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A national-scale geochemical and mineralogical survey of soils of the conterminous United States

In 2007, the US Geological Survey initiated a low-density (1 site per 1600 km 2 , c. 4800 sites) geochemical and mineralogical survey of soils of the conterminous USA. The ideal sampling protocol at each site includes a sample from 0–5 cm depth, a composite of the soil A horizon, and a sample from the soil C horizon. The <2-mm fraction of each sample is analyzed for Al, Ca, Fe, K, Mg, Na, S, Ti, Ag, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, In, La, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Sn, Sr, Te, Th, Tl, U, V, W, Y and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl, HNO 3 , HClO 4 and HF. Separate methods are used for As, Hg, Se and total C on this same size fraction. The major mineralogical components are determined by a quantitative X-ray diffraction method. Sampling was completed in 2010 with chemical and mineralogical analysis currently underway. Preliminary results for a swath from the central USA to Florida clearly show the effects of soil parent material and climate on the chemical and mineralogical composition of soils. A sample archive will be established and made available for future investigations.

Conterminous United States↗

Pb-concentrations and Pb-isotope ratios in soils collected along an east-west transect across the United States

Analytical results for Pb-concentrations and isotopic ratios from ca. 150 samples of soil A horizon and ca. 145 samples of soil C horizon collected along a 4000-km east&ndash;west transect across the USA are presented. Lead concentrations along the transect show: (1) generally higher values in the soil A-horizon than the C-horizon (median 21 vs. 16.5 mg/kg), (2) an increase in the median value of the soil A-horizon for central to eastern USA (Missouri to Maryland) when compared to the western USA (California to Kansas) (median 26 vs. 20 mg/kg) and (3) a higher A/C ratio for the central to eastern USA (1.35 vs. 1.14). Lead isotopes show a distinct trend across the USA, with the highest 206 Pb/ 207 Pb ratios occurring in the centre (Missouri, median A-horizon: 1.245; C-horizon: 1.251) and the lowest at both coasts (e.g., California, median A-horizon: 1.195; C-horizon: 1.216). The soil C-horizon samples show generally higher 206 Pb/ 207 Pb ratios than the A-horizon (median C-horizon: 1.224; A-horizon: 1.219). The 206 Pb/ 207 Pb-isotope ratios in the soil A horizon show a correlation with the total feldspar content for the same 2500-km portion of the transect from east-central Colorado to the Atlantic coast that shows steadily increasing precipitation. No such correlation exists in the soil C horizon. The data demonstrate the importance of climate and weathering on both Pb-concentration and 206 Pb/ 207 Pb-isotope ratios in soil samples and natural shifts thereof in the soil profile during soil-forming processes.

Applied Geochemistry↗

Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters

The formation of acid mine drainage from metals extraction or natural acid rock drainage and its mixing with surface waters is a complex process that depends on petrology and mineralogy, structural geology, geomorphology, surface-water hydrology, hydrogeology, climatology, microbiology, chemistry, and mining and mineral processing history. The concentrations of metals, metalloids, acidity, alkalinity, Cl - , F - and SO 4 2- found in receiving streams, rivers, and lakes are affected by all of these factors and their interactions. Remediation of mine sites is an engineering concern but to design a remediation plan without understanding the hydrogeochemical processes of contaminant mobilization can lead to ineffective and excessively costly remediation. Furthermore, remediation needs a goal commensurate with natural background conditions rather than water-quality standards that might bear little relation to conditions of a highly mineralized terrain. This paper reviews hydrogeochemical generalizations, primarily from US Geological Survey research, that enhance our understanding of the origin, transport, and fate of contaminants released from mined and mineralized areas. Mobility of potential or actual contaminants from mining and mineral processing activities depends on (1) occurrence : is the mineral source of the contaminant actually present? (2) abundance : is the mineral present in sufficient quantity to make a difference? (3) reactivity : what are the energetics, rates, and mechanisms of sorption and mineral dissolution and precipitation relative to the flow rate of the water? and (4) hydrology : what are the main flow paths for contaminated water? Estimates of relative proportions of minerals dissolved and precipitated can be made with mass-balance calculations if minerals and water compositions along a flow path are known. Combined with discharge, these mass-balance estimates quantify the actual weathering rate of pyrite mineralization in the environment and compare reasonably well with laboratory rates of pyrite oxidation except when large quantities of soluble salts and evaporated mine waters have accumulated underground. Quantitative mineralogy with trace-element compositions can substantially improve the identification of source minerals for specific trace elements through mass balances. Post-dissolution sorption and precipitation (attenuation) reactions depend on the chemical behavior of each element, solution composition and pH, aqueous speciation, temperature, and contact-time with mineral surfaces. For example, little metal attenuation occurs in waters of low pH (<3.5) and metals tend to maintain element ratios indicative of the main mineral or group of minerals from which they dissolved, except Fe, SiO 2 , and redox-sensitive oxyanions (As, Sb, Se, Mo, Cr, V). Once dissolved, metal and metalloid concentrations are strongly affected by redox conditions and pH. Iron is the most reactive because it is rapidly oxidized by bacteria and archaea and Fe(III) hydrolyzes and precipitates at low pH (1&ndash;3) which is related directly to its first hydrolysis constant, pK 1 = 2.2. Several insoluble sulfate minerals precipitate at low pH including anglesite, barite, jarosite, alunite and basaluminite. Aluminum hydrolyzes near pH 5 (pK 1 = 5.0) and provides buffering and removal of Al by mineral precipitation from pH 4&ndash;5.5. Dissolved sulfate behaves conservatively because the amount removed from solution by precipitation is usually too small relative to the high concentrations in the water column and relative to the flow rate of the water.

Applied Geochemistry↗

Acidification of Earth: An assessment across mechanisms and scales

In this review article, anthropogenic activities that cause acidification of Earth’s air, waters, and soils are examined. Although there are many mechanisms of acidification, the focus is on the major ones, including emissions from combustion of fossil fuels and smelting of ores, mining of coal and metal ores, and application of nitrogen fertilizer to soils, by elucidating the underlying biogeochemical reactions as well as assessing the magnitude of the effects. These widespread activities have resulted in (1) increased CO 2 concentration in the atmosphere that acidifies the oceans; (2) acidic atmospheric deposition that acidifies soils and bodies of freshwater; (3) acid mine drainage that acidifies bodies of freshwater and groundwaters; and (4) nitrification that acidifies soils. Although natural geochemical reactions of mineral weathering and ion exchange work to buffer acidification, the slow reaction rates or the limited abundance of reactant phases are overwhelmed by the onslaught of anthropogenic acid loading. Relatively recent modifications of resource extraction and usage in some regions of the world have begun to ameliorate local acidification, but expanding use of resources in other regions is causing environmental acidification in previously unnoticed places. World maps of coal consumption, Cu mining and smelting, and N fertilizer application are presented to demonstrate the complex spatial heterogeneity of resource consumption as well as the overlap in acidifying potential derived from distinctly different phenomena. Projected population increase by country over the next four decades indicates areas with the highest potential for acidification, so enabling anticipation and planning to offset or mitigate the deleterious environmental effects associated with these global shifts in the consumption of energy, mineral, and food resources.

Applied Geochemistry↗

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H 2 SO 4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl − concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.

Applied Geochemistry↗

Methylation of Hg downstream from the Bonanza Hg mine, Oregon

Speciation of Hg and conversion to methyl-Hg were evaluated in stream sediment, stream water, and aquatic snails collected downstream from the Bonanza Hg mine, Oregon. Total production from the Bonanza mine was >1360t of Hg, during mining from the late 1800s to 1960, ranking it as an intermediate sized Hg mine on an international scale. The primary objective of this study was to evaluate the distribution, transport, and methylation of Hg downstream from a Hg mine in a coastal temperate climatic zone. Data shown here for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from this area. Stream sediment collected from Foster Creek flowing downstream from the Bonanza mine contained elevated Hg concentrations that ranged from 590 to 71,000ng/g, all of which (except the most distal sample) exceeded the probable effect concentration (PEC) of 1060ng/g, the Hg concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in stream sediment collected from Foster Creek varied from 11 to 62ng/g and were highly elevated compared to regional baseline concentrations (0.11-0.82ng/g) established in this study. Methyl-Hg concentrations in stream sediment collected in this study showed a significant correlation with total organic C (TOC, R 2 =0.62), generally indicating increased methyl-Hg formation with increasing TOC in sediment. Isotopic-tracer methods indicated that several samples of Foster Creek sediment exhibited high rates of Hg-methylation. Concentrations of Hg in water collected downstream from the mine varied from 17 to 270ng/L and were also elevated compared to baselines, but all were below the 770ng/L Hg standard recommended by the USEPA to protect against chronic effects to aquatic wildlife. Concentrations of methyl-Hg in the water collected from Foster Creek ranged from 0.17 to 1.8ng/L, which were elevated compared to regional baseline sites upstream and downstream from the mine that varied from <0.02 to 0.22ng/L. Aquatic snails collected downstream from the mine were elevated in Hg indicating significant bioavailability and uptake of Hg by these snails. Results for sediment and water indicated significant methyl-Hg formation in the ecosystem downstream from the Bonanza mine, which is enhanced by the temperate climate, high precipitation in the area, and high organic matter.

Oregon↗

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW e ). Soil CO 2 degassing was quantified with 2663 CO 2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m −2 ) using published soil temperature heat flow functions. Both CO 2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO 2 emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO 2 emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO 2 emissions due to the loss of >99% of the original CO 2 content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO 2 release to the atmosphere from the high temperature reservoir at Ohaaki. The CO 2 flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO 2 flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m −2 d −1 ) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO 2 diffuses through porous media of the soil zone. For high-flux sites (>300 g m −2 d −1 ), the δ 13 CO 2 signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO 2 source for each respective upflow. Flux thresholds of <30 g m −2 d −1 for purely diffusive gas transport, between 30 and 300 g m −2 d −1 for combined diffusive–advective transport, and ⩾300 g m −2 d −1 for purely advective gas transport at Ohaaki were assigned. δ 13 CO 2 values and cumulative probability plots of CO 2 flux data both identified a threshold of ∼15 g m −2 d −1 by which background (atmospheric and soil respired) CO 2 may be differentiated from hydrothermal CO 2 .

Taupo Volcanic Zone↗

Recent paleorecords document rising mercury contamination in Lake Tanganyika

Recent Lake Tanganyika Hg deposition records were derived using 14 C and excess 210 Pb geochronometers in sediment cores collected from two contrasting depositional environments: the Kalya Platform, located mid-lake and more removed from watershed impacts, and the Nyasanga/Kahama River delta region, located close to the lake’s shoreline north of Kigoma. At the Kalya Platform area, pre-industrial Hg concentrations are 23 ± 0.2 ng/g, increasing to 74 ng/g in modern surface sediment, and the Hg accumulation rate has increased from 1.0 to 7.2 μg/m 2 /a from pre-industrial to present, which overall represents a 6-fold increase in Hg concentration and accumulation. At the Nyasanga/Kahama delta region, pre-industrial Hg concentrations are 20 ± 3 ng/g, increasing to 46 ng/g in surface sediment. Mercury accumulation rate has increased from 30 to 70 μg/m 2 /a at this site, representing a 2–3-fold increase in Hg concentration and accumulation. There is a lack of correlation between charcoal abundance and Hg accumulation rate in the sediment cores, demonstrating that local biomass burning has little relationship with the observed Hg concentration or Hg accumulation rates. Examined using a sediment focusing-corrected mass accumulation rate approach, the cores have similar anthropogenic atmospheric Hg deposition profiles, suggesting that after accounting for background sediment concentrations the source of accumulating Hg is predominantly atmospheric in origin. In summary, the data document an increase of Hg flux to the Lake Tanganyika ecosystem that is consistent with increasing watershed sediment delivery with background-level Hg contamination, and regional as well as global increases in atmospheric Hg deposition.

Tanzania, the Democratic Republic of the Congo , B↗

Delta Chromium-53/52 isotopic composition of native and contaminated groundwater, Mojave Desert, USA

Chromium(VI) concentrations in groundwater sampled from three contaminant plumes in aquifers in the Mojave Desert near Hinkley, Topock and El Mirage, California, USA, were as high as 2600, 5800 and 330 μg/L, respectively. δ 53/52 Cr compositions from more than 50 samples collected within these plumes ranged from near 0‰ to almost 4‰ near the plume margins. Assuming only reductive fractionation of Cr(VI) to Cr(III) within the plume, apparent fractionation factors for δ 53/52 Cr isotopes ranged from ε app = 0.3 to 0.4 within the Hinkley and Topock plumes, respectively, and only the El Mirage plume had a fractionation factor similar to the laboratory derived value of ε = 3.5. One possible explanation for the difference between field and laboratory fractionation factors at the Hinkley and Topock sites is localized reductive fractionation of Cr(VI) to Cr(III), with subsequent advective mixing of native and contaminated water near the plume margin. Chromium(VI) concentrations and δ 53/52 Cr isotopic compositions did not uniquely define the source of Cr near the plume margin, or the extent of reductive fractionation within the plume. However, Cr(VI) and δ 53/52 Cr data contribute to understanding of the interaction between reductive and mixing processes that occur within and near the margins of Cr contamination plumes. Reductive fractionation of Cr(VI) predominates in plumes having higher ε app , these plumes may be suitable for monitored natural attenuation. In contrast, advective mixing predominates in plumes having lower ε app , the highly dispersed margins of these plumes may be difficult to define and manage.

California↗

Distribution of Cu, Co, As, and Fe in mine waste, sediment, soil, and water in and around mineral deposits and mines of the Idaho Cobalt Belt, USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.

Idaho↗

Hydrozincite seasonal precipitation at Naracauli (Sardinia – Italy): Hydrochemical factors and morphological features of the biomineralization process

Hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] precipitation from Naracauli waters (SW Sardinia) is, among other things, promoted by a microbial community made up of a filamentous cyanobacterium ( Scytonema sp.) and a microalgae ( Chlorella sp.). Hydrozincite bioprecipitation is responsible for the natural removal of harmful metals, especially Zn, from the stream waters. Thus, hydrozincite could be used to attenuate metal pollution in mining waters. Information on environmental conditions which promote the biomineralization process is fundamental for the development of remediation strategies. This paper aims to investigate the variables controlling the biomineralization process, and seasonal variation of the hydrochemical factors that affect hydrozincite precipitation. Hydrozincite morphology varies depending on the environmental conditions. Specifically, changes were observed between samples collected in late spring and samples collected in summer, and among samples precipitated under different water flow conditions. According to field observations, correlated with speciation and equilibrium calculation, the maximum intensity in hydrozincite precipitation occurs in the late spring during rainy years. In these conditions, the hydraulic regime in the stream reaches stationary conditions, and saturation index values with respect to hydrozincite reach their highest values. Concomitantly, the Zn 2+ / CO 3 2 - "> CO32- molar ratio reaches values close to 1, indicating that kinetic processes have a role on the hydrozincite biomineralization process.

Sardinia↗

The significance of 24-norcholestanes, triaromatic steroids and dinosteroids in oils and Cambrian-Ordovician source rocks from the cratonic region of the Tarim Basin, NW China

Two oil families in Ordovician reservoirs from the cratonic region of the Tarim Basin are distinguished by the distribution of regular steranes, triaromatic steroids, norcholestanes and dinosteroids. Oils with relatively lower contents of C 28 regular steranes, C 26 20S, C 26 20R + C 27 20S and C 27 20R regular triaromatic steroids, dinosteranes, 24-norcholestanes and triaromatic dinosteroids originated from Middle–Upper Ordovician source rocks. In contrast, oils with abnormally high abundances of the above compounds are derived from Cambrian and Lower Ordovician source rocks. Only a few oils have previously been reported to be of Cambrian and Lower Ordovician origin, especially in the east region of the Tarim Basin. This study further reports the discovery of oil accumulations of Cambrian and Lower Ordovician origin in the Tabei and Tazhong Uplifts, which indicates a potential for further discoveries involving Cambrian and Lower Ordovician sourced oils in the Tarim Basin. Dinosteroids in petroleum and ancient sediments are generally thought to be biomarkers for dinoflagellates and 24-norcholestanes for dinoflagellates and diatoms. Therefore, the abnormally high abundance of these compounds in extracts from the organic-rich sediments in the Cambrian and Lower Ordovician and related oils in the cratonic region of the Tarim Basin suggests that phytoplankton algae related to dinoflagellates have appeared and might have flourished in the Tarim Basin during the Cambrian Period. Steroids with less common structural configurations are underutilized and can expand understanding of the early development history of organisms, as well as define petroleum systems.

Tarim Basin↗

Evolution of the chemistry of Fe bearing waters during CO 2 degassing

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO 2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO 2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO 2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO 2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO 2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO 2 removal at the flow rates measured.

Applied Geochemistry↗

Solute and geothermal flux monitoring using electrical conductivity in the Madison, Firehole, and Gibbon Rivers, Yellowstone National Park

The thermal output from the Yellowstone magma chamber can be estimated from the Cl flux in the major rivers in Yellowstone National Park; and by utilizing continuous discharge and electrical conductivity measurements the Cl flux can be calculated. The relationship between electrical conductivity and concentrations of Cl and other geothermal solutes (Na, SO 4 , F, HCO 3 , SiO 2 , K, Li, B, and As) was quantified at monitoring sites along the Madison, Gibbon, and Firehole Rivers, which receive discharge from some of the largest and most active geothermal areas in Yellowstone. Except for some trace elements, most solutes behave conservatively and the ratios between geothermal solute concentrations are constant in the Madison, Gibbon, and Firehole Rivers. Hence, dissolved concentrations of Cl, Na, SO 4 , F, HCO 3 , SiO 2 , K, Li, Ca, B and As correlate well with conductivity ( R 2 > 0.9 for most solutes) and most exhibit linear trends. The 2011 flux for Cl, SO 4 , F and HCO 3 determined using automated conductivity sensors and discharge data from nearby USGS gaging stations is in good agreement with those of previous years (1983–1994 and 1997–2008) at each of the monitoring sites. Continuous conductivity monitoring provides a cost- and labor-effective alternative to existing protocols whereby flux is estimated through manual collection of numerous water samples and subsequent chemical analysis. Electrical conductivity data also yield insights into a variety of topics of research interest at Yellowstone and elsewhere: (1) Geyser eruptions are easily identified and the solute flux quantified with conductivity data. (2) Short-term heavy rain events can produce conductivity anomalies due to dissolution of efflorescent salts that are temporarily trapped in and around geyser basins during low-flow periods. During a major rain event in October 2010, 180,000 kg of additional solute was measured in the Madison River. (3) The output of thermal water from the Gibbon River appears to have increased by about 0.2%/a in recent years, while the output of thermal water for the Firehole River shows a decrease of about 10% from 1983 to 2011. Confirmation of these trends will require continuing Cl flux monitoring over the coming decades.

Wyoming↗

Strontium isotope systematics of mixing groundwater and oil-field brine at Goose Lake in northeastern Montana, USA

Groundwater, surface water, and soil in the Goose Lake oil field in northeastern Montana have been affected by Cl − -rich oil-field brines during long-term petroleum production. Ongoing multidisciplinary geochemical and geophysical studies have identified the degree and local extent of interaction between brine and groundwater. Fourteen samples representing groundwater, surface water, and brine were collected for Sr isotope analyses to evaluate the usefulness of 87 Sr/ 86 Sr in detecting small amounts of brine. Differences in Sr concentrations and 87 Sr/ 86 Sr are optimal at this site for the experiment. Strontium concentrations range from 0.13 to 36.9 mg/L, and corresponding 87 Sr/ 86 Sr values range from 0.71097 to 0.70828. The local brine has 168 mg/L Sr and a 87 Sr/ 86 Sr value of 0.70802. Mixing relationships are evident in the data set and illustrate the sensitivity of Sr in detecting small amounts of brine in groundwater. The location of data points on a Sr isotope-concentration plot is readily explained by an evaporation-mixing model. The model is supported by the variation in concentrations of most of the other solutes.

Montana↗

Identification of contamination in a lake sediment core using Hg and Pb isotopic compositions, Lake Ballinger, Washington, USA

Concentrations and isotopic compositions of Hg and Pb were measured in a sediment core collected from Lake Ballinger, near Seattle, Washington, USA. Lake Ballinger has been affected by input of metal contaminants emitted from the Tacoma smelter, which operated from 1887 to 1986 and was located about 53 km south of the lake. Concentrations and loadings of Hg and Pb in Lake Ballinger increased by as much as three orders of magnitude during the period of smelting as compared to the pre-smelting period. Concentrations and loadings of Hg and Pb then decreased by about 55% and 75%, respectively, after smelting ended. Isotopic compositions of Hg changed considerably during the period of smelting (δ 202 Hg = −2.29‰ to −0.38‰, mean −1.23‰, n = 9) compared to the pre-smelting period (δ 202 Hg = −2.91‰ to −2.50‰, mean −2.75‰, n = 4). Variations were also observed in 206 Pb/ 207 Pb and 208 Pb/ 207 Pb isotopic compositions during these periods. Data for Δ 199 Hg and Δ 201 Hg indicate mass independent fractionation (MIF) of Hg isotopes in Lake Ballinger sediment during the smelting and post-smelting period and suggest MIF in the ore smelted, during the smelting process, or chemical modification at some point in the past. Negative values for Δ 199 Hg and Δ 201 Hg for the pre-smelting period are similar to those previously reported for soil, peat, and lichen, likely suggesting some component of atmospheric Hg. Variations in the concentrations and isotopic compositions of Hg and Pb were useful in tracing contaminant sources and the understanding of the depositional history of sedimentation in Lake Ballinger.

Washington↗

Hydrothermal contamination of public supply wells in Napa and Sonoma Valleys, California

Groundwater chemistry and isotope data from 44 public supply wells in the Napa and Sonoma Valleys, California were determined to investigate mixing of relatively shallow groundwater with deeper hydrothermal fluids. Multivariate analyses including Cluster Analyses, Multidimensional Scaling (MDS), Principal Components Analyses (PCA), Analysis of Similarities (ANOSIM), and Similarity Percentage Analyses (SIMPER) were used to elucidate constituent distribution patterns, determine which constituents are significantly associated with these hydrothermal systems, and investigate hydrothermal contamination of local groundwater used for drinking water. Multivariate statistical analyses were essential to this study because traditional methods, such as mixing tests involving single species (e.g. Cl or SiO 2 ) were incapable of quantifying component proportions due to mixing of multiple water types. Based on these analyses, water samples collected from the wells were broadly classified as fresh groundwater, saline waters, hydrothermal fluids, or mixed hydrothermal fluids/meteoric water wells. The Multivariate Mixing and Mass-balance (M3) model was applied in order to determine the proportion of hydrothermal fluids, saline water, and fresh groundwater in each sample. Major ions, isotopes, and physical parameters of the waters were used to characterize the hydrothermal fluids as Na–Cl type, with significant enrichment in the trace elements As, B, F and Li. Five of the wells from this study were classified as hydrothermal, 28 as fresh groundwater, two as saline water, and nine as mixed hydrothermal fluids/meteoric water wells. The M3 mixing-model results indicated that the nine mixed wells contained between 14% and 30% hydrothermal fluids. Further, the chemical analyses show that several of these mixed-water wells have concentrations of As, F and B that exceed drinking-water standards or notification levels due to contamination by hydrothermal fluids.

California↗