The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km²) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment.     

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.     

A quantitative interpretation of recent experimental results on stable carbon isotope fractionation by aerobic CH4-oxidizing bacteria

A quantitative model of recent laboratory experiments on carbon isotope fractionation by methane-oxidizing bacteria is proposed. The simulated experimental apparatus consists of a bacterial culture with a constant liquid volume, a gas headspace and a methane bubbling mechanism. The relative effects of bacterial growth and transport phenomena that do not depend on cell density are clarified. In all calculations, gas-liquid mass transfer is defined by unconstrained model parameters. Limited mass transfer from the culture into the headspace, rather than the incomplete dissolution of substrate-rich bubbles, seems to have caused an apparent decrease in the measured carbon isotope fractionation. The experimenters attributed this fractionation shift to a growing imbalance among kinetic rates as methane consumption by bacteria increases. Model predictions support this interpretation but also show that changes in carbon isotope fractionation in the course of the experiments cannot be unambiguously correlated with bacterial cell density unless gas-liquid mass transfer parameters are calibrated. Simulations of other laboratory experiments indicate that a reported change in carbon isotope fractionation could, in part at least, be the result of experimental conditions rather than the emergence of a different methane oxidation pathway postulated by the experimenters. A careful evaluation of mass transfer from the liquid culture into the gas headspace is warranted in this type of experiments since isotope fractionation factors are likely to be used in a wide variety of environmental contexts.     

Origin of the Oceanic Lithosphere

In a global examination of mid-ocean ridge basalt (MORB) glasscompositions, we find that Na₈–Fe₈–depth variationsdo not support modeling of MORBs as aggregates of melt compositionsgenerated over a large range of temperature and pressure. However,the Na₈–Fe₈ variations are consistent with the compositionalsystematics of solidus melts in the plagioclase–spinellherzolite transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O–FeO(CMASNF) system. For natural compositions, the P–T rangefor melt extraction is estimated to be 1·2–1·5GPa and 1250–1280°C. This P–T range is a closematch with the maximum P–T conditions for explosive pressure-releasevaporization of carbonate-bearing melts. It is proposed thatfracturing of the lithosphere induces explosive formation andescape of CO₂ vapor. This provides the vehicle for extractionof MORBs at a relatively uniform T and P. The upper portionof the CO₂-bearing and slightly melted seismic low-velocityzone flows toward the ridge, rises at the ridge axis to lower-lithospheredepths, melts much more extensively during this rise, and releasesMORB melts to the surface driven by explosively escaping CO₂vapor. The residue and overlying crust produced by this meltingthen migrate away from the ridge axis as new oceanic lithosphere.The entire process of oceanic lithosphere creation involvesonly the upper 140 km. When lithospheric stresses shift fractureformation to other localities, escape of CO₂ ceases, the vehiclefor transporting melt to the surface disappears, and ridgesdie. Inverse correlations of Na₈ vs Fe₈ for MORB glasses areexplained by mantle heterogeneity, and positive variations superimposedon the inverse variations are consistent with progressive extractionof melts from short, ascending melting columns. The uniformlylow temperatures of MORB extraction are not consistent withthe existence of hot plumes on or close to ocean ridges. Inthis modeling, the southern Atlantic mantle from Bouvet to about26°N is relatively homogeneous, whereas the Atlantic mantlenorth of about 26°N shows significant long-range heterogeneity.The mantle between the Charlie Gibbs and Jan Mayen fracturezones is strongly enriched in FeO/MgO, perhaps by a trappedfragment of basaltic crust. Iceland is explained as the productof this enrichment, not a hot plume. The East Pacific Rise,Galapagos Ridge, Gorda Ridge, and Juan de Fuca Ridge samplemantle that is heterogeneous over short distances. The mantlebeneath the Red Sea is enriched in FeO/MgO relative to the mantlebeneath the northern Indian Ocean.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

The occurrence and geochemistry of arsenic in groundwaters of the Newark basin of Pennsylvania

Elevated As concentrations in groundwater in the eastern United States have been recognized predominantly in the accretionary geologic terranes of northern New England. A retrospective examination of more than 18,000 existing groundwater samples from the Pennsylvania Department of Environmental Protection (PA DEP) Drinking Water and Sampling Information System database indicates that elevated groundwater As concentrations occur throughout the northern half of the Piedmont Province of Pennsylvania. Chemical analyses of 53 samples collected in 2005 from drinking water wells in this area all had detectable As, and 23% of these samples contained elevated (>133 nmol/L or >10 μg/L) concentrations of As. Elevated concentrations of As in the groundwater samples were most common in the Mesozoic sedimentary strata composed of sandstone and red mudstone with interbedded gray shale, and gray to black siltstone and shale. Arsenic was typically not elevated in groundwater of diabase intrusions of the Newark Basin or in crystalline and calcareous aquifers to the north of the Newark Basin. Geochemical parameters such as pH and oxidation–reduction potential can indicate mobility mechanisms of As in some regions. In this area, measured groundwater conditions were predominantly oxidizing (Eh > +50 mV), and more than 85% of samples contained arsenate as the dominant As species. Variations in pH were strongly correlated to the As concentration, with highest As concentrations observed at pH values greater than 6.4. The original source of As is most likely the black and gray shales that contain some arsenian pyrite with groundwater concentrations likely to be controlled by adsorption/desorption reactions with Fe oxides in the red mudstone aquifer materials.