of Zn from urban sources.

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels.

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

A Bayesian framework to unravel food, groundwater, and climate linkages: A case study from Louisiana.

Advancing our understanding of the connections among groundwater, food, and climate is critical to meet global food demands while optimizing water resources usage. However, our understanding of the linkages among groundwater, food, and climate is still limited. Here, we offer a Bayesian framework to simulate crop yield at a regional scale and quantify its relationships and associated uncertainty with climate, groundwater, agricultural, and energy-related variables. We implemented the framework in the rice-producing regions of Louisiana from 1960-2015. To build a parsimonious model, we used a probability-based variable selection approach to detect the key drivers of rice yield. Rice yield increased, groundwater declined, and area planted declined or did not change over 56yrs. The number of irrigation wells, groundwater level, air temperature, and area planted were found to be the key drivers of rice yield. The regression coefficients showed that rice yield was positively related to groundwater level, and negatively related to area planted and the number of irrigation wells. The limited influence of N fertilizer was noted on rice yield for the period when fertilizer data were available. The inverse relationship between rice yield and area planted pointed to the adaption of efficient crop management practices that maintained or increased yield, despite the decline in area planted. The farmers' ability to install irrigation wells during droughts sustained the yields over long-term but not short-term. This decline in rice yield in response to drought over the short-term might explain the negative relation between yield and irrigation wells. Overall, this work highlighted the uncertainty in relationships between rice yield and key drivers and quantified the intimate connection between food and groundwater. This work may have implications for managing two highly competing commodities (i.e., groundwater and food) in agricultural regions.

A Granger causality analysis of groundwater patterns over a half-century.

Groundwater depletion in many areas of the world has been broadly attributed to irrigation. However, more formal, data-driven, causal mechanisms of long-term groundwater patterns have not been assessed. Here, we conducted the first Granger causality analysis to identify the "causes" of groundwater patterns using the rice-producing parishes of Louisiana, USA, as an example. Trend analysis showed a decline of up to 6 m in groundwater level over 51 years. We found that no single cause explained groundwater patterns for all parishes. Causal linkages were noted between groundwater and area harvested, number of irrigation wells, summer precipitation totals, and drought. Bi-directional linkages were noted between groundwater and rice yield, suggesting feedback between both time series. Causal linkages were absent between groundwater and many drivers where significant correlations were noted, highlighting the importance of using robust causal relationships over illusive correlations to detect the cause. These results advance our understanding of groundwater dynamics and can reveal a key connection between food and groundwater.

Zinc isotope investigation of surface and pore waters in a mountain watershed impacted by acid rock drainage.

The pollution of natural waters with metals derived from the oxidation of sulfide minerals like pyrite is a global environmental problem. However, the metal loading pathways and transport mechanisms associated with acid rock drainage reactions are often difficult to characterize using bulk chemical data alone. In this study, we evaluated the use of zinc (Zn) isotopes to complement traditional geochemical tools in the investigation of contaminated waters at the former Waldorf mining site in the Rocky Mountains, Colorado, U.S.A. Geochemical signatures and statistical analysis helped in identifying two primary metal loading pathways at the Waldorf site. The first was characterized by a circumneutral pH, high alkalinity, and high Zn/Cd ratios. The second was characterized by acidic pHs and low Zn/Cd ratios. Zinc isotope signatures in surface water samples collected across the site were remarkably similar (the δ(66)Zn, relative to JMC 3-0749-L, for most samples ranged from 0.20 to 0.30‰±0.09‰ 2σ). This probably suggests that the ultimate source of Zn is consistent across the Waldorf site, regardless of the metal loading pathway. The δ(66)Zn of pore water samples collected within a nearby metal-impacted wetland area, however, were more variable, ranging from 0.20 to 0.80‰±0.09‰ 2σ. Here the Zn isotopes seemed to reflect differences in groundwater flow pathways. However, a host of secondary processes might also have impacted Zn isotopes, including adsorption of Zn onto soil components, complexation of Zn with dissolved organic matter, uptake of Zn into plants, and the precipitation of Zn during the formation of reduced sulfur species. Zinc isotope analysis proved useful in this study; however, the utility of this isotopic tool would improve considerably with the addition of a comprehensive experimental foundation for interpreting the complex isotopic relationships found in soil pore waters.

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria.

Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ(65)Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ(65)Cu(solution-solid) = δ(65)Cu(solution) - δ(65)Cu(solid)) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to -0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ(65)Cu(solution-solid) ranging from ~+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ(65)Cu of natural waters and soils is probably considerable.

Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake.

In this work, we use stable Zn and Cu isotopes to identify the sources and timing of the deposition of these metals in a sediment core from Lake Ballinger near Seattle, Washington, USA. The base of the Lake Ballinger core predates settlement in the region, while the upper sections record the effects of atmospheric emissions from a nearby smelter and rapid urbanization of the watershed. delta(66)Zn and delta(65)Cu varied by 0.50 per thousand and 0.29 per thousand, respectively, over the 500 year core record. Isotopic changes were correlated with the presmelter period ( approximately 1450 to 1900 with delta(66)Zn = +0.39 per thousand +/- 0.09 per thousand and delta(65)Cu = +0.77 per thousand +/- 0.06 per thousand), period of smelter operation (1900 to 1985 with delta(66)Zn = +0.14 +/- 0.06 per thousand and delta(65)Cu = +0.94 +/- 0.10 per thousand), and postsmelting/stable urban land use period (post 1985 with delta(66)Zn = 0.00 +/- 0.10 per thousand and delta(65)Cu = +0.82 per thousand +/- 0.12 per thousand). Rapid early urbanization during the post World War II era increased metal loading to the lake but did not significantly alter the delta(66)Zn and delta(65)Cu, suggesting that increased metal loads during this time were derived mainly from mobilization of historically contaminated soils. Urban sources of Cu and Zn were dominant since the smelter closed in the 1980s, and the delta(66)Zn measured in tire samples suggests tire wear is a likely source of Zn.

Cd and proton adsorption onto bacterial consortia grown from industrial wastes and contaminated geologic settings.

To model the effects of bacterial metal adsorption in contaminated environments, results from metal adsorption experiments involving individual pure stains of bacteria must be extrapolated to systems in which potentially dozens of bacterial species are present. This extrapolation may be made easier because bacterial consortia from natural environments appear to exhibit similar metal binding properties. However, bacteria that thrive in highly perturbed contaminated environments may exhibit significantly different adsorptive behavior. Here we measure proton and Cd adsorption onto a range of bacterial consortia grown from heavily contaminated industrial wastes, groundwater, and soils. We model the results using a discrete site surface complexation approach to determine binding constants and site densities for each consortium. The results demonstrate that bacterial consortia from different contaminated environments exhibit a range of total site densities (approximately a 3-fold difference) and Cd-binding constants (approximately a 10-fold difference). These ranges for Cd binding constants may be small enough to suggest that bacteria-metal adsorption in contaminated environments can be described using relatively few "averaged" bacteria-metal binding constants (in conjunction with the necessary binding constants for competing surfaces and ligands). However, if additional precision is necessary, modeling parameters must be developed separately for each contaminated environment of interest.