Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d’Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.     

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg⁻¹. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants’ roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils.     

Dissolved metals and associated constituents in abandoned coal-mine discharges,Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s⁻¹, with a median of 18.4 L s⁻¹. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-μm pore-size filter) SO₄ (34–2000), Fe (0.046–512), Mn (0.019–74), and Al (0.007–108) varied widely. Predominant metalloid elements were Si (2.7–31.3 mg L⁻¹), B (<1–260 μg L⁻¹), Ge (<0.01–0.57 μg L⁻¹), and As (<0.03–64 μg L⁻¹). The most abundant trace metals, in order of median concentrations (range in μg/L), were Zn (0.6–10,000), Ni (2.6–3200), Co (0.27–3100), Ti (0.65–28), Cu (0.4–190), Cr (<0.5–72), Pb (<0.05–11) and Cd (<0.01–16). Gold was detected at concentrations greater than 0.0005 μg L⁻¹ in 97% of the samples, with a maximum of 0.0175 μg L⁻¹. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in μg/L), were Y (0.11–530), Ce (0.01–370), Sc (1.0–36), Nd (0.006–260), La (0.005–140), Gd (0.005–110), Dy (0.002–99) and Sm (<0.005–79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH.     

The presence of anomalous trace element levels in present day Jamaican soils and the geochemistry of Late-Miocene or Pliocene phosphorites

High levels of Cd and Zn in Jamaican soils observed in geochemical surveys are related to the presence of phosphorites of possible Late-Miocene or Pliocene age. The trace element and REE geochemistry of the phosphorites, together with SEM studies, indicate a guano origin for the phosphorites. No specific host minerals for Cd could be identified in the fossiliferous phosphorite which is characterized by uniquely high levels of Cd, Zn, Ag, Be, U and Y. However, in the soil Cd is present in lithiophorite and a complex history of pedological development is preserved in the aluminous–goethite present in the soil. The unique guano signature is preserved in the soil despite the fact that guanos themselves have either not been observed or have been destroyed by continuing karst and soil development. The phosphorite geochemical signature can be traced in the data of a 1988 island-wide soil geochemical survey, identifying areas where the Palaeo-environment that supported bird ‘rookeries’ existed in the Late-Miocene or Pliocene.     

Geochemical characterization of surface waters and groundwater resources in the Managua area (Nicaragua,Central America)

This paper reports new geochemical data on dissolved major and minor constituents in surface waters and ground waters collected in the Managua region (Nicaragua), and provides a preliminary characterization of the hydrogeochemical processes governing the natural water evolution in this area. The peculiar geological features of the study site, an active tectonic region (Nicaragua Depression) characterized by active volcanism and thermalism, combined with significant anthropogenic pressure, contribute to a complex evolution of water chemistry, which results from the simultaneous action of several geochemical processes such as evaporation, rock leaching, mixing with saline brines of natural or anthropogenic origin. The effect of active thermalism on both surface waters (e.g., saline volcanic lakes) and groundwaters, as a result of mixing with variable proportions of hyper-saline geothermal Na–Cl brines (e.g., Momotombo geothermal plant), accounts for the high salinities and high concentrations of many environmentally-relevant trace elements (As, B, Fe and Mn) in the waters. At the same time the active extensional tectonics of the Managua area favour the interaction with acidic, reduced thermal fluids, followed by extensive leaching of the host rock and the groundwater release of toxic metals (e.g., Ni, Cu). The significant pollution in the area, deriving principally from urban and industrial waste-water, probably also contributes to the aquatic cycling of many trace elements, which attain concentrations above the WHO recommended limits for the elements Ni (∼40 μg/l) and Cu (∼10 μg/l) limiting the potential utilisation of Lake Xolotlan for nearby Managua.     

The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.