Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu₃SnS₄, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu₃SnS₄ crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)₂Cu(II)SnS₄ and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.     

The distribution of Cu(II) and the magnetic properties of the synthetic analogue of tetrahedrite: Cu12Sb4S13

A wide investigation of the synthetic analogue of tetrahedrite, Cu₁₂Sb₄S₁₃, has been performed by a combination of several techniques, magnetisation and differential scanning calorimetric measurements, cw, and pulsed EPR spectroscopy, to obtain complementary information about the presence and the distribution of Cu(II). The high temperature susceptibility of the sample accounts for two Cu(II) per formula unit, in agreement with the charge balance. However, strong antiferromagnetic interactions, observed even at room temperature, are associated with a transition at 83(3) K. At lower temperatures a residual susceptibility is observed. At 4.2 K ESEEM experiments enabled observation of the chemical environment of the residual paramagnetic species. Cu(II) was found randomly distributed in the M(1) site. The statistical presence of nearest neighbouring Cu(II) ions justify the observed antiferromagnetic interactions and transition. Nevertheless, isolated paramagnetic ions have been determined below the Néel temperature: they are mainly located near the surface of the grains. A colour centre, previously observed in natural samples, has been also identified.     

The unusual magnetic properties of kuramite–stannite pseudobinary series: a SQUID and EPR survey

The magnetic properties of the synthetic Cu₃SnS₄ (kuramite)–Cu₂FeSnS₄ (stannite) pseudobinary series were investigated by means of electron paramagnetic resonance (EPR) spectroscopy, at room temperature, and by magnetometry, in the range 2–300 K. The system is particularly complex, from both chemical and crystal chemical points of view, in particular with respect to the metal valence states and the local ordering in the different terms of the series. Nevertheless, recent successes in synthesising nanostructured kuramite foster the interest to ascertain the bulk magnetic properties of these important semiconducting phases. The obtained results allowed to ascertain that a variable lack of local ordering in the Cu_3–x Fe _x SnS₄ (x < 0.85) samples induce the raise of strong metal–sulphur–metal superexchange interactions, that result in the appearance of marked deviations from the single-ion behaviour, typical for pure stannite. Ferro- and antiferromagnetic interactions are in fact observed at relatively high temperatures (~150 K). A possible role played by Cu(I)–Fe(III) was revealed by the EPR measurements. The Cu-rich terms of the series (x < 0.1) are characterised by dynamic resonant disorder (i.e. time-evolving delocalisation of the formally divalent valence state for Cu among the nearest neighbouring Cu-sites), in addition to the Cu–Fe–Sn static disorder verified along the whole series. Both factors concurring to a non-periodic arrangement of paramagnetic ions in the lattice have the main effect to drastically broaden the EPR lines.     

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.     

Characterisation of the antiferromagnetic transition of Cu<Subscript>2</Subscript>FeSnS<Subscript>4</Subscript>, the synthetic analogue of stannite

Magnetisation measurements were performed on the synthetic analogue of stannite, Cu₂FeSnS₄, in order to characterise the antiferromagnetic transition at low temperature, evidenced by Bernardini et al. (2000). Temperature and field dependence of the material were checked by means of static magnetisation measurements, carried out scanning the magnetic fields up to 12 T and temperatures in the range 1.4–20 K, while ac susceptibility data were collected at different frequencies ranging from 1.8 to 510 Hz. Both static and dynamic magnetisation data, performed above and below the Néel temperature, 6.1(2) K, confirm stannite to order antiferromagnetically at a long-range scale. Moreover, an increase of both the magnetic anisotropy and the exchange interaction, with respect to the Mn-analogue (Fries et al. 1997), has been observed.     

Hydrogen bonding in basic copper salts: a spectroscopic study of malachite,Cu2(OH)2CO3, and brochantite,Cu4(OH)6SO4

Infrared and Raman spectra of the basic copper salts malachite, Cu₂(OH)₂CO₃, and brochantite, Cu₄(OH)₆SO₄, as well as of deuterated and ¹³C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH^? ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO₄ ^2-, CO₃ ^2-, and OH^? ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH^? ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430–590 cm^?1 and 420–520 cm^?1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding.     

Mineralogy and textural relationships among sulphosalts and related minerals in the Bleikvassli Zn-Pb-(Cu) deposit, Nordland, Norway

Several distinct assemblages of Pb-Sb, Pb-As, Cu-Pb-Sb and Cu-Fe-Zn-Sn sulphosalts are identified in sulphide samples from Bleikvassli mine, Norway. Detailed optical microscopy and electron probe microanalysis have permitted investigation of textural relationships between minerals and compositional variations between different ore types. Tetrahedrite, typically containing 10–16?wt.% Ag (rare freibergite containing 25–30?wt.% Ag has also been identified in two samples), stannite (Cu₂(Fe>Zn)SnS₄), and meneghinite, CuPb₁₃Sb₇S₂₄, are widely distributed as trace constituents throughout massive pyritic and galena-rich ores. Native antimony and pyrargyrite occur in trace amounts in all ore types, as the breakdown products of earlier sulphosalts. Several distinct types of wall-rock mineralisation are present at Bleikvassli. Of considerable mineralogical interest are the coarse-grained sulphide mobilisates within the wall rock which contain a distinct?and characteristic suite of Pb-As sulphosalts:?tennantite?+?jordanite (Pb₁₄As₆S₂₃)?+?seligmannite (CuPbAsS₃) ± dufrenoysite (Pb₂As₂S₅). Bournonite (CuPbSbS₃) is the only Sb-bearing sulphosalt recognised in significant amounts within the mobilisates, meneghinite and tetrahedrite being conspicuously absent. These mobilisates display considerable Au enrichment; electrum can be confirmed, intimately associated with jordanite and tennantite. Appreciable Sb (up to 3?wt.%) is contained within galena in the mobilisates, in contrast to galena from massive ores which contains only negligible Sb. Contents of Ag and Bi in galena vary considerably in all ore types, but confirm earlier suggestions that galena is a major Ag-carrier at Bleikvassli. Boulangerite (Pb₅Sb₄S₁₁), jamesonite (FePb₄Sb₆S₁₄) and gudmundite (FeSbS) occur in trace amounts. Sn-sulphosalts are represented by kësterite, (Cu₂(Zn> Fe)SnS₄), but commonly zoned with respect to Zn/Fe ratio, in the mobilisates, rather than by stannite. A rare type of mobilisate, also in the wall rock, in which chalcocite and bornite are the main minerals, contains native Ag, stromeyerite (AgCuS), mckinstryite ((Ag,Cu)₂?S), Ag-free tetrahedrite, an unnamed Cu-Ag-Fe sulphide (Cu₃Ag₂FeS₄) and native Bi, myrmekitically intergrown with chalcocite. Although a comprehensive genetic model for the wall-rock mineralisation at Bleikvassli is largely impossible given the limitations in the present state of knowledge regarding mechanisms involved in remobilisation processes, a multi-stage model of remobilisation during regional metamorphism is considered to best explain the observations. An interplay of different solid- and liquid-state remobilisation mechanisms, in various combinations, is required to account for the macro- and microscopic observations. Remobilisation probably began during the earlier stages of metamorphism, with crystallisation and further remobilisation taking place during the entire metamorphic cycle, giving rise to the extensive chemical and mineralogical diversity observed today. Preserved mineral assemblages and their textural relationships reflect a complex sequence of replacement and decomposition reactions taking place during the latest phase of late-metamorphic crystallisation and subsequent cooling.     

Some electrical properties of fahlore Cu10(Zn,Fe)2(As,Sb)4S13

Natural Zn-tennantite Cu_10.10Ag_0.04(Zn_1.29-Fe_0.67)_1.96(As_3.04Sb_0.89)_3.93S_12.98 from Beresovskoe, Urals, behaves as an ordinary semiconductor in the temperature range 300–400 K and frequency range 10⁸–2.8·10¹⁰ Hz, and no ionic component conductivity is observed. This contrasts with the behaviour of synthetic tetrahedrites (both Cu-rich and Cu-poor) which are solid electrolytes. These results can be related to the number of vacancies per formula unit and the substitution scheme for the divalent metals in fahlore.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe₂O₃) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH)₆ polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe₂(OH)₂(H₂O)₈Cu(OH)₄and Fe₃(OH)₄(H₂O)₁₀Cu₂(OH)₆ clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO₄H_n)ⁿ⁻⁶ and Fe(O,OH)₆ polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH)₂. Having identified the bidentate (FeOH)₂Cu(OH)₂⁰ and tridentate (Fe₃O(OH)₂)Cu₂(OH)₃⁰ surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions

     

Fahlore thermochemistry: Gaps inside the (Cu,Ag)<Subscript>10</Subscript>(Fe,Zn)<Subscript>2</Subscript>(Sb,As)<Subscript>4</Subscript>S<Subscript>13</Subscript> cube

Possible topologies of miscibility gaps in arsenian (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores are examined. These topologies are based on a thermodynamic model for fahlores whose calibration has been verified for (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ fahlores, and conform with experimental constraints on the incompatibility between As and Ag in (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores, and with experimental and natural constraints on the incompatibility between As and Zn and the nonideality of the As for Sb substitution in Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores. It is inferred that miscibility gaps in (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores have critical temperatures several °C below those established for their Sb counterparts (170 to 185°C). Depending on the structural role of Ag in arsenian fahlores, critical temperatures for (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores may vary from comparable to those inferred for (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores, if the As for Sb substitution stabilizes Ag in tetrahedral metal sites, to temperatures approaching 370°C, if the As for Sb substitution results in an increase in the site preference of Ag for trigonal-planar metal sites. The latter topology is more likely based on comparison of calculated miscibility gaps with compositions of fahlores from nature exhibiting the greatest departure from the Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ and (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ planes of the (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlore cube.     

An easy and fast IC-CL procedure for the monitoring of Cu(II) and Co(II) in environmental samples

A luminol chemiluminescence (CL) detection/flow injection analysis technique coupled with ion chromatography (IC) has been employed for the determination of low levels of Cu(II) and Co(II) in drinking water samples. The detection system was the CL of luminol/perborate or luminol/percarbonate in alkaline medium catalyzed by these transition metals. Oxalic acid in a solution of KOH and N(CH₃)₄OH was used as an eluent in the IC to improve the column selectivity (Dionex CS5A). Concentration and pH of the eluent affected simultaneously the CL intensity and the retention times (t _R). Under the elution conditions used here, the retention times of both metal ions were much greater when the concentration of oxalic acid was decreased. Thus, R _t(_Cu) = 2.15 min and t _R(_Co) = 4.50 min were measured at 80 mM oxalic acid concentration, while t _R raised to 4.12 and 18 min for Cu(II) and Co(II), respectively, using a 10-mM concentration, but on the other hand, the CL signals showed substantially higher values when the concentration of oxalic acid was lesser in the eluent. An optimum oxalic acid concentration of 20 mM and an eluent pH = 4.7 were selected in order to have reproducible signals with a total analysis time of 10 min. The optimum flow rate for the mobile phase was 1.5 mL min^?1. The concentration and pH of the postcolumn reagents also affected the CL signal, obtaining optimum concentrations of 5 mM for both oxidants (perborate or percarbonate) and luminol, this last dissolved in a 0.1-M borate buffer at pH 12. The optimum flow rate for the postcolumn reagents was 1 mL min^?1. Linear calibrations for both transition metal ions were established, with calculated detection limits of 0.15 ng mL^?1 for Co(II) and 0.20 μg mL^?1 for Cu(II). Others ions commonly present in natural waters showed little or no interference. The method was successfully applied to water samples spiked with Cu(II) and Co(II), obtaining recoveries in the range of 85–128%, depending on the metal concentrations.     

Composition and solubility of precipitated copper(II) arsenates

Equilibrium reactions involving Cu(II) and As(V) have been studied with respect to formation of complexes in aqueous solutions as well as formation of solid phases. Potentiometric titrations performed at 25 °C (I = 0.1 M Na(Cl)) and at different Cu to As ratios gave no evidence for the existence of Cu(II) arsenate complexes in solution below the pH of the precipitation boundaries (pH ≈ 4), irrespective of the Cu to As ratio and pH. Mixing of solutions of Cu(II) and As(V) at different proportions and adjusting pH to values ranging from 4 to 9 resulted in precipitation of five different solid phases. The elemental composition of the solids was determined using X-ray Photoelectron Spectroscopy, and Environmental Scanning Microscopy-Field Emission Gun equipped with an energy dispersive spectroscopy detector. The average Cu/As ratio was determined by dissolving the solids. Total soluble concentrations of the components Cu(II) and As(V), as well as the basicity of the solid phases were determined by analysis of aqueous solutions. Based upon these experimental data the stoichiometric composition of the solid phases and their stability were determined. The resulting equilibrium model includes the solid phases Cu₃(AsO₄)₂, Cu₃(AsO₄)(OH)₃, Cu₂(AsO₄)(OH), Cu₅Na(HAsO₄)(AsO₄)₃ and Cu₅Na₂AsO₄)₄, where Cu₅Na(HAsO₄)(AsO₄)₃ and Cu₅Na₂(AsO₄)₄ have not been reported previously. In 0.1 M Na(Cl), Na⁺ was found to be a significant component in two of the solid phases. The Cu₅Na₂(AsO₄)₄ was formed in weakly alkaline conditions with pNa < 2.5. Stability constants for all solid phases have been determined. Distribution diagrams as well as predominance area (pNa-pH) diagrams are presented to illustrate stability fields of the different solid phases.     

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO₃ electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (⁶⁵Cu/⁶³Cu) and Zn (⁶⁶Zn/⁶⁴Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (α_soln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δ_soln-solid) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).     

The crystal structure of arsentsumebite, Pb2Cu[(As, S)O4]2(OH)

Summary The crystal structure of arsentsumebite, ideally, Pb₂Cu[(As, S)O₄]₂(OH), monoclinic, space group P2₁/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?³, Z = 2, d_calc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb₂ Me(XO₄)₂(Z) where Me = Cu²⁺, Mn²⁺, Zn²⁺, Fe²⁺, Fe³⁺; X = S, Cr, V, As, P; Z = OH, H₂O. Members of this group include tsumebite, Pb₂Cu(SO₄)(PO₄)(OH), vauquelinite, Pb₂Cu(CrO₄)(PO₄)(OH), brackebuschite, Pb₂ (Mn, Fe)(VO₄)₂(OH), arsenbracke buschite, Pb₂(Fe, Zn)(AsO₄)₂(OH, H₂O), fornacite, Pb₂Cu(AsO₄)(CrO₄)(OH), and feinglosite, Pb₂(Zn, Fe)[(As, S)O₄]₂(H₂O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO₆ octahedra and M–T represents corner sharing between octahedra and XO₄ tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)₂(AsO₄)₂ (OH, H₂O)₂ and tsumcorite-group minerals Me(1)Me(2)₂(XO₄)₂(OH, H₂O)₂. Received June 24, 2000; revised version accepted February 8, 2001     

Strukturverfeinerung von Libethenit Cu2(OH)PO4

Inhalt Eine mit zweidimensionalen Fouriermethoden durchgeführte Strukturverfeinerung bestätigt die vonH. Heritsch (1940) für Libethenit bestimmte Struktur. Von der daraus resultierenden kristallchemischen Formel Cu^[4+2] Cu^[5] (OH) [PO₄] ist sowohl die Strukturanalogie mit Andalusit und Adamin als auch die zu gleichen Teilen auftretende Sechser- und Fünferkoordination des zweiwertigen Kupfers in Libethenit abzulesen.

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Surface complexation model for multisite adsorption of copper(II) onto kaolinite

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ inner-sphere complexes on variable-charge ≡AlOH sites and as Cu²⁺ on ion exchangeable ≡X--H⁺ sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH)₆ polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH)₂Cu(OH)₂⁰, tridentate (≡Al₃O(OH)₂)Cu₂(OH)₃⁰ and ≡X--Cu²⁺ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

     

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.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.