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A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2???. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Elevated naturally occurring arsenic in a semiarid oxidizing system, Southern High Plains aquifer, Texas, USA

High groundwater As concentrations in oxidizing systems are generally associated with As adsorption onto hydrous metal (Al, Fe or Mn) oxides and mobilization with increased pH. The objective of this study was to evaluate the distribution, sources and mobilization mechanisms of As in the Southern High Plains (SHP) aquifer, Texas, relative to those in other semiarid, oxidizing systems. Elevated groundwater As levels are widespread in the southern part of the SHP (SHP-S) aquifer, with 47% of wells exceeding the current EPA maximum contaminant level (MCL) of 10 μg/L (range 0.3–164 μg/L), whereas As levels are much lower in the north (SHP-N: 9% ⩾ As MCL of 10 μg/L; range 0.2–43 μg/L). The sharp contrast in As levels between the north and south coincides with a change in total dissolved solids (TDS) from 395 mg/L (median north) to 885 mg/L (median south). Arsenic is present as arsenate (As V) in this oxidizing system and is correlated with groundwater TDS (Spearman’s ρ = 0.57). The most likely current source of As is sorbed As onto hydrous metal oxides based on correlations between As and other oxyanion-forming elements (V, ρ = 0.88; Se, ρ = 0.54; B, ρ = 0.51 and Mo, ρ = 0.46). This source is similar to that in other oxidizing systems and constitutes a secondary source; the most likely primary source being volcanic ashes in the SHP aquifer or original source rocks in the Rockies, based on co-occurrence of As and F ( ρ = 0.56), oxyanion-forming elements and SiO 2 ( ρ = 0.41), which are found in volcanic ashes. High groundwater As concentrations in some semiarid oxidizing systems are related to high evaporation. Although correlation of As with TDS in the SHP aquifer may suggest evaporative concentration, unenriched stable isotopes (δ 2 H: −65 to −27; δ 18 O: −9.1 to −4.2) in the SHP aquifer do not support evaporation. High TDS in the SHP aquifer is most likely related to upward movement of saline water from the underlying Triassic Dockum aquifer. Mobilization of As in other semiarid oxidizing systems is caused by increased pH; however, pH in the SHP aquifer is near neutral (10–90 percentiles, 7.0–7.6). Although many processes, such as competitive desorption with SiO 2 , VO 4 , or PO 4 , could be responsible for local mobilization of As in the SHP aquifer, the most plausible explanation for the regional As distribution and correlation with TDS is the counterion effect caused by a change from Ca- to Na-rich, water as shown by the high correlation between As and Na/(Ca) 0.5 ratios ( ρ = 0.57). This change in chemistry is related to mixing with saline water that moves upward from the underlying Dockum aquifer. This counterion effect may mobilize other anions and oxyanion-forming elements that are correlated with As (F, V, Se, B, Mo and SiO 2 ). Competition among the oxyanions for sorption sites may enhance As mobilization. The SHP case study has similar As sources to those of other semiarid, oxidizing systems (original volcanic ash source followed by sorption onto hydrous metal oxides) but contrasts with these systems by showing lack of evaporative concentration and pH mobilization of As but counterion mobilization of As instead in the SHP-S aquifer.

Texas↗

Contaminants from Cretaceous black shale: I. Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na 2 SO 4 ) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m −2 ) enriches soil moisture in Na and residual SO 4 . Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Colorado↗

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↗

Mineralogical and geochemical consequences of the long-term presence of CO2 in natural reservoirs: An example from the Springerville-St. Johns Field, Arizona, and New Mexico, U.S.A

The Springerville-St. Johns CO2 field in eastern Arizona and western New Mexico is one of more than a dozen gas fields developed within the Colorado Plateau and Southern Rocky Mountain region. Extensive travertine (CaCO3) deposits record a long history of CO2 migration and leakage to the atmosphere. The oldest travertine deposits may have formed during the initial filling of the CO2 reservoir when groundwaters exsolved CO2 upon reaching the surface. The youngest travertine deposits are associated with springs on the floor of the Little Colorado River valley, but travertine deposition appears to be insignificant today. Older deposits occur up to 325 m above the valley floor. Geologic relationships suggest travertine deposition began in the late Pleistocene after volcanic activity ended at ???0.3 Ma. Most of the CaCO3 could have been derived from dissolution of the underlying limestones and dolomites. Interactions between the reservoir fluids and rocks were observed in core samples from one of the intervals that produced dry gas. These reactions resulted in the dissolution of carbonate cements and detrital feldspars and the formation of dawsonite and kaolinite. Geochemical simulations suggest that the dawsonite could have been deposited when the CO2 fugacity reached 20 bars and that the kaolinite formed as the CO2 fugacity decreased. Corrosion of drill pipe by acidic waters and a pronounced HCO3 anomaly above the CO2 reservoir provide evidence of a continuing flux of CO2 from depth. CO2 storage occurs primarily as dissolved carbonate species and as gas accumulations. Only a small percentage of the CO2 was sequestered in secondary minerals. ?? 2005 Elsevier B.V. All rights reserved.

Chemical Geology↗

Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

Chemical Geology↗

Chemical and stable isotopic composition of water and gas in the Fort Union Formation of the Powder River Basin, Wyoming and Montana: Evidence for water/rock interaction and the biogenic origin of coalbed natural gas

Significant amounts (> 36 million m3/day) of coalbed methane (CBM) are currently being extracted from coal beds in the Paleocene Fort Union Formation of the Powder River Basin of Wyoming and Montana. Information on processes that generate methane in these coalbed reservoirs is important for developing methods that will stimulate additional production. The chemical and isotopic compositions of gas and ground water from CBM wells throughout the basin reflect generation processes as well as those that affect water/rock interaction. Our study included analyses of water samples collected from 228 CBM wells. Major cations and anions were measured for all samples, δDH2O and δ18OH2O were measured for 199 of the samples, and δDCH4 of gas co-produced with water was measured for 100 of the samples. Results show that (1) water from Fort Union Formation coal beds is exclusively Na–HCO3-type water with low dissolved SO4 content (median < 1 mg/L) and little or no dissolved oxygen (< 0.15 mg/L), whereas shallow groundwater (depth generally < 120 m) is a mixed Ca–Mg–Na–SO4–HCO3 type; (2) water/rock interactions, such as cation exchange on clay minerals and precipitation/dissolution of CaCO3 and SO4 minerals, account for the accumulation of dissolved Na and depletion of Ca and Mg; (3) bacterially-mediated oxidation–reduction reactions account for high HCO3 (270–3310 mg/L) and low SO4 (median < 0.15 mg/L) values; (4) fractionation between δDCH4 (− 283 to − 328 per mil) and δDH2O (− 121 to − 167 per mil) indicates that the production of methane is primarily by biogenic CO2 reduction; and (5) values of δDH2O and δ18OH2O (− 16 to − 22 per mil) have a wide range of values and plot near or above the global meteoric water line, indicating that the original meteoric water has been influenced by methanogenesis and by being mixed with surface and shallow groundwater.

International Journal of Coal Geology↗

Organic substances in produced and formation water from unconventional natural gas extraction in coal and shale

Organic substances in produced and formation water from coalbed methane (CBM) and gas shale plays from across the USA were examined in this study. Disposal of produced waters from gas extraction in coal and shale is an important environmental issue because of the large volumes of water involved and the variable quality of this water. Organic substances in produced water may be environmentally relevant as pollutants, but have been little studied. Results from five CBM plays and two gas shale plays (including the Marcellus Shale) show a myriad of organic chemicals present in the produced and formation water. Organic compound classes present in produced and formation water in CBM plays include: polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, alkyl phenols, aromatic amines, alkyl aromatics (alkyl benzenes, alkyl biphenyls), long-chain fatty acids, and aliphatic hydrocarbons. Concentrations of individual compounds range from < 1 to 100 μg/L, but total PAHs (the dominant compound class for most CBM samples) range from 50 to 100 μg/L. Total dissolved organic carbon (TOC) in CBM produced water is generally in the 1–4 mg/L range. Excursions from this general pattern in produced waters from individual wells arise from contaminants introduced by production activities (oils, grease, adhesives, etc.). Organic substances in produced and formation water from gas shale unimpacted by production chemicals have a similar range of compound classes as CBM produced water, and TOC levels of about 8 mg/L. However, produced water from the Marcellus Shale using hydraulic fracturing has TOC levels as high as 5500 mg/L and a range of added organic chemicals including, solvents, biocides, scale inhibitors, and other organic chemicals at levels of 1000 s of μg/L for individual compounds. Levels of these hydraulic fracturing chemicals and TOC decrease rapidly over the first 20 days of water recovery and some level of residual organic contaminants remain up to 250 days after hydraulic fracturing. Although the environmental impacts of the organics in produced water are not well defined, results suggest that care should be exercised in the disposal and release of produced waters containing these organic substances into the environment because of the potential toxicity of many of these substances.

International Journal of Coal Geology↗

Nature's refineries — Metals and metalloids in arc volcanoes

Chemical data for fumaroles and for atmospheric gas and ash plumes from active arc volcanoes provide glimpses of the rates of release of metal and metalloids, such as Tl and Cd, from shallow and mid-crust magmas. Data from copper deposits formed in ancient volcanoes at depths of up to about 1500 m in the fractures below paleo-fumaroles, and at around 2000–4000 m in association with sub-volcanic intrusions (porphyry copper deposits) provide evidence of sub-surface deposition of Cu–Au–Ag–Mo and a range of other minor elements including Te, Se, As and Sb. These deposits, or ‘sinks’, of metals consistently record sustained histories of magmatic gas streaming through volcanic systems interspersed by continuing intrusive and eruptive activity. Here we integrate data from ancient and modern volcanic systems and show that the fluxes of metals and metalloids are controlled by a) the maintenance of fracture permeability in the stressed crust below volcanoes and b) the chemical processes that are triggered as magmatic gas, initially undersaturated with metals and metalloids, expands from lithostatic to very low pressure conditions through fracture arrays. The recognition of gas streaming may also account for the phenomenon of ‘excess degassing’, and defines an integral, but generally understated, component of active volcanic systems – a volcanic gas core – that is likely to be integral to the progression of eruptions to Plinean state. Destabilization of solvated molecular metal and metalloid species in magmatic gas mixtures and changes in their redox state are triggered, as it expands to the surface by abrupt pressure drops, or throttles' in the fracture array that guides expansion to the surface. The electronically harder, low electronegativity metals, such as copper and iron, deposit rapidly in response to expansion followed more slowly by arsenic with antimony as sulfosalts. Heavy, large radius, softer elements such as bismuth, lead, and thallium along with cadmium are strongly fractionated along the way, eventually venting their excess along with SO 2 , CO 2 , and other components of the carrier gas, into the atmosphere. These elements, many of which are toxic, may also be dispersed by mixing with groundwater in the permeable crust below volcanoes and generate potential health risks due to Hg, As, and Se contamination of drinking water resources.

Earth-Science Reviews↗

Noble gas geochemistry investigation of high CO2 natural gas at the LaBarge Platform, Wyoming, USA

A regional sampling of gases from thermal springs near the LaBarge Field, Wyoming, USA to determine the extent of the total carbon dioxide system (TCDS) indicates that the system may extend up to 70 km to the northwest of the field. Geochemical evidence from noble gas isotopes, stable element isotopes, and gas composition provide the foundation for these conclusions. Samples from Soda Springs to the west and Grand Teton National Park to the north do not exhibit the potentially diagnostic LaBarge gas chemistry and represent an absolute maximum potential extent of the system. Additional sampling to the south and east as well as in-fill sampling in regions previously sampled are necessary to refine these preliminary TCDS boundaries.

Wyoming↗

Hydrologic response of groundwater and streamflow to natural and anthropogenic drivers of change in headwaters of the upper Colorado River basin during recent wet (1982–1999) and drought (2000–2022) conditions

Study region: Headwaters of the upper Colorado River basin (UCOL), USA Study focus: Surface-water and groundwater numerical models incorporating water-use information were used to investigate changes in climate, water use, and simulated hydrologic responses of snow processes, evapotranspiration, groundwater, and streamflow during recent wet (1982–1999) and drought (2000–2022) periods in the headwater subregions of the upper Colorado River basin. New hydrologic insights for the region: Decreases in average streamflow between wet and drought periods ranged from 20 % in the Colorado River headwaters subregion to 23 % in the Gunnison River headwaters subregion. Like streamflow, average surface runoff was statistically less during the drought than the wet period, with decreases from 24–31 % in the headwaters. On a volume basis, runoff decreases were greater than streamflow decreases in both the Colorado River and Gunnison River headwaters. Although the amount of water-year groundwater discharge to streams remained nearly the same between the wet and drought periods, groundwater as a percentage of streamflow increased between the wet and drought periods, highlighting the importance of groundwater in sustaining streamflow during drought conditions. Multiple linear regression analyses revealed that snowmelt-only models were better than the best precipitation and temperature models at explaining streamflow variability from all headwater subregions for both the wet and drought periods.

Arizona, Colorado, New Mexico, Utah, Wyoming↗

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5 mg L-1. These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.

Environmental Pollution↗

On the nature of the dirty ice at the bottom of the GISP2 ice core

We present data on the triple Ar isotope composition in trapped gas from clean, stratigraphically disturbed ice between 2800 and 3040m depth in the GISP2 ice core, and from basal dirty ice from 3040 to 3053m depth. We also present data for the abundance and isotopic composition of O 2 and N 2 , and abundance of Ar, in the basal dirty ice. The Ar/N 2 ratio of dirty basal ice, the heavy isotope enrichment (reflecting gravitational fractionation), and the total gas content all indicate that the gases in basal dirty ice originate from the assimilation of clean ice of the overlying glacier, which comprises most of the ice in the dirty bottom layer. O 2 is partly to completely depleted in basal ice, reflecting active metabolism. The gravitationally corrected ratio of 40 Ar/ 38 Ar, which decreases with age in the global atmosphere, is compatible with an age of 100-250ka for clean disturbed ice. In basal ice, 40 Ar is present in excess due to injection of radiogenic 40Ar produced in the underlying continental crust. The weak depth gradient of 40 Ar in the dirty basal ice, and the distribution of dirt, indicate mixing within the basal ice, while various published lines of evidence indicate mixing within the overlying clean, disturbed ice. Excess CH 4 , which reaches thousands of ppm in basal dirty ice at GRIP, is virtually absent in overlying clean disturbed ice, demonstrating that mixing of dirty basal ice into the overlying clean ice, if it occurs at all, is very slow. Order-of-magnitude estimates indicate that the mixing rate of clean ice into dirty ice is sufficient to maintain a steady thickness of dirty ice against thinning from the mean ice flow. The dirty ice appears to consist of two or more basal components in addition to clean glacial ice. A small amount of soil or permafrost, plus preglacial snow, lake or ground ice could explain the observations.

Earth and Planetary Science Letters↗

Network analysis of a regional fishery: Implications for management of natural resources, and recruitment and retention of anglers

Angler groups and water-body types interact to create a complex social-ecological system. Network analysis could inform detailed mechanistic models on, and provide managers better information about, basic patterns of fishing activity. Differences in behavior and reservoir selection among angler groups in a regional fishery, the Salt Valley fishery in southeastern Nebraska, USA, were assessed using a combination of cluster and network analyses. The four angler groups assessed ranged from less active, unskilled anglers (group One) to highly active, very skilled anglers (group Four). Reservoir use patterns and the resulting network communities of these four angler groups differed; the number of reservoir communities for these groups ranged from two to three and appeared to be driven by reservoir location (group One), reservoir size and its associated attributes (groups Two and Four), or an interaction between reservoir size and location (group Three). Network analysis is a useful tool to describe differences in participation among angler groups within a regional fishery, and provides new insights about possible recruitment of anglers. For example, group One anglers fished reservoirs closer to home and had a greater probability of dropping out if local reservoir access were restricted.

Fisheries Research↗