Soil properties controlling Zn speciation and fractionation in contaminated soils

We determined the speciation of Zn in 49 field soils differing widely in pH (4.1–7.7) and total Zn content (251–30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.     

Ammonium in thermal waters of Yellowstone National Park: Processes affecting speciation and isotope fractionation

Dissolved inorganic nitrogen, largely in reduced form (), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH₄(T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH₄(T) concentration and δ¹⁸O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH₄(T) and other solutes in some areas. The isotopic composition of dissolved NH₄(T) is highly variable (δ¹⁵N = −6‰ to +30‰) and is positively correlated with pH values. In comparison to likely δ¹⁵N values of nitrogen source materials (+1‰ to +7‰), high δ¹⁵N values in hot springs with pH >5 are attributed to isotope fractionation associated with loss by volatilization. NH₄(T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative δ¹⁵N values that are attributed to condensation. NH₄(T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH₄(T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.     

Selenium fractionation and speciation in rocks, soils, waters and plants in polluted surface mine environment

A fractionation and speciation was performed to determine the distribution of selenium (Se) species in major components of quartzite surface mine environment (rocks, mine tailings, soils, stream sediments, surface waters and plants) in obov, Slovakia. A three-step sequential extraction procedure was utilised for the fractionation of Se in mine tailings and soils. The first extractant in order to evaluate the soluble and ligand exchangeable fraction of Se (0.1 mol/l K₂HPO₄ + KH₂PO₄ at pH 7.0) solubilized up to 15% of total Se content. The second step (0.1 mol/l K₂S₂O₈ at 90°C) which extracted Se associated or occluded with organic matter released 13 – 45% of total selenium. The decomposition of the residue (HNO₃ + H₂SO₄ 1+1) was used to solubilize the remaining 35–88% of total Se as the final step. The recovery of the procedure was between 97 and 106%. Selenate predominated in natural river and lake waters about pH 7.0 (>95%) but in acid mine leakings up to 40% of selenite was found. In the plants (birch leaves, grass leaves and roots) collected from the area acidified by mine leakings no significant accumulation of selenium was observed. The correlation between total Se and S in the rocks from the mine gives an evidence of the common origin of these elements in the studied area.     

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Mathematical simulation of the carbon isotopic fractionation between huminitic coals and related methane

In order to estimate the isotope fractionation effect between coals and methane during coalification a maturity-related fractionation model has been developed for coals and reservoir gases of NW Germany which is based on empirical data. Assuming that observed isotope shifts of the convertible carbon of coals of different maturities are related to a loss of methane during coalification and that this shift can be described by a Rayleigh distillation process, functions with preselected fractionation factors were fitted to measured isotope data of the convertible carbon of coals. The best approximation of theoretical and measured data was achieved with a low fractionation factor (α_c= 1.003). Using this model theoretical methane carbon isotope data were determined and compared to the isotopic composition of reservoir methanes of NW Germany. Although the methane isotope data of reservoir gases and the related maturity of the coals show a slight scatter, the theoretical data plot within the same range and follow the increase of the ¹³C concentration of reservoir gases with increasing maturity of the coals.     

Phosphorus speciation in surface sediments of a hypertrophic lake,Southwestern China: insights from fractionation and 31P NMR

Acta Geochimica - Phosphorus (P) species in surface sediments from a shallow, hypertrophic lake, Lake Dianchi, China, were investigated by P fractionation and 31P nuclear magnetic resonance (NMR)...     

REE fractionation,mineral speciation,and supergene enrichment of the Bear Lodge carbonatites,Wyoming, USA

The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ¹⁸O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO₄³⁻/CO₃²⁻ and F⁻/CO₃²⁻ ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.     

Isotopic fractionation and reaction kinetics between Cr(III) and Cr(VI) in aqueous media

The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H₂O₂ under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H₂O₂ as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.     

Speciation and fractionation of phosphorus in biosolids-amended soils: effects of water treatment residual nanoparticles

Phosphorus (P) speciation and fractionation are useful tools for assessing P mobility and potential transfer to water bodies. The current study aims to evaluate drinking water treatment residual nanoparticles (nWTRs) effects on P species in biosolids-amended soils using sequential chemical fractionation and mineral equilibrium model. Three different soil types were selected (El-Bostan, Kafr El-Dawar, Borg Al-Arab), amended with biosolids (3%), and different rates of nWTRs were applied. The P fractionation results revealed that addition of nWTRs to biosolids-amended El-Bostan soil increased the immobile aluminum phosphates from 27.30 to 88.90, 92.20, and 94.93% at 0.10, 0.20, and 0.30% application rate, respectively. Similar trend was noticed in Kafr El-Dawar soil. In Borg Al-Arab soil, nWTRs significantly (p < 0.05) increased aluminum phosphate to only 71.73% at the highest application rate (0.30%) due to its high content of calcium carbonate (35.70%). Similarly, phosphorous speciation analysis revealed that application of nWTRs significantly increased the proportions of immobile phosphate form (P sorbed to Al hydroxide) and amorphous sodium aluminum phosphate. Thus, water degradation via eutrophication can be minimized by applying nWTRs to biosolids-amended soils.     

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

The stoichiometry and stability of arsenic gaseous complexes were determined in the system As-H₂O ± NaCl ± HCl ± H₂S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As^(III) and As^(V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As^(III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As^(III) was measured from 250 to 450°C at the saturated vapor pressure of the system (P_sat) with a special titanium reactor that allows in situ sampling of the vapor phase. The values of partition coefficients for arsenious acid (H₃AsO₃) between an aqueous solution (pure H₂O) and its saturated vapor (K = mAs_vapor /mAs_liquid) were found to be independent of As^(III) solution concentrations (up to ∼1 to 2 mol As/kg) and equal to 0.012 ± 0.003, 0.063 ± 0.023, and 0.145 ± 0.020 at 250, 300, and 350°C, respectively. These results are interpreted by the formation, in the vapor phase, of As(OH)₃(gas), similar to the aqueous As hydroxide complex dominant in the liquid phase. Arsenic chloride or sulfide gaseous complexes were found to be negligible in the presence of HCl or H₂S (up to ∼0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As^(III)-H₂O (±NaCl) solutions up to 500°C demonstrate that the As(OH)₃ complex dominates As speciation both in dense H₂O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As^(III) measured in the H₂O-NaCl system up to 450°C are consistent with the As speciation derived from these spectroscopic measurements and can be described by a simple relationship as a function of the vapor-to-liquid density ratio and temperature. Arsenic^(III) partitioning between vapor and As-concentrated solutions (>2 mol As/kg) or As₂O₃ solid is consistent with the formation, in the vapor phase, of both As₄O₆ and As(OH)₃. Arsenic^(V) (arsenic acid, H₃AsO₄) vapor-liquid partitioning at 350°C for dilute aqueous solution was interpreted by the formation of AsO(OH)₃ in the vapor phase.The results obtained were combined with the corresponding properties for the aqueous As(III) hydroxide species to generate As(OH)₃(gas) thermodynamic parameters. Equilibrium calculations carried out by using these data indicate that As(OH)₃(gas) is by far the most dominant As complex in both volcanic gases and boiling hydrothermal systems. This species is likely to be responsible for the preferential partition of arsenic into the vapor phase as observed in fluid inclusions from high-temperature (400 to 700°C) Au-Cu (-Sn, -W) magmatic-hydrothermal ore deposits. The results of this study imply that hydrolysis and hydration could be also important for other metals and metalloids in the H₂O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.     

Exploring Cd,Cu, Pb,and Zn dynamic speciation in mining and smelting-contaminated soils with stable isotopic exchange kinetics

The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E₁) with a kinetic rate constant k₁ having values around 1 min⁻¹ and a much slower exchangeable pool (E₂) with k₂ ranging from 0.0001 min⁻¹ to 0.001 min⁻¹. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k₁ values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k₂ values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils.     

Oxygen solubility and speciation in sulphide-rich mattes

Sulphide-rich liquids are common in magmatic environments forming over a wide range of temperature, pressure, fO₂ and fS₂. They are economically important because they sequester valuable metals such as Cu, Ni, Au and Pt from silicate melts. The presence of accessory amounts of primary oxides associated with sulphide mineralisations is often ignored or unexplained. Experimental work has shown that large amounts of oxygen can dissolve into mattes at fO₂ typical of terrestrial environments. At the quartz-fayalite-magnetite fO₂ buffer, the molar fraction of O in the matte exceeds that of S, placing the composition of the matte to the magnetite side of the mss (monosulphide solid solution)-magnetite join in the Fe-S-O system. However, sulphides crystallise before magnetite in most sulphide mineralisations and are much more abundant. Moreover, the speciation of O in a matte is not well known. Here we report the results of an experimental study of the solubility of O in mattes as a function of fS₂, fO₂, temperature, and composition. We confirm previous observations that Ni and Cu have a negative effect on the solubility of O in mattes. We show evidence for the existence of FeSO as a structural constituent of mattes in the Fe-S-O system. We present a simple parameterisation of the amount of O dissolved in mattes under relevant geological conditions, and use this parameterisation to discuss mechanisms for the crystallisation of primary spinels associated with sulphides in the Kambalda massive sulphide deposit (Western Australia) and the Sudbury Igneous Complex (Ontario, Canada).     

Biogeochemistry of nitrous oxide in groundwater in a forested ecosystem elucidated by nitrous oxide isotopomer measurements

The biological and physical controls on microbial processes that produce and consume N₂O in soils are highly complex. Isotopomer ratios of N₂O, with abundance of ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O, and ¹⁴N¹⁴N¹⁸O relative to ¹⁴N¹⁴N¹⁶O, are promising for elucidation of N₂O biogeochemistry in an intact ecosystem. Site preference, the nitrogen isotope ratio of the central nitrogen atom minus that of the terminal nitrogen atom, is useful to distinguish between N₂O via hydroxylamine oxidation and N₂O via nitrite reduction.We applied this isotopomer analysis to a groundwater system in a temperate coniferous-forested ecosystem. Results of a previous study at this location showed that the N₂O concentration in groundwater varied greatly according to groundwater chemistry, i.e. NO₃⁻, DOC, and DO, although apportionment of N₂O production to nitrification or denitrification was ambiguous. Our isotopic analysis (δ¹⁵N and δ¹⁸O) of NO₃⁻ and N₂O implies that denitrification is the dominant production process of N₂O, but definitive information is not derived from δ¹⁵N and δ¹⁸O analysis because of large variations in isotopic fractionations during production and consumption of N₂O. However, the N₂O site preference and the difference in δ¹⁵N between NO₃⁻ and N₂O indicate that nitrification contributes to total N₂O production and that most measured N₂O has been subjected to further N₂O reduction to N₂. The implications of N₂O biogeochemistry derived from isotope and isotopomer data differ entirely from those derived from conventional concentration data of DO, NO₃⁻, and N₂O. That difference underscores the need to reconsider our understanding of the N cycle in the oxic-anoxic interface.     

Calcium isotope fractionation in calcite and aragonite

Calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite. Precipitation temperatures ranged from 0 to 28°C. Calcium isotope fractionation shows a temperature dependence in accordance with previous observations: 1000 · ln(α_cc) = −1.4 + 0.021 · T (°C) for calcite and 1000 · ln(α_ar) = −1.9 + 0.017 · T (°C) for aragonite. Within uncertainty the temperature slopes are identical for the two polymorphs. However, at all temperatures calcium isotopes are more fractionated in aragonite than in calcite. The offset in δ^44/40Ca is about 0.6‰. The underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals, or to different Ca reaction behavior at the solid-liquid interface. Recently, the observed temperature dependence of the Ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting (Lemarchand et al., 2004). We show that this mechanism can in principle also be applied to CaCO₃ precipitation in natural environments in normal marine settings. Following this model, Ca isotope fractionation in marine Ca carbonates is primarily controlled by precipitation rates. On the other hand the larger Ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates. The rate control model of Ca isotope fractionation predicts a strong dependence of the Ca isotopic composition of carbonates on ambient CO₃²⁻ concentration. While this model is in general accordance with our observations in marine carbonates, cultured specimens of the planktic foraminifer Orbulina universa show no dependence of Ca-isotope fractionation on the ambient CO₃²⁻ concentration. The latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water.     

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ⁶⁵Cu < 6.99) in comparison to the terrestrial crust (δ⁶⁵Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ⁶⁵Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ⁶⁵Cu ≈ 0).An increase of δ⁶⁵Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ^66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn²⁺ vs. Cu⁺), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity.     

The effects of soil type and chemical treatment on nickel speciation in refinery enriched soils: A multi-technique investigation

Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km² of land with Ni concentrations exceeding the Canadian Ministry of the Environment’s remedial action level of 200 mg kg⁻¹. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale ‘Kotodesh’, a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability.Stirred-flow dissolution experiments using pH 4 HNO₃ showed that Ni release from the limed Quarry muck and Welland loam soils was reduced (∼0.10%) relative to the unlimed soils (∼2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 μm in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils.The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne refinery. We provide the first evidence that Ni-Al LDH phases can form in anthropogenically enriched mineral field soils at circumneutral pH, and can lead to a reduction in Ni mobility. In the organic soils Ni is strongly complexed by soil organic matter; a property enhanced with liming. Interestingly, increased accumulation of Ni by A. murale grown in the limed muck and loam soils indicates that the plant may be capable of removing Ni from those fractions typically considered unavailable to most plants.     

Lithium speciation in aqueous fluids at high P and T studied by ab initio molecular dynamics and consequences for Li-isotope fractionation between minerals and fluids

Ab initio molecular dynamics simulations are performed to study the speciation changes in lithium bearing aqueous fluids at high temperature (T = 1000 K) and high pressures, P, between about 0.3 and 6.0 GPa. The simulations show a linear increase in Li coordination with fluid density, from 3.2 to about five in the considered pressure range. Towards low densities, associated LiF complexes are becoming increasingly stable, which is quantified by evaluating the dynamic behavior of the respective species. In the high-density region, HF complexes are observed. The differences in speciation may be related to structural changes of the solvent under compression. At a fluid density of 1.2 g/cm³, kinks in the pressure dependences of the oxygen–oxygen nearest neighbor distance and the oxygen–oxygen coordination are observed, which indicates a change in compaction mechanism. Assuming that the Li coordination difference between crystal and fluid is a major determinant for the isotopic fractionation between minerals and fluids, we expect only a small pressure dependence of the Li isotopic fractionation between Li bearing fluids and minerals. Our simulation results are consistent with experimental data that show reverse fractionation of ⁷Li between fluid and mineral, when Li is in tetrahedral instead of octahedral coordination in the crystal.     

Analysis and speciation of selenium ions in mine environments

 Aqueous extracts of five mine soil samples and a set of selenite (SeO₃ ^2–)–selenate (SeO₄ ^2–) solutions (0.5, 1, 5, 10 and 25 mg/l) were speciated using atomic absorption spectroscopy with hydride generation (AAS-HG) and ion chromatography (IC) to compare these methods for Se speciation. In another experiment, a SeO₃ ^2––SeO₄ ^2––SO₄ ^2– solution (25 mg/l) was reacted with CaO, MgO, MnO₂, CuO, La₂O₃, and WO₃ to evaluate the relative distribution of the Se species and SO₄ ^2– in the SORB (sorbed ions that were desorbed by NaOH), SOLN (equilibrium concentrations), CMPX (irreversibly sorbed and neutral ion pair complexes) fractions. The AAS-HG method was capable of analyzing Se as low as 0.002 mg/l, which was below the detection limit of IC. High concentration of SO₄ ^2– affected the chromatographic Se speciation either by shifting or overlapping Se peaks, in which AAS-HG was more useful. However, IC was capable of speciating aqueous SeO₃ ^2––SeO₄ ^2– directly without any sample pretreatment, whereas AAS-HG measured SeO₃ ^2–+SeO₄ ^2–, and SeO₃ ^2– in separate runs and SeO₄ ^2– was calculated from the difference, i.e., spectrophotometric speciation was an indirect method. For both Se species, AAS-HG and IC data were comparable within detection standard deviations. Ratios of different Se species at measured soil pH and pe indicated that SeO₃ ^2– or SeO₄ ^2– would be the dominant Se species; the p(SeO₄ ^2–/SeO₃ ^2–) values further suggested SeO₄ ^2– would be the major solution species. Except for CaO and MgO treatments, the %SeO₃ ^2– in the SORB fraction was ≥%SeO₄ ^2–. In the SOLN fraction %SeO₄ ^2– was ≥%SeO₃ ^2– for all oxides but CaO, whereas in the CMPX fraction this order was observed for only CaO and MnO₂. The %SeO₃ ^2– was highest in the SOLN fraction for all oxides but MgO and La₂O₃ for these two oxides SeO₃ ^2– dominated in CMPX and SORB fractions, respectively. The SOLN fraction also contained the highest %SeO₄ ^2– for all oxides but MgO which retained SeO₄ ^2– primarily in the SORB fraction. The %SeO₃ ^2– and %SeO₄ ^2– in the CMPX fraction were highest for MgO, thus, suggesting a possible formation of MgSeO₃ ⁰ and MgSeO₄ ⁰. A similar trend of SORB %SO₄ ^2– and SORB %SeO₄ ^2– was attributed to the analogous adsorption mechanisms (outer-sphere complexation). For all oxides but MgO, %SO₄ ^2– was <%SeO₄ ^2– in the SOLN fraction and ≥%SeO₄ ^2– in the CMPX fraction. Comparative ionic distributions provide an overall picture of the relative abundance of different Se species in various fractions associated with different oxides present in micro- and macrolevels in soils and geological materials. Received: 27 December 1995 · Accepted: 29 April 1997     

Improvement on the treatment of thick oil sewage by using integrated biochemical treatment technology

Sewage treatment station in oilfield needs a new process to meet the desired requirements. A new process was proposed to meet the discharge standards, which consisted of the following sub-processes: electrochemical treatment → coagulation treatment → integrated biochemical treatment of moving bed biofilm reactor and membrane bio-reactor → combined treatment process of macroporous adsorption resin. Electrochemical treatment included 5 electrolytic cells, total volume of which was 10 L. The PFS was chosen as the coagulants in the coagulation treatment, and the removal rate of COD could reach 66% when the dosage of PFS was 500 mg/L. The biochemical treatment consisted of anoxic tank, aerobic tank and membrane zone, and the removal rate of COD was about 55–70% when HRT was 12 h. SD300 resin was chosen as the best adsorbent in the treatment using macroporous adsorption resin. In addition, the effluent COD after coagulation treatment process becomes about 180 mg/L, the effluent COD after biological treatment becomes about 50 mg/L, and the last effluent COD with the macroporous adsorption resin becomes about 20 mg/L. The three-dimensional fluorescence spectrum was used to analyze the differences in types of organic matters in water samples between the raw water and the treated one. The results demonstrated that the new process meets the needs of wastewater treatment.