Applied Geochemistry (v.17, #4)

Current Lit Survey (III-XXVII).

Organic C burial rates and C–S relationships were investigated in the Holocene sediment sequences of 3 shallow polymictic coastal lagoons in the southern Baltic Sea to better understand the biogeochemical cycling of C and S in these environmental systems. The results show that these lagoons may have a considerable influence on the environmental status of the southern Baltic Sea area in having the potential to act as a temporary sink or source for heavy metals. High organic C accumulation rates (Corg-AR) can be observed in the sediments due to a high organic matter supply from land and a high productivity of the water bodies as a result of eutrophication. However, organic C burial does not increase as a result of increasing sediment accumulation rates (SAR). Even when high sedimentation rates do occur, there appears to be a thorough recycling and resuspension of the sediment enhancing the biological decay of organic matter before burial or the removal of organic matter from the system by transport. That is why high SAR in the coastal lagoons do not enhance pyrite formation, and thereby permanent fixing of heavy metals in the sediments, to the extent that could be expected from their magnitude. Initially there is a high potential for a temporary binding of heavy metals, but the latter are likely to be subject to mobilization and redistribution within the sediments and the water column. The patterns of burial of organic and mineral matter are different from those observed in the present-day Baltic Proper, implying possible important links in deposition between the central and coastal areas of the Baltic Sea and implications for C cycling in the ecosystem of the Baltic Sea.

Surprisingly little is known about the relationship between the labile phases removed by sequential extraction procedures and those liberated by single leaches that minimally impact the alumino-silicate matrix of solids. This investigation examines the relationship between the summed concentrations of Al, Co, Cu, Fe, Mn, Ni, Pb and Zn released by an optimized 3-step standardized sequential extraction procedure and those released by a single 0.5 M HCl leach. Thirty-nine representative soil and road deposited sediment samples were examined from an urban watershed, in Honolulu, Hawaii, which has been shown to have a high degree of traffic-associated pollution. Properties of samples analyzed varied widely and exhibited a range in cation exchange capacities from 7 to 59 cmolc/kg, pH values from 3.5 to 7.9, and organic C contents from 1 to 29%. Results indicate that the dilute HCl leach was slightly more aggressive than the sequential procedure as it removed significantly more Al, Cu, Fe, Mn and Ni; though no significant differences were observed between Co, Pb and Zn concentrations liberated by the two approaches. Both approaches showed limited dissolution of the crystal lattice with ⩽9% of the total Al liberated. Regardless of approach, element mobility was the same with the order being: Pb>Mn>Zn>Co≈Cu>Ni>Fe ∼ Al. Regression analysis indicated highly significant (P<0.0001) logarithmic relationships between the two digestion procedures, with coefficients of determination (r 2) ⩾92% for all elements except Fe (54%) and Ni (64%). Further support for the strong relationships between elements liberated by both digestions was gained from geochemical contrasts between anomalous and background levels and concentration enrichment ratios. This was particularly true for Pb and Zn, the most anthropogenically enhanced trace metals in the watershed. All data indicated that a dilute HCl leach was a valuable, rapid, and cost-effective analytical tool in contamination assessment.

Enzyme LeachSM (EL) soil surveys were undertaken over known epithermal Au mineralisation at El Mozo and Llano Largo, Azuay, Ecuador to assess the utility of the technique for identifying such deposits in the Ecuadorian Andes. The results indicate the development of both apical- and oxidation-type EL anomalies over auriferous structures at the two sites, the former systematically incorporating Au, and the latter Cl and Br. The spectrum of elements responsive to mineralisation at El Mozo (Cl, Br, I, La, Ce, Nd, Cu, Pb, Au, As, Sb, Ag, Zr, Sr) was found to be considerably greater than at Llano Largo (Cl, Br, Au, As, Sb, Ag, Zn), probably reflecting the contrasting high- and low-sulphidation assemblages of the two prospects. Ratios of EL versus aqua-regia extractable trace element concentrations ranged from 1:<100 for Mn to 1:>400 for chalcophile elements such as Pb, Sb, As, Bi and Ag. Strong correlations between the concentrations of several analytes (including Mn, Sr, Cu, Co, As) extracted by the two procedures indicate, however, that EL datasets are extensively influenced by bulk matrix composition. Spatial variations of EL extractable Mn were found to exert no major influence on apical or oxidation suite anomaly patterns at El Mozo. However, Mn-normalisation of halogen data for Llano Largo elucidated otherwise obscure oxidation features, potentially related to Au mineralisation. Ratios between elements subject to apical enrichment and those of the oxidation suite (e.g. Cl/Au and Bi/Br) were found to highlight known Au targets with improved clarity. The formation mechanism of the recorded Au anomalies is uncertain, but may involve physical enrichment of Au in the soil during pedogenesis with subsequent in-situ formation of (EL soluble) Au halide complexes. The strength of such apical features is, in part, probably a function of the minimal depths to mineralisation which characterise El Mozo and Llano Largo. Oxidation halos formed by volatile non-metallic elements such as Cl and Br may, therefore, provide more valuable EL pathfinders for more deeply concealed epithermal targets.

Changes in the sorption capacity of Coastal Plain sediments due to redox alteration of mineral surfaces by Elizabeth P Knapp; Janet S Herman; Aaron L Mills; George M Hornberger (387-398).
Chemical characteristics of grain coatings in a Coastal Plain sandy aquifer on the Eastern Shore of Virginia were investigated where sediments have been exposed to distinct groundwater redox conditions. Dissolved O2 was 5.0 to 10.6 mg L−1 in the regionally extensive aerobic groundwater, whereas in a narrow leachate plume it was only <0.001 to 0.9 mg L−1. The amount of dissolved Fe in the aerobic groundwater was only 0.005 to 0.01 mg L−1, but it was 12 to 47 mg L−1 in the anaerobic zone. The amount of extractable Fe was an order of magnitude higher for the aerobic sediments than for the anaerobic sediments indicating that reductive dissolution removed the oxide coatings. The capacity for anion sorption on the sediment surfaces, as indicated by the sorption of 35SO4 2-, was an order of magnitude higher in the aerobic vs. anaerobic sediments. The presence of anaerobic groundwater did not significantly alter the amount of extractable Al oxides on the surface of the sediments, and those coatings helped to maintain a high surface area. The removal of the Fe oxides from the grain surfaces under anaerobic conditions was solely responsible for the significant reduction of SO4 sorption observed. This loss of capacity for anion sorption could lead to more extensive transport of negatively charged constituents such as some contaminant chemicals or bacteria that may be of concern in groundwater.

Experimental study and modeling of the sorption of uranium(VI) onto olivine-rock by F.Z. El Aamrani; L. Duro; J. de Pablo; J. Bruno (399-408).
The sorption of U(VI) onto the surface of olivine has been experimentally investigated at 25 °C under an air atmosphere as a function of pH, solid surface to volume ratio and total U concentration. Sorption has been observed to decrease as the extent of carbonate complexation of U(VI) in solution increases, which is attributed to the competition between aqueous and solid ligands for the coordination of U. The experimental results have been interpreted by means of two different approaches: (1)a semi-empirical model, exemplified by the application of a Langmuir isotherm and (2) a non-electrostatic thermodynamic surface complexation model which includes the formation of the surface species: >SO–UO2 + and >SO–UO2(OH). The following stability constants for these species have been determined from the thermodynamic analysis: K(>SO–UO2 +)=289±71 and K(>SO–UO2(OH))=(3.4±0.4)×10−6. The comparison of the sorption of U onto olivine with granites of different origin indicate that the use of this mineral as additive to the backfill of deep high level nuclear waste repositories could retard the migration of U from the repository to the geosphere.

Iron oxide precipitates are abundant in small stream systems of NW Mississippi, USA especially during the wet winter months. The properties of these specific materials are unknown even though they have the potential to influence soil physical properties and adsorb chemical pollutants in sediment environments. Streamwater and associated precipitates were collected from 4 representative streams at Cedar Creek (CC), Lee's Creek (LC), Spring Creek (SC), and Toby Creek (TC) during winter flow periods. Precipitate specimens were characterized for mineralogy, color, and solubility in oxalate (o), dithionite (d), and HNO3. Chemical composition of the water was dominated by Ca, Na, Mg, and K, in that order, at an average pH of 7.0. X-ray diffraction (XRD) and differential scanning calorimeter (DSC) data indicated that the precipitates were primarily poorly ordered ferrihydrite (CC, TC) and lepidocrocite (LC, SC). The Feo/Fed ratios were 0.40 (CC), 0.68 (LC), 0.66 (SC), and 0.67 (TC). Organic C contents were 80.6, 38.0, 63.0, and 51.3 g kg−1 for the same samples. Precipitate color was uniform among sites, averaging 6.7 YR 4.8/6.2. After oxalate extraction, redness increased slightly in the CC and SC specimens, and decreased in the others. Extraction with dithionite depleted the red color in all specimens, but had less effect on the CC and SC samples which retained hues at 7.9 and 7.3 YR, respectively. Dithionite extractable P equaled 1.02 (CC), 0.72 (LC), 0.56 (SC), and 0.99 (TC) g kg−1. The results from this study indicated that: (1) the precipitates are either primarily poorly ordered ferrihydrite or lepidocrocite; (2) the solubility of ferrihydrite in both oxalate and dithionite is influenced by C contents; and (3) the redder, ferrihydrite specimens contain the greatest P concentrations.

The quality of water in streams that are contaminated by acid drainage from mines and from the weathering of mineralized rocks improves as the water flows downstream. The purpose of this study was to investigate the geochemical processes that occur in one such stream and to determine the fate of the trace metals that are removed from the water. The stream chosen for this purpose was the Snake River, Summit County, Colorado, which is affected by natural acid rock-drainage (ARD) containing SO4, Al, Fe, and various trace elements such as Zn, Cu, Pb, Ni, and others. Most of the Fe in the Snake River is removed from solution by the oxidation of Fe2+ to Fe3+ and the subsequent precipitation of Fe-oxyhydroxides that form a massive ferricrete deposit near the springs that feed the river. Further downstream, the Snake River (pH=3.0) mixes with water from Deer Creek (pH= 7.0) thereby increasing its pH to 6.3 and causing SO4-rich precipitates of Al-oxyhydroxide to form. The precipitates and associated organic C complexes sorb trace metals from the water and thus have high concentrations of certain elements, including Zn (540–11,400 ppm), Cu (34–221 ppm), Pb (90–340 ppm), and Ni (11–197 ppm). The concentrations of these elements in the precipitates that coat the streambed rise steeply in the zone of mixing and then decline downstream. The trace element concentrations of the water in the mixing zone at the confluence with Deer Creek decrease by 75% or more and are up to 3 orders of magnitude lower than those of the precipitates. Sorption curves for Zn, Cu, Pb, Ni, and SO4 were derived by stepwise neutralization of a sample of Snake River water (collected above the confluence with Deer Creek) and indicate that the trace metals are sorbed preferentially with increasing pH in the general order Pb, Cu, Zn, and Ni. Sulfate is removed between pH 4 and 5 to form an Al-hydroxysulfate and/or by sorption to microcrystalline gibbsite. The sorption data determined from the neutralization experiment were used to account for the downstream decrease of trace-metal concentrations in the precipitates. The results of this study demonstrate that the partitioning of trace metals in the Snake River is not only a function of pH, but also depends on the progressive removal of trace metals as the water of the Snake River flows through its confluence with Deer Creek. The chemical composition of the water also determines what compounds precipitate with increasing pH.

A steady state geochemical model has been developed to assist in understanding surface-catalysed oxidation of aqueous Fe(II) by O2(aq), which occurs rapidly at circumneutral pH. The model has been applied to assess the possible abiotic removal of Fe(II)(aq) from alkaline ferruginous mine water discharges using engineered reactors with high specific-surface area filter media. The model includes solution and surface speciation equilibrium, oxidation kinetics of dissolved and adsorbed Fe(II) species and mass transfer of O2(g). Limited field data for such treatment of a mine water discharge were available for model development and assessment of possible parameter values. Model results indicate that an adsorption capacity between 10−6 and 10−5 mol l−1 is sufficient for complete removal, by oxidation, of the Fe(II)(aq) load at the discharge. This capacity corresponds approximately to that afforded by surface precipitation of Fe(III) oxide onto plastic trickling filter media typically used for biological treatment of wastewater. Extrapolated literature values for microbial oxidation of Fe(II)(aq) by neutrophilic microbial populations to the simulated reactor conditions suggested that the microbially-mediated rate may be several orders-of-magnitude slower than the surface-catalysed oxidation. Application of the model across a range of mine water discharge qualities shows that high Fe(II)(aq) loadings can be removed if the discharge is sufficiently alkaline. Additional reactor simulations indicate that reactor efficiency decreases dramatically with pH in the near acid region, coinciding with the adsorption edge for Fe2+ on Fe oxyhydroxide. Alkaline discharges thus buffer pH within the range where Fe(II)(aq) adsorbs onto the accreting Fe hydroxide mineral surface, and undergoes rapid catalytic oxidation. The results suggest that the proposed treatment technology may be appropriate for highly ferruginous alkaline discharges, typically associated with abandoned deep coal mines.

Processing waters contain up to 10 mg l−1 dissolved As at the Macraes mine, New Zealand, and this is all removed by adsorption as the water percolates through a large earth dam. Laboratory experiments were set up to identify which mineral is the most effective substrate for this adsorption of As. The experiments were conducted using infrared (IR) spectroscopy of thin mineral films adhering to a ZnSe prism. Silicates, including kaolinite, adsorbed only small amounts of As which was readily washed off. Hydrated Fe oxides (HFO) were extremely effective at adsorbing As, particularly the natural amorphous HFO currently being deposited from dam discharge waters at the Macraes mine. An adsorption isotherm determined for this natural material has the adsorption constant, K ads=(1.9±0.4)×104 M−1, and the substrate becomes saturated with adsorbed As when solution concentrations exceed about 50 mg l−1. Saturation is not being reached at the Macraes mine. Arsenic adsorbed on to natural HFO has a distinctive IR spectrum with the absorption peak varying from 800 cm−1 (alkaline solutions) to 820 cm−1 (neutral to acid solutions). Much of this adsorbed As is strongly bound and difficult to wash off. Arsenate ions adsorb in a bidentate structure which may be a precursor for scorodite crystallisation.

Irreversible water–rock mass transfer accompanying the generation of the neutral, Mg–HCO3 and high-pH, Ca–OH spring waters of the Genova province, Italy by Jessica Bruni; Marco Canepa; Giovanni Chiodini; Roberto Cioni; Francesco Cipolli; Antonio Longinelli; Luigi Marini; Giulio Ottonello; Marino Vetuschi Zuccolini (455-474).
In a recent survey of the spring waters of the Genova province, many neutral Mg–HCO3 waters and some high-pH, Ca–OH waters were found in association with serpentinites. All the springs are of meteoric origin as indicated by the stable isotopes of water and dissolved N2 and Ar. Interaction of these meteoric waters with serpentinites determines a progressive evolution in the chemistry of the aqueous phase from an immature Mg-rich, SO4–Cl facies of low salinity to an intermediate Mg–HCO3 facies (pH 7.0–8.5, PCO2 10−3.5–10−2.5 bar, Eh 150–250 mV), and to a mature Ca–OH facies (pH 10–12, PCO2 10−9.4−10−10.6 bar, Eh-390 to-516 mV). The irreversible water–rock mass transfer leading to these chemical changes in the aqueous phase was simulated through reaction path modeling, assuming bulk dissolution of a local serpentinite, and the precipitation of gibbsite, goethite, calcite, hydromagnesite, kaolinite, a montmorillonite solid mixture, a saponite solid mixture, sepiolite, and serpentine. The simulation was carried out in two steps, under open-system and closed-system conditions with respect to CO2, respectively. The calculated concentrations agree with analytical data, indicating that the computed water-rock mass transfer is a realistic simulation of the natural process. Moreover, the simulation elucidates the role of calcite precipitation during closed-system serpentinite dissolution in depleting the aqueous solution of C species, allowing the concurrent increment in Ca and the acquisition of a Ca–OH composition. Calcium–OH waters, due to their high pH, tend to absorb CO2, precipitating calcite. Therefore, these waters might be used to sequester anthropogenic CO2, locally preventing environmental impact to the atmosphere.

Trace metal concentrations in soils and in stream and estuarine sediments from a subtropical urban watershed in Hawaii are presented. The results are placed in the context of historical studies of environmental quality (water, soils, and sediment) in Hawaii to elucidate sources of trace elements and the processes responsible for their distribution. This work builds on earlier studies on sediments of Ala Wai Canal of urban Honolulu by examining spatial and temporal variations in the trace elements throughout the watershed. Natural processes and anthropogenic activity in urban Honolulu contribute to spatial and temporal variations of trace element concentrations throughout the watershed. Enrichment of trace elements in watershed soils result, in some cases, from contributions attributed to the weathering of volcanic rocks, as well as to a more variable anthropogenic input that reflects changes in land use in Honolulu. Varying concentrations of As, Cd, Cu, Pb and Zn in sediments reflect about 60 a of anthropogenic activity in Honolulu. Land use has a strong impact on the spatial distribution and abundance of selected trace elements in soils and stream sediments. As noted in continental US settings, the phasing out of Pb-alkyl fuel additives has decreased Pb inputs to recently deposited estuarine sediments. Yet, a substantial historical anthropogenic Pb inventory remains in soils of the watershed and erosion of surface soils continues to contribute to its enrichment in estuarine sediments. Concentrations of other elements (e.g., Cu, Zn, Cd), however, have not decreased with time, suggesting continued active inputs. Concentrations of Ba, Co, Cr, Ni, V and U, although elevated in some cases, typically reflect greater proportions attributed to natural sources rather than anthropogenic input.

Geochemical trends in metal-contaminated fiord sediments near a former lead–zinc mine in West Greenland by Bo Elberling; Gert Asmund; Helmar Kunzendorf; Eirik J Krogstad (493-502).
Disposal of sulfidic waste in marine environments implies an environmental risk due to potential release and spreading of heavy metals to sediments and biota on a regional scale. However, tailings disposal in marine systems is practised in several places. Fiord sediments near Black Angel Mine in West Greenland are contaminated by Pb and Zn as a result of mining activity and marine disposal in the period 1973–1990. Chemical analyses were performed on 6 fiord sediment cores collected up to 10 km away from the disposal area and included heavy metal analysis, high-resolution stable Pb isotope stratigraphy and radiochemical dating (210Pb). The results were used for evaluating spatial and temporal distribution of anthropogenic heavy metals from the marine disposal. A significant accumulation of Pb and Zn on a regional scale is still observed 9 years after mine closure. Stable Pb-isotope data provide a unique fingerprint of the mining-related Pb sources in the area. Today spreading of mining-related Pb up to 10 km away from the mining area accounts for more than 80% of total Pb in sediment deposited within the last 100 years.

The solubility of rhodochrosite (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments by Dorthe L Jensen; Jens K Boddum; Jens Christian Tjell; Thomas H Christensen (503-511).
Natural groundwaters are often reported to be highly supersaturated with the carbonate minerals siderite (FeCO3) and rhodochrosite (MnCO3). The kinetics of precipitation and dissolution were determined in the light of new determinations of the solubility products of siderite and rhodochrosite. Laboratory experiments showed that the precipitation kinetics of siderite and rhodochrosite were much slower than that of calcite, and also much slower than their dissolution kinetics. Experiments with supersaturated solutions failed to reach steady state within 474 days in the case of siderite, whereas steady state for rhodochrosite was reached after 140 days. Suspensions of siderite and rhodochrosite crystals reached steady state after 10 and 80 days, respectively. The solubility product of siderite (−log K S0(FeCO3)) was 11.03 ± 0.10 for dried crystals and 10.43 ± 0.15 for wet crystals. For rhodochrosite the solubility product (−log K S0(MnCO3)) was 11.39 ± 0.14 for dried crystals and 12.51 ± 0.07 for wet crystals. The solubility product determined from supersaturated solutions was −log K S0(MnCO3)=11.65 ± 0.14. The observed slow precipitation kinetics of siderite and rhodochrosite might explain the apparent supersaturation that is often reported for anaerobic aquatic environments.

Reply to the comment on “Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy” by Mahendra P. Verma by Pasquale Panettiere; Gianni Cortecci; Enrico Dinelli; Alberto Bencini; Massimo Guidi (515-516).