The influence of surface oxidation of chalcocite on its floatability and ethyl xanthate sorption

The results obtained from measurements of potassium ethyl xanthate (EtXK) sorption by synthetic chalcocite (Cu₂S) and the results of chalcocite floatability measurements are presented.Five chalcocite samples, denoted as Cu₂S A, B, C, D and E, were used for the measurements. Chalcocite samples of 60–75 μm were prepared in the same manner but were kept under conditions which differed in their degree to prevent surface oxidation by atmospheric oxygen.Chalcocite surface oxidation has a strong effect both on xanthate sorption and on chalcocite floatability. The maximal amount of xanthate abstracted (Q_max) by chalcocite samples from deoxygenated solutions after a long sorption period increases with increasing oxidation of the samples. The Q_max values give information concerning the total amount of surface oxidation products.Chalcocite decreases its floatability with increasing surface oxidation. Most oxidized chalcocite samples required an about 100 times greater collector consumption to obtain the same flotation results than the least-oxidized samples studied.     

Relating spatial and temporal variability in sediment chlorophylla and carbohydrate distribution with erodibility of a tidal flat

Trends in the spatial distribution of chlorophylla (chla) and colloidal and total carbohydrates on the Molenplaat tidal flat in the Westerschelde estuary, Netherlands, reflected spatial differences in physical properties of the sediment. Results from a Spearman Rank Order Correlation indicated that many of the physical and biological measures covaried. Multiple regression analyses describing the relationship between colloidal carbohydrates and sediment properties resulted in several highly significant equations, although in all cases chla was able to predict colloidal carbohydrate content. Relationships between sediment surface chla and colloidal carbohydrate, and sediment erodibility (i.e., critical erosion threshold, U_crit, and mass of sediment eroded at a velocity of 30 cm s^?1) determined in annular flume experiments were examined. Overall sediment erodibility was lowest (i.e., high thresholds, low mass eroded) for the siltiest sediments in June 1996 when chla and colloidal carbohydrates were high (56.9 μg gDW^?1 and 320.6 μg gluc.equ. gDW^?1, respectively), and greatest (i.e., low thresholds, high mass eroded) at the sandier sediments in September 1996, when chla and colloidal carbohydrates were low (1.0 μg gDW^?1 and 5.7 μg gluc.equ. gDW^?1, respectively). When sediments were grouped according to relative silt content, the most significant relationships were found in muddy sand with a finegrained fraction (<63 μm) of 25–50%. Thresholds of erosion increased, while mass of sediment eroded decreased, with increasing chla and colloidal carbohydrate. A similar trend was observed for the sand-muddy sand (63 μm 10–25%). In the sand (63 μm 0–10%), there were no relationships for U_crit, whereas mass eroded appeared to increase with increasing chla and colloidal carbohydrate. The increased carbohydrate may stick sand grains together, altering the nature of erosion from rolling grains to clumps of resuspension.     

Ammonium excretion by benthic invertebrates and sediment-water nitrogen flux in the Gulf of Mexico near the Mississippi River outflow

Benthic macroinvertebrate biomass and ammonium excretion rates were measured at four stations in the Gulf of Mexico near the Mississippi River mouth. Calculated areal excretion rates were then compared to sediment-water nitrogen fluxes measured in benthic bottom lander chambers at similar stations to estimate the potential importance of macroinvertebrate excretion to sediment nitrogen mineralization. Excretion rates for individual crustaceans (amphipods and decapods) was 2–21 nmoles NH₄ ⁺ (mg dry weight)^?1 h^?1. The mean excretion rates for the polychaetes, Paraprionaspio pinnata [6–12 nmoles NH₄ ⁺ (mg dry weight)^?1h^?1] and Magelona sp. [27–53 nmoles NH₄ ⁺ (mg dry weight)^?1h^?1], were comparable or higher than previous measurements for similar size benthic or pelagic invertebrates incubated at the same temperature (22±1°C). Although the relatively high rates of excretion by these selective feeders may have been partially caused by experimental handling effects (e.g., removal from sediment substrates), they probably reflected the availability of nitrogen-rich food supplies in the Mississippi River plume. When the measured weight-specific rates were extrapolated to total areal biomass, areal macroinvertebrate excretion estimates ranged from 7 μmole NH₄ ⁺ m^?2h^?1 at a 40-m deep station near the river mouth to 18 μmole NH₄ ⁺ m^?2h^?1 at a shallower (28-m deep) station further from the river mouth. The net flux of ammonium and nitrate from the sediments to the water measured in bottom lander chambers in the same region were 15–53 μmole NH₄ ⁺ m^?2h^?1 and ?25–21 μmole NO₃ ^? m^?2h^?1. These results suggest that excretion of NH₄ ⁺ by macroinvertebrates could be a potentially important component of benthic nitrogen regeneration in the Mississippi River plume-Gulf shelf region.     

Application of the photoacoustic method for characterization of natural galena (PbS)

Electron transport properties of single crystal and polycrystalline natural mineral galena (PbS) samples from the Trep?a mine, Yugoslavia, were determined using the photoacoustic frequency transmission technique. Their thermal diffusivity (D _T≈0.16 × 10^?5 m² s^?1), the coefficient of diffusion (D between 0.15×10^?2 0.16×10^?2 m² s^?1) and lifetime of the excess carrier (τ≈35 μs and the front and rear recombination velocity (s _g≈65.5 m s^?1 and s _b≈66.4 m s^?1, respectively), were calculated by comparing the experimental results and the theoretical photoacoustic amplitude and phase signals. The lattice parameter obtained by X-ray work was a?=5.936?Å. The free carrier concentration of these single-crystal samples was measured using the Hall method (N?=?3×10¹⁸ cm^?3). Measurements of the optical reflectivity of the same samples, as a function of wavelength, in the infrared and far infrared ranges, were performed. In the far infrared range a free electron plasma frequency was observed and numerically analyzed, using the least-squares fitting procedure. The values of optical parameters were calculated and the value of the free carrier concentration obtained by the Hall method was confirmed.     

Effect of fish and mesozooplankton manipulation on the phytoplankton community in the Patos Lagoon estuary,Southern Brazil

An enclosure experiment in the Patos Lagoon estuary, southern Brazil (32°S, 52°W) investigated the response of phytoplankton to the enhancement of mesozooplankton and fish abundance. Addition of nutrients (NO₃ ^? and PO₄ ^?) stimulated the growth of 3–20 μm diameter phytoplankton, especially the diatomCylindrotheca closterium, which, in turn, was heavily grazed by the dominant mesozooplankter, the copepodAcartia tonsa. Acartia did not consume small (2–3 μm) autotrophic flagellates and the cyanobacteriaAnabaena sp., despite their high cell number. Largest grazing ofC. closterium by the copepod occurred only after a decrease of ciliate abundance. The addition of mesozooplankton did not change the levels of primary production, but it significantly increased the phytoplankton assimilation number. Highest chlorophylla concentrations were measured in enclosures stocked with juveniles of the fishXenomelaniris brasiliensis. The large phytoplankton biomass and low mesozooplankton abundance found in this treatment indicates an, effective predator-mediated action on the phytoplankton community.     

Flotation of germanium n and p with potassium ethyl xanthate

Steady-state potential of the germanium electrode, flotation tests and results of spectrophotometric ATR (Attenuated Total Reflection) measurements of germanium surface in the presence and absence of potassium ethyl xanthate are presented.On the basis of the steady-state potentials of the germanium electrode in ethyl xanthate solutions, the standard potential E⁰ of the reaction: Ge + 2EtX^? = Ge (EtX)₂ + 2e is estimated. The pH ranges of the dixanthogen (EtX)₂ and the germanium xanthate Ge(EtX)₂ species predominance in the bulk solution are calculated. It has been established that flotation of germanium is greater than the natural floatability (in the absence of collectors) in the pH ranges where (EtX)₂ or Ge (EtX)₂ are present in the bulk solution. Spectrophotometric results reveal the presence of (EtX)₂ and Ge (EtX)₂ on the surface in the same pH ranges as is calculated for the bulk reactions.No significant differences in the surface properties and the flotation behaviour between germanium n and p have been found.     

Photosynthetic production and biomass of the subtropical seagrass halodule wrightii along an estuarine gradient

Seasonal patterns of aboveground and belowground biomass, leaf chlorophyll (chl) content, and in situ differences in photosynthetic parameters were examined in the shoal grass Halodule wrightii along an estuarine gradient in the western Gulf of Mexico. Continuous measurements of biomass were collected over a 5-yr period (1989–1994) with respect to several abiotic factors in three estuarine systems that were characterized by significant differences in salinity and ambient dissolved inorganic nitrogen (DIN; NO₂ ^?+NO₃ ^?) regimes that ranged from 5–25‰ (0–80 μM DIN) in the Guadalupe estuary to 35–55‰ (0–9 μM DIN) in the upper Laguna Madre, Photosynthesis versus irradiance (P vs. I) parameters, measured from December 1989 to April 1991, showed no significant differences among the three sites, and there were no significant differences in leaf chlorophyll content and chl a:b ratios among sites over the entire 5-yr period. Saturation irradiance in Halodule wrightii is estimated at 319 μmoles photons m^?2 s^?1 based on measurements collected at the three sites over a 2-yr period. No strong seasonal variations were observed in total plant biomass, but root:shoot ratios (RSR) showed a clear pattern of maximum RSR values in winter and minimum values in summer. There were no significant differences in RSR among sites, and no consistent correlations could be established between plant parameters and sediment porewater NH₄ ⁺, salinity, or temperature. Sediment porewater NH₄ ⁺ values generally ranged from 50 μM to 400 μM (average 130–150 μM) but could not be correlated with significant differences in sediment composition between the sites. The high productivity of Halodule wrightii under a variety of light, nutrient, and salinity conditions explains its ubiquitous distribution and opportunistic strategy as a colonizing species. However, the persistence of a dense algal bloom in Laguna Madre coincident with low DIN levels (<5 μM) contradicts previously accepted relationships on nutrient stimulation of algal growth, and provides strong evidence that water quality parameters for estuarine seagrasses are decidedly estuarine-specific. Consequently, a knowledge of the long-term history of estuarine systems is critical to habitat managers, who are required to establish minimum water quality criteria for the protection of submerged aquatic vegetation in estuarine systems. *** DIRECT SUPPORT *** A01BY074 00028     

Estimation of source parameters and attenuation using digital waveforms of Al-Ays 2009 earthquake,Saudi Arabia

On 19 May 2009, an earthquake sequence of M _w?=?4.8 occurred at 25.20°N 37.76°E about 60 km onshore of the Red Sea coastline, Saudi Arabia. In the present study, the digital waveform data from the largest four events were used to estimate the source parameters and attenuation characteristics along the source-to-station path in the Arabian Shield. A grid search technique, combined with an assumption of circular source model, was applied to find the best-fit spectral amplitude over the space parameters: long period spectral level (Ω ₀), corner frequency (f ₀) and asymptotic high-frequency fall-off (γ). Consequently, the spectral parameters were used to estimate source parameters: seismic moment, fault radius (assumed circular rupture model) and stress drop. Seismic moments are founded to be within the range of 2.34E+14 to 2.83E+16 Nm and their corresponding moment magnitudes range from 3.5 to 4.8; the fault radius ranges from 369 to 1,498 m, and stress drops are observed in the range of 8.7 to 32.0 b. The spectral slopes beyond the corner frequency displayed ω ^?2.4 to ω ^?2.6 behaviours in contrast with Brune's source model of ω ^?2. This finding requires more detailed investigations on large data sets to distinguish the behaviour mechanism of the spectral slopes at high frequencies. By taking the ratio between observed and calculated spectra, the attenuation curves for P and S waves were derived along the source-to-station paths. The preliminarily results exhibited high quality factors of Q _α?=?3,883 and Q _β?=?3,530 for P and S waves, respectively. To this end, the ratio Q _β/Q _α is founded to be slightly less than unity indicating that the body waves from source-to-station paths crossed a crustal volume that is partially saturated with fluids causing lower attenuation effect on P waves than on S waves in the Arabian Shield.     

Formation and recognition of alkyl xanthyl thiosulphates in sulphide ore flotation liquors

Alkyl xanthyl thiosulphates (R.OCSS.S₂O₃^?) (RXT^?) are formed in solution by mild oxidation (e.g. by I₂) of solutions containing both xanthate and thiosulphate. They can also be formed by reaction of Cu²⁺ with xanthate and thiosulphate, reaction of dixanthogen with thiosulphate, and by reaction of xanthate with tetrathionate; these last three reactions can occur in flotation pulps in slightly acid or alkaline solutions (pH 5–10).Alkyl xanthyl thiosulphates are stable in acid and neutral solution; the solutions have a UV absorption maximum at 289 nm. In strongly alkaline solution (pH 12) RXT^? decomposes within a few minutes to yield a xanthate (mostly) plus a little perxanthate. At pH 10 this decomposition to xanthate takes about 48 h. At pH 7–9 RXT^? is relatively stable. RXT^? is not extracted from aqueous solution with common solvents (chloroform, iso-octane, cyclohexane, or ether). It forms a water-insoluble adduct with cetyltrimethyl-ammonium bromide (CTAB); this adduct can be extracted into chloroform, and the extract has a UV absorption maximum at 296 nm.RXT^? was found in solutions from the gangue-sulphide flotation section at Renison Ltd, the zinc flotation circuit and the copper flotation circuit at Mount Isa Mines Ltd, and the lead flotation section of The Zinc Corporation Ltd. The presence of RXT^? in operating flotation plants has various practical and theoretical implications.     

Heat of formation of petalite, LiAlSi4O10

The enthalpy of formation of petalite, LiAlSi₄O₁₀, has been measured using high-temperature solution calorimetry. The measurements were carried out in a Calvet-type twin micro calorimeter at 728?°C. A 2PbO?·?B₂O₃ melt was used as a solvent. Tabulated heats of formation of the components and tabulated heat capacities of the reactants and the product (Robie and Hemingway 1995) were used to calculate the standard heat of formation of petalite from the measured heats of solution. The calculations yielded a mean value of Δ _f H ^pet _298.15=?4872±5.4 kJ mol^?1. This value may be compared to the heat of formation of Δ _f H ^pet _298.15= ?4886.5±6.3 kJ mol^?1 determined by the HF solution calorimetry by Bennington et?al. (1980). Faßhauer et?al. (1998) combined thermodynamic data with phase-equilibrium results to obtain best-fit thermodynamic results using the Bayes method, in order to derive an internally consistent dataset for phases in the NaAlSiO₄– LiAlSiO₄–Al₂O₃–SiO₂–H₂O system. They determined ?4865.6?±?0.8?kJ?mol^?1 as the enthalpy of formation of petalite, a value that is appreciably closer to the enthalpy found in this work.     

Carbon dioxide concentration and atmospheric flux in the Hudson River

We made direct measurements of the partial pressure of CO₂ (P_{CO 2}) in the tidal-freshwater portion of the Hudson River Estuary over a 3.5-yr period. At all times the Hudson was supersaturated in CO₂ with respect to the atmosphere. P_{CO 2} in surface water averaged 1125±403 (SD) μatm while the atmosphere averaged 416±68 μatm. Weekly samples at a single, mid-river station showed a pronounced and reproducible seasonal cycle with highest values (～2000 μatm) in mid-to-late summer, and lowest values (～500 μatm) generally in late winter. Samples taken along the length of the 190-km section of river showed a general decline in CO₂ from north to south. This decline was most pronounced in summer and very slight in spring. Diel and vertical variation were small relative to the standing stock of CO₂. Over six diel cycles, all taken during the algal growing season, the mean range was 300±114 μatm. CO₂ tended to increase slightly with depth, but the gradient was small, about 0.5 μmol m^?1, or an increase of 190 μatm from top to within 1 m of the bottom. For a large subset of the samples (n=452) we also calculated CO₂ from measurements of pH and total DIC. Calculated and measured values of CO₂ were in reasonably good agreement and a regression of calculated versus measured values had a slope of 0.85±0.04 and an r₂ of 0.60. Combining our measurements with recent experimental studies of gas exchange in the Hudson, we estimate that the Hudson releases CO₂ at a rate of 70–162 g C m^?2 yr^?1 from the river to the atmosphere.     

Diagrams of electrochemical equilibria of the system copper-potassium ethylxanthate-water at 25°C

On the basis of thermodynamic calculations, diagrams of metastable electrochemical equilibria of the system copper-potassium ethylxanthate-water, at 25°C were constructed. The equilibria equations and diagrams for the total activity of [EtX^?] + [HEtX] + 2 [(EtX)₂] (equalling 10^?1, 10^?4 and 10^?7 mol/dm³), are presented. The practical conclusions resulting from these diagrams for the flotation of native copper are discussed.     

Effect of surface oxidation and iron contents on xanthate ions adsorption of synthetic sphalerites

Abstraction of xanthate ions from solution by copper-activated synthetic sphalerites with various iron contents was measured. It was found that raising the iron content in the samples caused a decrease in xanthate ions abstraction. For sphalerite samples characterized by the same percentage of iron deoxidized surfaces took up more xanthate ions than oxidized surfaces.Surface coverage by EtX^? ions was determined to be less than one monolayer. These values were compared with copper ion coverage at sphalerite surface. The amount of EtX^? ions abstracted from solution was noted to be independent of the pH of the solution in the range from 6 to 10 pH units, above $\text{pH}\text{=10}$ a decrease in the abstraction was observed.     

Uptake of Cu2+ by the calcium carbonates vaterite and calcite as studied by continuous wave (cw) and pulse electron paramagnetic resonance

The investigation of the Cu²⁺ uptake by the calcium carbonate minerals vaterite and calcite with continuous wave and pulse electron paramagnetic resonance (EPR) yields information on a molecular scale about the relevant complexation reactions at the mineral–water interface. The structural assignment is based on changes in the coordination geometry of the copper complexes. Magnetic interactions of the unpaired Cu²⁺ electron with nuclei of ¹³C-labeled carbonate ligands and protons from water or hydroxyl ligands in the first and second coordination spheres of the cation are detected by pulse EPR techniques. Our results show that the Cu²⁺ ions are rapidly dehydrated upon adsorption on the mineral surface. The strong surface binding is due to monodentate coordination to three or four carbonate surface ions, comparable to chelate complexation in solution. The formation of square-planar or square-pyramidal copper complexes at exposed surface sites like kinks and steps yields a convincing explanation for the inhibition of calcium carbonate growth and dissolution. Upon recrystallization the Cu²⁺ ions are integrated into the calcite lattice where they exhibit a dynamic Jahn–Teller effect. The resulting local lattice distortions are expected to destabilize the Cu_xCa_(1−x)CO₃(s) solid solution. Our results support the concept of a dynamic calcium carbonate surface, covered by a thin, structured surface layer. The detailed structural information obtained for Cu²⁺ provides a better understanding of the interaction of other metal ions with calcium carbonate minerals.     

Application of a new Raman microprobe spectrometer to nondestructive analysis of sulfate and other ions in individual phases in fluid inclusions in minerals

Rosascoet al. (1975), reported the first successful application of laser-excited Raman spectroscopy for the identification and nondestructive partial analysis of individual solid, liquid, and gaseous phases in selected fluid inclusions. We report here the results of the application of a new instrument, based on back-scattering, that eliminates many of the previous stringent sample limitations and hence greatly expands the range of applicability of Raman spectroscopy to fluid inclusions.Fluid inclusions in many porphyry copper deposits contain 5–10 μm ‘daughter’ crystals thought to be anhydrite but too small for identification by the previous Raman technique. Using the new instrument, we have verified that such daughter crystals in quartz from Bingham, Utah, are anhydrite. They may form by leakage of hydrogen causing internal autooxidation of sulfide ion. Daughter crystals were also examined in apatite (Durango, Mexico) and emerald (Muzo, Colombia).Valid analyses of sulfur species in solution in small fluid inclusions from ore deposits would be valuable, but are generally impossible by conventional methods. We present a calibration procedure for analyses for SO₄^2? in such inclusions from Bingham, Utah (12,000 ± 4000 ppm) and Creede, Colo. (probably < 500 ppm). A fetid Brazilian quartz, originally thought to contain liquid H₂S, is shown to contain only HS^? in major amounts.     

Assessment of soil losses and siltation of the K’sob hydrological system (semiarid area—East Algeria)

Soil losses and siltation of the hydrological system (watershed–dam) of K’sob were obtained using direct and indirect methods. The Wadi K’sob watershed of 1,484 km², average slope of 0.14, and average elevation of 1,060 m is located in a semiarid climate. The average annual rainfall is 341 mm and the mean annual water discharge is 0.89 m³/s. Data from the Medjez gauging station located 6 km upstream of the dam, are the daily liquid flow and instantaneous concentrations of suspended sediments. Over a time period from 1973 to 2010, the relationship between water and sediment discharges is quantified by the equation: Q _s?=?5.6 Q ^1.31. Thus, in view of the availability data on a daily scale, the assessment of soil erodibility of the K’sob watershed was used to estimate specific soil losses of 203 t?km^?2?year^?1or 301,000 t eroded annually from the K’sob basin. The bathymetric measurements of the sediment volumes deposited in the K’sob dam, has quantified the annual siltation of 0.8 hm³, corresponding to an average erodibility of the K’sob watershed of 809 t?km^?2?year^?1. However, when adding the volume of sediment removed by the dredging operation and de-silting by the valves during heavy floods, the value of soil losses is 2,780 t?km^?2?year^?1. The indirect assessment of soil erodibility of the basin was obtained by applying two models: the quantitative geomorphological analysis (QGA) and PISA model (prediction of silting in the artificial reservoirs, in Italian: Previsioni dell’Interimento nei Serbatoi Artificiali) using physical and climatic factors in the watershed. The obtained results by QGA method underestimate specific soil losses of 524 t?km^?2?year^?1. The PISA model gives a value of 2,915 t?km^?2?year^?1, which is close to the value obtained by bathymetric measurements. This study concludes that PISA model is most suitable to estimate soil loss and siltation of the K’sob hydrological system.     

Biogeochemical cycling in an organic-rich coastal marine basin 4. An organic carbon budget for sediments dominated by sulfate reduction and methanogenesis

In situ carbon flux measurements and calculated burial rates are utilized to construct an organic carbon budget for the upper meter of sediment at a single station in Cape Lookout Bight, a small marine basin located on the Outer Banks of North Carolina, U.S.A. (34°37′N, 76°33′W). Of 149 ± 20 mole · m^?2 · yr^?1 of total organic carbon deposited, 35.6 ± 5.2 mole · m^?2 · yr^?1 is recycled to overlying waters, 84 ± 18% as ∑CO₂ and 16 ± 8% as CH₄. Approximately 68 ± 20% of the upward carbon flux is supported by sulfate reduction while 32 ± 16% takes place as the result of underlying methanogenesis. Measured ∑CO₂ and CH₄ sediment-water fluxes range seasonally from 1900–6300 and 50–2500 μmole · m^?2 · hr^?1 respectively.The mean residence time of metabolizable organic carbon in the upper 80 cm of sediment is approximately four months with greater than 98% of the calculated total remineralization taking place within three years. In spite of large upward fluxes of methane, larger molecules derived from metabolizable sedimentary organic carbon appear to be the dominant reductants for dissolved sulfate.     

Calorimetric determination of the standard enthalpy of formation of stannite,Cu<Subscript>2</Subscript>FeSnS<Subscript>4</Subscript>

The standard enthalpy of formation of stannite (Cu₂FeSnS₄) was calculated from the calorimetric measurements of the reactions of its formation from simple synthetic sulfides: Cu₂S + FeS₂ + SnS → Cu₂FeSnS₄ and ₂CuS + FeS + SnS → Cu₂FeSnS₄. Using published data for the binary sulfides, the standard enthalpy of formation of stannite from the elements was determined as ΔfH°_298.15(Cu₂FeSnS₄) =–(417.28 ± 2.28) kJ mol^–1.     

Redox control of arsenic mobilization in Bangladesh groundwater

Detailed hydrochemical measurements, δ³⁴S_SO4 and ³H analyses were performed on 37 groundwater samples collected during February 1999, January and March 2000 from 6 locations in eastern and southeastern Bangladesh to examine redox processes that lead to As mobilization in groundwater. The study sites were chosen based on available nation-wide As surveys to span the entire spectrum of As concentrations in Bangladesh groundwater, and to represent 3 of 5 major geological units of the Ganges-Brahmaputra Delta: uplifted Pleistocene terrace, fluvial flood plain and delta plain. Arsenic was found to be mobilized under Fe-reducing conditions in shallow aquifers (<35 m depth), presumably of Holocene age. It remained mobile under SO₄-reducing conditions, suggesting that authigenic sulfide precipitation does not constitute a significant sink for As in these groundwaters. The redox state of the water was characterized by a variety of parameters including dissolved O₂, NO₃⁻, Mn²⁺, Fe²⁺ concentrations, and SO₄²⁻/Cl⁻ ratios. High dissolved [As] (> 50 μg/l; or > 0.7 μM ) were always accompanied by high dissolved [HCO₃⁻] (> 4 mM), and were close to saturation with respect to calcite. Groundwater enriched in As (200–800 μg/l; or 2.7–10.7 μM) and phosphate (30–100 μM) but relatively low in dissolved Fe (5–40 μM) probably resulted from re-oxidation of reducing, As and Fe enriched water. This history was deduced from isotopic signatures of δ³⁴S_SO4 and ³H₂O (³H) to delineate the nature of redox changes for some of the reducing groundwaters. In contrast, As is not mobilized in presumed Pleistocene aquifers, both shallow (30–60 m) and deep (150–270 m), because conditions were not reducing enough due to lack of sufficient O₂ demand.     

Theoretical studies of the electronic structure of copper in tetrahedral and triangular coordination with sulfur

Molecular orbital calculations are presented for the copper-sulfur polyhedral clusters CuS ₄ ^7? , CuS ₄ ^6? , CuS ₃ ^5? and CuS ₃ ^4? , which occur in many minerals. Calculated and experimental optical and X-ray energies are found to be in good agreement. The crystal field orbitals of Cu⁺ in tetrahedrally coordinated sulfides are found to be less tightly bound than the S3p nonbonding orbitals by about 2–3 eV whereas the e and t ₂ crystal field orbitals are split by about 1 eV. The crystal field splitting of Cu²⁺ in tetrahedral coordination is about 0.7–0.8 eV while the separation of the S3p nonbonding orbitals and the partially filled t ₂ crystal field orbital is about 2 eV. In triangular coordination both the Cu⁺ and Cu²⁺ crystal field orbitals are more stable than in tetrahedral coordination, more widely split and more strongly mixed with the S3p orbitals. CuS is shown to be unstable as the mixed oxidation state compound Cu^2+III (Cu^+IV)₂S^2?(S ₂ ^2? ); rather each Cu is predicted to have a fractional oxidation state and partially-empty crystal field orbitals.