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At least 325 records · Page 18Linked to original sources

Contrasting mobilization of elements in contact with sediment from Lake Roosevelt and the Upper Columbia River, Washington, USA

Trace element contamination is known to be widely present in sediment of Lake Roosevelt and the riverine reach of the Columbia River in Washington State, USA due to discharges from several smelters and numerous mines dating back to the mid-1800's. In this study, the concentrations of aqueous elements in contact with bed sediment from the lake and river were examined under varying degrees of physical mixing and time scales. Contrasting geochemical processes affecting aqueous concentrations were inferred from the release of major ions (Ca and Si), elements enriched in metallurgical smelter slag (Cu and Sb), and redox-sensitive species (Fe, Mn, Mo and U). Releases of major ions reflect the contrasting sediment substrates along the length of the river and large reservoir. Calcium released from carbonate minerals and slag particles was most pronounced in regions of carbonate bedrock and near sediment deposits with a large component of slag material, while Si released from unconsolidated glacial/fluvial sediment increased with increasing distance downstream. Sb release was a consistent indicator of slag presence and weathering, possibly because its anionic nature inhibits readsorption onto metal oxides. In contrast, Cu release was quite variable, likely due to varying degrees of copper readsorption or co-precipitation onto metal oxides. The release of Mo and U appeared to be affected by redox conditions, which were assessed using aqueous Fe and Mn concentrations.

Washington↗

Cinnamon gulch revisited: Another look at separating natural and mining-impacted contributions to instream metal load

Baseline, premining data for streams draining abandoned mine lands is virtually non existent, and indirect methods for estimating premining conditions are needed to establish realistic, cost effective cleanup goals. One such indirect method is the proximal analog approach, in which premining conditions are estimated using data from nearby mineralized areas that are unaffected by mining. In this paper, we combine the proximal analog approach with a quantitative mass balance framework using data from a spatially-detailed synoptic sampling campaign. The combined approach is applied to Cinnamon Gulch, a headwater stream with numerous draining adits. Synoptic sampling results indicate that three of the top five metal sources are affected by mining activities, and stream segments draining these sources account for a large percentage of overall metal loading within the study reach. These initial calculations overestimate the effects of mining, as the affected stream segments were likely acidic and metal rich prior to mining. Premining loads and concentrations were therefore determined through a replacement approach in which the chemistry of each mining-affected stream segment is revised based on proximal analog concentrations. The revised loading profiles indicate that 15–17% of the Al, Cd, Cu, Mn, Ni, and Zn loads are attributable to mining, whereas the mining contribution for Pb is 40%. Premining concentrations of Al, Cd, Cu, Mn, and Zn are estimated to be in excess of aquatic life standards over the length of the study reach.

Colorado↗

Application of hydrologic-tracer techniques to the Casargiu adit and Rio Irvi (SW-Sardinia, Italy): Using enhanced natural attenuation to reduce extreme metal loads

Hydrologic tracer techniques were applied to Rio Irvi (SW Sardinia), a stream affected by mine drainage, allowing the calculation of stream discharge and metal loads and comparison to other streams. The calculated discharge showed a continuous increase from near 21.2 L/s to 29.1 L/s. Cumulative loads of mine-related constituents, including the Casargiu adit inflow, were large, with more than 9900 kg/day of SO 4 2− , 2370 kg/day of Zn, 550 kg/day of Fe and 172 kg/day of Mn. The greatest measurable inflow source of metals, other than the Casargiu adit, was an acidic tributary (L4), but most sources of instream metal load were related to dispersed groundwater inflows. Some of those groundwater inflows were related to non-flowing tributaries. Calculations of the cumulative instream metal load, excluding the Casargiu adit inflow, indicated increases of 1250 kg/day for SO 4 2 , 858 kg/day for Zn - , 137 kg/day gain for Fe and 60 kg/day for Mn. Rio Irvi Zn load was extreme for a stream of this size and discharge. A comparison with two other mine-affected rivers in Sardinia indicated the loading in Rio Irvi was two to three orders of magnitude greater. This difference was attributed to different geochemical conditions, but also to a lack of a biogeochemical barrier like that seen to be acting along and below the riverbed in Rio San Giorgio. Several years of intense vegetation growth in the river bed of Rio San Giorgio created a biogeochemical barrier to metal loading, and the cumulative Zn load there was near 8 kg/day, despite being a drainage with a greater mass of mine wastes to contribute to the load.

Sardinia↗

Combined radiogenic (87Sr/86Sr, 234U/238U) and stable (δ88Sr) isotope systematics as tracers of anthropogenic groundwater contamination within the Williston Basin USA

The Williston Basin has produced oil and gas from conventional structural and stratigraphic traps for more than 60 years. The advent of horizontal drilling and hydraulic fracturing of shale in the Devonian-Mississippian Bakken Formation has increased the production of oil in this basin from areas that partially overlap the prairie pothole region of North America. Massive scale of oil production in the Williston Basin increases the risk of accidental releases of coproduced formation water (brine) into the environment. The prairie pothole region is named for a multitude of small lakes and wetlands that provide critical habitat for waterfowl and other wildlife. The increased risks raise the importance of developing robust tracers that can identify the source(s) and quantity of contamination of this premier wetland ecosystem. Radiogenic 87 Sr/ 86 Sr and 234 U/ 238 U isotope tracers are widely used in hydrological studies to detect potential sources of groundwater contamination. Here, we used paired 87 Sr/ 86 Sr and δ 88 Sr values in wetland water, which is essentially shallow groundwater at the Goose Lake and Fuller sites in Montana and North Dakota where produced water contamination was previously established. We also analyzed brines from the Bakken Formation and Mississippian Charles Formation to evaluate potential sources of contamination. This is the first attempt to combine these isotope tracers to estimate a magnitude of groundwater contamination by the oil-field produced water. Moreover, because U +6 is soluble in water under subaerial oxidizing conditions and the U +4 content is orders of magnitude lower (pg/g levels) in reducing brines, the 234 U/ 238 U isotope tracer is insensitive to brine contamination. However, it elucidates potential variability of uncontaminated end-members and, therefore, helps to improve the accuracy of estimated degrees of brine contamination based on binary mixing relationships. In addition, U isotopes in groundwater have a potential for detecting some U-rich anthropogenic contaminants (e.g., phosphate fertilizers). Using these isotopic systematics we confirm previous conclusions that surface water and shallow groundwater in two studied sites are variably contaminated by produced water and estimate the degree of the contamination at ∼7% in a sample collected close to a brine tank and <0.5% in most other samples. The U isotope analyses in combination with the Sr isotope results help outline variable groundwater pathways and uncontaminated end-members. Also, U isotopes show no appreciable groundwater contamination from U-enriched P-fertilizers. Our study in the Williston Basin demonstrates the potential of using combined radiogenic ( 87 Sr/ 86 Sr, 234 U/ 238 U) and non-traditional stable (δ 88 Sr) isotopic systematics as tracers of anthropogenic contamination in surface and groundwater systems.

Montana, North Dakota↗

Cadmium isotope fractionation during coal combustion: Insights from two U.S. coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of ∼70% amorphous Al-Si-rich glasses and ∼30% mineral phases of quartz (SiO 2 ) and mullite (Ai 6 Si 2 O 13 ). The Cd isotope compositions (δ 114 Cd, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from −0.51 to +0.47‰) are distinctively heavier than those of BA samples (−0.75 to −0.52‰) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+1.10 to +7.09‰), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (−0.43 to +1.18‰). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.

New Mexico, Ohio↗

Four-dimensional isotopic approach to identify perchlorate sources in groundwater: Application to the Rialto-Colton and Chino subbasins, southern California (USA)

Perchlorate (ClO 4 − ) in groundwater can be from synthetic or natural sources. Natural sources include ClO 4 − associated with historical application of imported natural nitrate fertilizer from the Atacama Desert of Chile, and indigenous ClO 4 − that accumulates locally in arid regions from atmospheric deposition. The Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California, includes two mapped ClO 4 − plumes from known military/industrial sources. Larger areas downgradient from those plumes, and in the Chino subbasin to the southwest, also contain ClO 4 − . Perchlorate from wells was analyzed for chlorine and oxygen stable isotope ratios (δ 37 Cl, δ 18 O, Δ 17 O) and radioactive chlorine-36( 36 Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotopic data show that synthetic ClO 4 − was the dominant source within the mapped plumes. Downgradient from the mapped plumes, and in the Chino subbasin, the dominant source of ClO 4 − was related to past agricultural use of Chilean (Atacama) nitrate fertilizer. The 36 Cl and δ 18 O data indicate that wells having predominantly synthetic or Atacama ClO 4 − also contained small fractions of indigenous ClO 4 − . Little or no differences were observed in isotopic composition or ClO 4 − source with depth in depth-dependent data from selected wells. Indigenous ClO 4 − was most evident in upgradient wells having ClO 4 − concentrations <1 μg/L, consistent with its occurrence as a background constituent throughout the region. Stable isotope ratios of chlorine and oxygen and 36 Cl isotopic abundance data provided relatively unambiguous discrimination of synthetic and Atacama sources in most wells having ClO 4 − concentrations greater than 1 μg/L.

California↗

Radium attenuation and mobilization in stream sediments following oil and gas wastewater disposal in western Pennsylvania

Centralized waste treatment facilities (CWTs) in Pennsylvania discharged wastewater from conventional and unconventional oil and gas (O&G) wells into surface waters until 2011, when a voluntary request from the Pennsylvania Department of Environmental Protection (PA DEP) encouraged recycling rather than treating and discharging unconventional O&G wastewater. To determine the effect of this request on the occurrence of radium in streams, we sampled sediments at five CWTs that processed conventional O&G wastewater from 2011 to 2017 and compared results to published data. Despite the policy change in 2011 that reduced disposal of unconventional wastes (i.e., Marcellus) to surface water in Pennsylvania, the continued disposal of conventional O&G wastewater led to elevated radium activities in sediments at the point of discharge that were often hundreds of times higher than background. While these elevated activities were also present in downstream sediments (1.5× higher than background), the elimination of unconventional O&G wastewater disposal through the CWTs since 2011 decreased radium loading to the stream by approximately 95%. Sequential extractions and geochemical modeling using PHREEQC indicate that radium likely co-precipitates with barite or barite-celestite solid solutions and accumulates in the sediment as treated O&G effluent enters the stream. Adsorption of “exchangeable” radium, barium , and strontium on hydrous iron and manganese oxide coatings on fine-grained stream sediments is an important radium sequestration mechanism further downstream that can decrease the cation concentrations and potential for radio-barite co-precipitation. Radium downstream of CWTs was more abundant and more available for dissolution and desorption than radium in upstream sediments.

Pennsylvania↗

Factors affecting the occurrence of lead and manganese in untreated drinking water from Atlantic and Gulf Coastal Plain aquifers, eastern United States—Dissolved oxygen and pH framework for evaluating risk of elevated concentrations

Groundwater samples collected during 2012 and 2013 from public-supply wells screened in the Atlantic and Gulf Coastal Plain aquifers of the eastern and southeastern U.S. rarely contained lead or manganese concentrations that exceeded drinking-water limits, despite having corrosive characteristics. Data indicate that the occurrence of dissolved lead and manganese in sampled groundwater, prior to its distribution or treatment, was related to several explanatory factors including the presence of source minerals, hydrologic position along the flow path, water-rock interactions, and associated geochemical conditions such as pH and dissolved oxygen (DO) concentrations. Elevated concentrations of lead compared to health-based benchmarks were associated with groundwater that is acidic (pH ≤ 6.5), oxygenated (DO ≥ 2 mg/L), and closer to recharge zones (relatively young water). Elevated concentrations of manganese were associated with groundwater that is acidic to neutral (pH ≤ 7.5), has low DO (<2 mg/L), and further from recharge zones (relatively old). Under these geochemical conditions, minerals that could sequester lead or manganese tended to be undersaturated, and adsorption by hydrous ferric oxide was limited. Under neutral to alkaline pH conditions, precipitation of impure calcium carbonate or phosphate compounds containing traces of lead or manganese (solid solutions) could maintain low concentrations of the trace elements. Additionally, adsorption of lead or manganese cations by hydrous ferric oxides (HFO) could be another attenuating factor where conditions are oxidizing and dissolved inorganic carbon concentrations are relatively low. A DO/pH framework was developed as a screening tool for evaluating risk of elevated lead or manganese, based on the occurrence of elevated lead and manganese concentrations and the corresponding distributions of DO and pH in the Atlantic and Gulf Coastal Plain aquifers. Validation of the DO/pH framework was accomplished using an independent national dataset that showed consistent results for elevated lead (pH ≤ 6.5; DO ≥ 2 mg/L) and manganese (pH ≤ 7.5; DO < 2 mg/L).

Atlantic and Gulf Coastal Plain aquifers↗

Groundwater quality of a public supply aquifer in proximity to oil development, Fruitvale Oil Field, Bakersfield, California

Due to concerns over the effects of oil production activities on groundwater quality in California, chemical, isotopic, dissolved gas and age-dating tracers were analyzed in samples collected from public-supply wells and produced-water sites in the Fruitvale oil field (FVOF). A combination of newly collected and historical data was used to determine whether oil formation fluids have mixed with groundwater used for public supply and what the potential pathways for the migration of oil formation fluids into groundwater may be. Stable isotopes of water (δ 2 H and δ 18 O) and age dating ( 3 H, 3 He trit , SF 6 and 14 C) tracers in groundwater samples were consistent with the Kern River being the main source of recharge to aquifers. The distribution of major ion concentrations and pH with distance from the Kern River indicate that natural processes were the primary controls on groundwater salinity. Two of 14 groundwater samples had δ 13 C-DIC values (−2.4 to +1.9 per mil) consistent with mixtures of <1 to about 9 percent oil-field water. Concentrations of TDS in groundwater samples were generally much lower (129–1,200 milligrams per liter (mg/l), median 216 mg/l) than produced water samples (586–24,930 mg/l, median 2,717 mg/l), suggesting that any mixing of oil-field water with groundwater has not significantly affected groundwater salinity. Trace concentrations of thermogenic methane were detected in three groundwater samples that did not have dissolved inorganic or isotopic indicators consistent with mixing of oil-field water, suggesting that stray gases may have migrated from the subsurface via preferential pathways such as leaky well bores into groundwater aquifers. Low concentrations of petroleum hydrocarbons were detected in samples that also contained anthropogenic VOCs and components of post- and pre-1950s recharge, indicating that petroleum hydrocarbons could have come from subsurface and/or surface sources. Overall, the results of this study indicated that groundwater currently used for public supply in the FVOF was of good quality with little, if any, effects from oil production activities. This may be due in part to the relatively rapid flushing of the aquifer system by recharge from the Kern River.

California↗

Potential for increased hydrothermal arsenic flux during volcanic unrest: Implications for California water supply

The hydrothermal systems associated with the restless high-threat volcanoes at Lassen and Long Valley, California, each release large amounts of arsenic (As) to surface waters – ~6 and ~8 metric tons/yr, respectively. The hydrothermal As output can increase during volcanic unrest, as illustrated by a two-fold increase during unrest at Lassen in 2014–15. During that period of unrest, increased As concentrations and fluxes were measured up to 75 km downstream from the Lassen source, in Mill Creek near the confluence with the Sacramento River. In eastern California, the Long Valley hydrothermal system feeds into the Los Angeles Aqueduct (LAA), and the Los Angeles Department of Water and Power (LADWP) actively manages the LAA system to remove hydrothermal As. In 1980, during a series of ~ M w 6 earthquakes, the discharge of a particular group of hydrothermal vents in Long Valley increased approximately 7-fold, though the total increase in As flux to the LAA system at that time is unknown. The likely mechanism for increased hydrothermal discharge in each case is permeability enhancement due to strong ground motion. A review of the global literature on earthquake hydrology suggests a worst-case scenario of a roughly 10-fold increase in permeability, with commensurate increase in the hydrothermal As flux persisting for days to months. Here we evaluate the potential impact of such increases in hydrothermal As flux on the California water-supply system.

California↗

Sources, fate, and flux of geothermal solutes in the Yellowstone and Gardner Rivers, Yellowstone National Park, WY

The total discharge and thermal output from the numerous hydrothermal features in Yellowstone National Park (YNP) can be estimated from the chloride (Cl) flux in the Madison, Yellowstone, Falls, and Snake Rivers. Monitoring the Cl flux in these four major rivers provides a holistic view of the hydrothermal output from YNP and changes in the Cl flux may indicate changes in geothermal or magmatic activity. In this study, the source, fate, and flux of geothermal solutes in the Yellowstone River and Gardner Rivers were determined. Beginning in 2012, the fluxes of geothermal solutes, including Cl, were determined at monitoring sites in the Yellowstone and Gardner Rivers downstream of geothermal inputs within YNP. A method was developed using specific conductance as a surrogate measure for solute concentrations at these monitoring sites. Combining continuous (15-min) specific conductance and discharge data, Cl and other geothermal solute fluxes were determined at both sites and approximately 32% of the Cl flux exiting YNP is from the Yellowstone River watershed. Synoptic sampling of river water and discharge measurements were performed during low-flow conditions of September 2014 allowed for the determinations of geothermal solute sources and their downstream fate. Thus, the contribution of geothermal solutes from the various geothermal areas at the downstream monitoring sites was quantified. The thermal features draining into Yellowstone Lake account for 34% of the Cl flux at the Yellowstone River monitoring site which is located approximately 5 km north of YNP. The Gardner River, which captures geothermal water from Mammoth Hot Springs, is responsible for 22% of the Cl at the Yellowstone River monitoring site. Because the Yellowstone River watershed is large and contains numerous thermal areas, knowing the source and fate of geothermal solutes is import baseline information that can be used to identify future changes in thermal activity.

Wyoming↗

Formation and prevention of pipe scale from acid mine drainage at Iron Mountain and Leviathan Mines, California, USA

Pipelines carrying acid mine drainage (AMD) to treatment plants commonly form pipe scale, an Fe(III)-rich precipitate that forms inside the pipelines and requires periodic and costly cleanout and maintenance. Pipelines at Iron Mountain Mine (IMM) and Leviathan Mine (LM) in California carry acidic water from mine sources to a treatment plant and have developed pipe scale. Samples of scale and AMD were collected from both mine sites for mineralogical, microbiological, and chemical analysis. The scale mineralogy was primarily schwertmannite with minor amounts of poorly crystalline goethite. Although the bulk composition of the scale was similar along the length of the pipeline at IMM, the number of iron-oxidizing bacteria and concentrations of associated trace elements decreased along the flow-path inside the pipeline. Laboratory batch experiments with unfiltered AMD from IMM and LM showed that Fe(II) oxidation was driven by microbial activity when the pH was <5. A remediation strategy of decreasing the pH to <2.2 was tested through geochemical modeling and laboratory experiments. These experiments indicated that scale formation could be prevented by decreasing the pH, which could be achieved at IMM by mixing source waters. However, the presence of Fe(III)-rich scale in a pipeline buffers the pH to higher values that may affect the efficacy of this remedial approach.

California↗

Antimony mobility during the early stages of stibnite weathering in tailings at the Beaver Brook Sb deposit, Newfoundland

The aqueous speciation and mineralogy of antimony (Sb) in waters and tailings at Beaver Brook antimony deposit have been analyzed to understand Sb mobility during the initial stages of stibnite (Sb2S3) weathering in a near-surface environment. Dissolution of stibnite in oxidizing conditions releases Sb in drainage water and Sb is incorporated into the mineral structures of several secondary minerals. The most abundant Sb host in Beaver Brook tailings is primary stibnite, which dissolves, releasing Sb(III) to the pore water which rapidly oxidizes to Sb¬(V). The maximum concentration of Sb in tailings pore water is 26.4 mg/L and only 0.9% is in form of Sb(III). In all surface water, Sb concentration ranges from 0.01 to 26.1 mg/L (average 9.4 mg/L) and is mostly present in its Sb(V) (98.9 to 99.2 % of total Sb). The secondary minerals containing Sb formed in tailings impoundment, include tripuhyite-like Sb-Fe oxides (FeSbO4) where Sb is an important part of their structure with variable Fe/Sb ratios and Sb concentrations of up to 37.8% by weight (average of 21.7%). These are important Sb host phases in the top 30 cm of tailings. Iron oxides enriched in Sb, such as goethite (FeOOH), where Sb (average of 3.9% by weight) is adsorbed or incorporated in the structure are common but represent less than 1.3 % of the total mass of Sb. The elevated Mg concentrations in tailing ponds and pore water promote the precipitation of brandholzite (Mg[Sb(OH)6]2·6H2O) (in association with gypsum) during dry periods, which is easily dissolved during rainy periods. Brandholzite dissolution may significantly contribute to the concentration of dissolved Sb, together with stibnite dissolution, whereas Sb-Fe oxides are stable in the neutral pH, oxidized surface environment. Arsenic (As) accompanies Sb in all media but its behaviour differs from that of Sb. The source of As is arsenopyrite, which decomposes more slowly than stibnite. This may be due to the formation of oxidation rims on arsenopyrite grains composed of Fe, As, S, Sb and Ca which slow the dissolution, whereas no rims are seen on stibnite. Also, despite similar As and Sb concentration in bulk tailings, the concentration of Sb in drainage water is higher than that of As. In pore water, As(III) is the dominant oxidation state of As suggesting that the oxidation of dissolved As is slower than that of Sb.

Newfoundland↗

Batch extraction method to estimate total dissolved solids (TDS) release from coal refuse and overburden

A rapid batch extraction method was evaluated to estimate potential for total dissolved solids (TDS) release by 65 samples of rock from coal and gas-bearing strata of the Appalachian Basin in eastern USA. Three different extractant solutions were considered: deionized water (DI), DI equilibrated with 10% CO 2 atmosphere (DI + CO 2 ), or 30% H 2 O 2 under 10% CO 2 (H 2 O 2 +CO 2 ). In all extractions, 10 g of pulverized rock (<0.5-mm) were mixed with 20 mL of extractant solution and shaken for 4 h at 50 rpm and 20–22 °C. The 65 rock samples were classified as coal (n=3), overburden (n = 17), coal refuse that had weathered in the field (n = 14), unleached coal refuse that had oxidized during indoor storage (n = 20), gas-bearing shale (n = 10), and pyrite (n = 1). Extracts were analyzed for specific conductance (SC), TDS, pH, and major and trace elements, and subsequently speciated to determine ionic contributions to SC. The pH of extractant blanks decreased in the order DI (6.0), DI + CO 2 (5.1), and H 2 O 2 +CO 2 (2.6). The DI extractant was effective for mobilizing soluble SO 4 and Cl salts. The DI + CO 2 extractant increased weathering of carbonates and resulted in equivalent or greater TDS than the DI leach of the same material. The H 2 O 2 +CO 2 extractant increased weathering of sulfides (and carbonates) and resulted in the greatest TDS production and lowest pH values. Of the 65 samples, 19 had leachate chemistry data from previous column experiments and 35 were paired to 10 field sites with leachate chemistry data. When accounting for the water-to-rock ratio, TDS from DI and DI + CO 2 extractions were correlated to TDS from column experiments while TDS from H 2 O 2 +CO 2 extractions was not. In contrast to column experiments, field SC was better correlated to SC measured from H 2 O 2 +CO 2 extractions than DI extractions. The field SC and SC from H 2 O 2 +CO 2 extractions were statistically indistinguishable for 7 of 9 paired data sets while SC from DI extractions underestimated field SC in 5 of 9 cases. Upscaling comparisons suggest that (1) weathering reactions in the field are more aggressive than DI water or synthetic rainwater extractants used in batch or column tests, and (2) a batch extraction method utilizing 30% H 2 O 2 (which is mildly acidic without CO 2 enrichment) could be effective for identifying rocks that will release high amounts of TDS.

Applied Geochemistry↗

Natural attenuation can lead to environmental resilience in mine environment

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

Sardinia↗

Assessing mercury distribution using isotopic fractionation of mercury processes and sources adjacent and downstream of a legacy mine district in Tuscany, Italy

Mercury (Hg) concentrations and isotopic compositions in a range of sample types collected from the legacy Abbadia San Salvatore Mine (ASSM) area were used to evaluate the distribution of Hg in the region. The district generated more than 100,000 metric tons of Hg releasing extensive amounts of gaseous Hg emissions and producing large amounts of mine waste calcine from which Hg can be mobilized into the local and regional environments. Direct and indirect impact from cinnabar ore mining and processing resulted in elevated Hg concentrations in the calcine, soils, lake and stream sediments, and fish samples collected at and downstream of ASSM. The contribution of Hg from the different sources and processes resulted in a wide range of 202Hg and 199Hg isotopic compositions (-2.25 to 0.96‰, -0.12 to 0.72‰ respectively). Fish samples resulted in negative values for 202Hg (-0.53 to -1.21‰) and positive Hg (0.12 to 0.73‰). Primary cinnabar ore and present-day geothermal water and precipitate showed distinctly negative 202Hg (-0.96 to -2.25‰), whereas waste calcine were enriched in 202Hg (202Hg from about -1 to +1‰); soils and sediments show intermediate compositions, reflecting different extents of contributions from the various Hg sources and processes. These sources and processes of Hg include weathering cinnabar, gaseous Hg emissions from ore processing, and geothermal activity to a lesser extent. Hg speciation in concert with Hg isotope ratios can better ascertain source attribution and assist in identifying Hg pathways into the environment to distinguish the more bioavailable forms of Hg entering the ecosystem.

Tuscany↗

Making ‘chemical cocktails’ – Evolution of urban geochemical processes across the periodic table of elements

Urbanization contributes to the formation of novel elemental combinations and signatures in terrestrial and aquatic watersheds, also known as ‘chemical cocktails.’ The composition of chemical cocktails evolves across space and time due to: (1) elevated concentrations from anthropogenic sources, (2) accelerated weathering and corrosion of the built environment, (3) increased drainage density and intensification of urban water conveyance systems, and (4) enhanced rates of geochemical transformations due to changes in temperature, ionic strength, pH, and redox potentials. Characterizing chemical cocktails and underlying geochemical processes is necessary for: (1) tracking pollution sources using complex chemical mixtures instead of individual elements or compounds; (2) developing new strategies for co-managing groups of contaminants; (3) identifying proxies for predicting transport of chemical mixtures using continuous sensor data; and (4) determining whether interactive effects of chemical cocktails produce ecosystem-scale impacts greater than the sum of individual chemical stressors. First, we discuss some unique urban geochemical processes which form chemical cocktails, such as urban soil formation, human-accelerated weathering, urban acidification-alkalinization, and Freshwater Salinization Syndrome. Second, we review and synthesize global patterns in concentrations of major ions, carbon and nutrients, and trace elements in urban streams across different world regions and make comparisons with reference conditions. In addition to our global analysis, we highlight examples from watersheds in the Baltimore-Washington DC area, USA, which show increased transport of major ions, trace metals, and nutrients across streams draining a well-defined land-use gradient. Urbanization increased the concentrations of multiple major and trace elements in streams draining human-dominated watersheds compared to reference conditions. Chemical cocktails of major and trace elements were formed over diurnal cycles coinciding with changes in streamflow, dissolved oxygen, pH, and other variables measured by high-frequency sensors. Some chemical cocktails of major and trace elements were also significantly related to specific conductance (p < 0.05), which can be measured by sensors. Concentrations of major and trace elements increased, peaked, or decreased longitudinally along streams as watershed urbanization increased, which is consistent with distinct shifts in chemical mixtures upstream and downstream of other major cities in the world. Our global analysis of urban streams shows that concentrations of multiple elements along the periodic table significantly increase when compared with reference conditions. Furthermore, similar biogeochemical patterns and processes can be grouped among distinct mixtures of elements of major ions, dissolved organic matter, nutrients, and trace elements as chemical cocktails. Chemical cocktails form in urban waters over diurnal cycles, decades, and throughout drainage basins. We conclude our global review and synthesis by proposing strategies for monitoring and managing chemical cocktails using source control, ecosystem restoration, and green infrastructure. We discuss future research directions applying the watershed chemical cocktail approach to diagnose and manage environmental problems. Ultimately, a chemical cocktail approach targeting sources, transport, and transformations of different and distinct elemental combinations is beneficial to more holistically monitor and manage the emerging impacts of chemical mixtures in the world's fresh waters.

Applied Geochemistry↗

Lead speciation, bioaccessibility and source attribution in Missouri's Big River watershed

The Southeast Missouri Lead District is among the most productive lead deposits exploited in modern times. Intensive mining conducted prior to regulations resulted in a legacy of lead contaminated soil, large piles of mine tailings and elevated childhood blood lead levels. This study seeks to identify the source of the lead contamination in the Big River and inform risk to the public. Isotopic analysis indicated the mine tailing piles at the head of the Big River are the primary source of the lead contamination. The isotopic signature of the lead in these mine tailings matched the lead over 100 km downstream. All of the other potential lead sources investigated had different isotopic signatures. Lead concentrations in soils and sediments decrease with distance downstream of the mine tailings piles. Additionally, the speciation of the lead changes from predominantly mineralized forms, such as galena, to adsorbed lead. This is reflected in the in-vitro bioaccessibility assay (IVBA) analysis which shows higher bioaccessibility further downstream, demonstrating the importance of speciation in risk evaluation.

Missouri↗