Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ⁶⁵Cu, δ⁶⁶Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g⁻¹ Cu and 2084 μg g⁻¹ Zn in the organic horizons. The δ⁶⁵Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ⁶⁶Zn_IRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ⁶⁶Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ⁶⁶Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ⁶⁶Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.     

High precision iron isotope measurements of meteoritic material by cold plasma ICP-MS

The first cold plasma ICP-MS (inductively coupled plasma mass spectrometer) Fe isotope study is described. Application of this technique to the analyses of Fe isotopes in a number of meteorites is also reported. The measurement technique relies on reduced temperature operation of the ICP source to eliminate pervasive molecular interferences from Ar complexes associated with conventional ICP-MS. Instrumental mass bias corrections are performed by sample-standard bracketing and using Cu as an external mass bias drift monitor. Repeated measurements of a terrestrial basalt reference sample indicate an external reproducibility of ± 0.06 ‰ for δ⁵⁶Fe and ± 0.25 ‰ for δ⁵⁸Fe (1 σ). The measured iron isotopic compositions of various bulk meteorites, including irons, chondrites and pallasites are identical, within error, to the composition of our terrestrial basalt reference sample suggesting that iron mass fractionation during planet formation and differentiation was non-existent. Iron isotope compositions measured for eight chondrules from the unequilibrated ordinary chondrite Tieschitz range from −0.5 ‰ < δ⁵⁶Fe_chondrules < 0.0 ‰ relative to the terrestrial/meteorite average. Mechanisms for fractionating iron in these chondrules are discussed.     

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ⁶⁶Zn and δ⁶⁵Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (^66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Comparative stable isotope geochemistry of Ni, Cu, Zn, and Fe in chondrites and iron meteorites

High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes.The observed variations of the ⁶²Ni/⁵⁸Ni, ⁶¹Ni/⁵⁸Ni, and ⁶⁰Ni/⁵⁸Ni ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no ⁶⁰Ni anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45‰ per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation.     

Microscale oxygen isotopic exchange and magnetite formation in the Ningqiang anomalous carbonaceous chondrite

We report in situ measurements of O-isotopic compositions of magnetite, olivine and pyroxene in chondrules of the Ningqiang anomalous carbonaceous chondrite. The petrographic setting of Ningqiang magnetite is similar to those in oxidized-CV chondrites such as Allende, where magnetite is found together with Ni-rich metal and sulfide in opaque assemblages in chondrules. Both magnetite and silicate oxygen data fall close to the carbonaceous-chondrite-anhydrous-mineral line with relatively large ranges in δ¹⁸O in magnetite (−4.9 to +4.2‰) and in silicates (−15.2 to −4.5‰). Magnetite and silicates are not in O-isotopic equilibrium: the weighted average Δ¹⁷O (=δ¹⁷O − 0.52 × δ¹⁸O) values of magnetite are 1.7 to 3.6‰ higher than those of the silicates in the same chondrules. The petrological characteristics and O-isotopic disequilibrium between magnetite and silicates suggest the formation of Ningqiang magnetite by the oxidation of preexisting metal grains by an aqueous fluid during parent body alteration. The weighted average Δ¹⁷O of −3.3 ± 0.3‰ is the lowest magnetite value measured in unequilibrated chondrites and there is a positive correlation between Δ¹⁷O values of magnetite and silicates in each chondrule. These observations indicate that, during aqueous alteration in the Ningqiang parent asteroid, the water/rock ratio was relatively low and O-isotopic exchange between the fluid and chondrule silicates occurred on the scale of individual chondrules.     

Re-partitioning of Cu and Zn isotopes by modified protein expression

Cu and Zn have naturally occurring non radioactive isotopes, and their isotopic systematics in a biological context are poorly understood. In this study we used double focussing mass spectroscopy to determine the ratios for these isotopes for the first time in mouse brain. The Cu and Zn isotope ratios for four strains of wild-type mice showed no significant difference (δ⁶⁵Cu -0.12 to -0.78 permil; δ⁶⁶Zn -0.23 to -0.48 permil). We also looked at how altering the expression of a single copper binding protein, the prion protein (PrP), alters the isotope ratios. Both knockout and overexpression of PrP had no significant effect on the ratio of Cu isotopes. Mice brains expressing mutant PrP lacking the known metal binding domain have δ⁶⁵Cu isotope values of on average 0.57 permil higher than wild-type mouse brains. This implies that loss of the copper binding domain of PrP increases the level of ⁶⁵Cu in the brain. δ⁶⁶Zn isotope values of the transgenic mouse brains are enriched for ⁶⁶Zn to the wild-type mouse brains. Here we show for the first time that the expression of a single protein can alter the partitioning of metal isotopes in mouse brains. The results imply that the expression of the prion protein can alter cellular Cu isotope content.     

Nature of volatile depletion and genetic relationships in enstatite chondrites and aubrites inferred from Zn isotopes

Enstatite meteorites include the undifferentiated enstatite chondrites and the differentiated enstatite achondrites (aubrites). They are the most reduced group of all meteorites. The oxygen isotope compositions of both enstatite chondrites and aubrites plot along the terrestrial mass fractionation line, which suggests some genetic links between these meteorites and the Earth as well.For this study, we measured the Zn isotopic composition of 25 samples from the following groups: aubrites (main group and Shallowater), EL chondrites, EH chondrites and Happy Canyon (impact-melt breccia). We also analyzed the Zn isotopic composition and elemental abundance in separated phases (metal, silicates, and sulfides) of the EH4, EL3, and EL6 chondrites. The different groups of meteorites are isotopically distinct and give the following values (‰): aubrite main group (−7.08 < δ⁶⁶Zn < −0.37); EH3 chondrites (0.15 < δ⁶⁶Zn < 0.31); EH4 chondrites (0.15 < δ⁶⁶Zn < 0.27); EH5 chondrites (δ⁶⁶Zn = 0.27 ± 0.09; n = 1); EL3 chondrites (0.01 < δ⁶⁶Zn < 0.63); the Shallowater aubrite (1.48 < δ⁶⁶Zn < 2.36); EL6 chondrites (2.26 < δ⁶⁶Zn < 7.35); and the impact-melt enstatite chondrite Happy Canyon (δ⁶⁶Zn = 0.37).The aubrite Peña Blanca Spring (δ⁶⁶Zn = −7.04‰) and the EL6 North West Forrest (δ⁶⁶Zn = 7.35‰) are the isotopically lightest and heaviest samples, respectively, known so far in the Solar System. In comparison, the range of Zn isotopic composition of chondrites and terrestrial samples (−1.5 < δ⁶⁶Zn < 1‰) is much smaller ( [Luck et al., 2005] and [Herzog et al., 2009]).EH and EL3 chondrites have the same Zn isotopic composition as the Earth, which is another example of the isotopic similarity between Earth and enstatite chondrites. The Zn isotopic composition and abundance strongly support that the origin of the volatile element depletion between EL3 and EL6 chondrites is due to volatilization, probably during thermal metamorphism. Aubrites show strong elemental depletion in Zn compared to both EH and EL chondrites and they are enriched in light isotopes (δ⁶⁶Zn down to −7.04‰). This is the opposite of what would be expected if Zn elemental depletion was due to evaporation, assuming the aubrites started with an enstatite chondrite-like Zn isotopic composition. Evaporation is therefore not responsible for volatile loss from aubrites. On Earth, Zn isotopes fractionate very little during igneous processes, while differentiated meteorites show only minimal Zn isotopic variability. It is therefore very unlikely that igneous processes can account for the large isotopic fractionation of Zn in aubrites. Condensation of an isotopically light vapor best explains Zn depletion and isotopically light Zn in these puzzling rocks. Mass balance suggests that this isotopically light vapor carries Zn lost by the EL6 parent body during thermal metamorphism and that aubrites evolved from an EL6-like parent body. Finally, Zn isotopes suggest that Shallowater and aubrites originate from distinct parent bodies.     

Petrographic and oxygen-isotopic study of refractory forsterites from R-chondrite Dar al Gani 013 (R3.5-6), unequilibrated ordinary and carbonaceous chondrites

We have conducted petrographic, chemical and in-situ oxygen isotopic studies of refractory forsterites from unequilibrated ordinary and carbonaceous chondrites as well as an unequilibrated R-chondrite. Refractory forsterites occur in all types of unequilibrated chondrites and all have very similar chemical composition with low FeO and high refractory lithophile element (RLE) contents. Refractory forsterites are typically enriched in ¹⁶O relative to ‘normal’ olivine independent of the bulk O-isotope ratios of the parent meteorites. Analyses of refractory forsterites spread along a Δ¹⁷O mixing line with Δ¹⁷O ranging from +2 to −10‰. Due to similarities in oxygen isotopes and chemical compositions, we conclude that refractory forsterites of various types of chondrites come from a single common reservoir. Implications of this hypothesis for the chemical and O-isotope evolution of silicates in the early solar nebular are discussed.     

Zn isotopic fractionation caused by sorption on goethite and 2-Lines ferrihydrite

Zn isotopic fractionation caused by sorption on 2-Lines ferrihydrite (Fh2L) and goethite was investigated to assess the role of reactions at the Fe-oxyhydroxide/water interface in changes of the isotopic distribution of Zn. Since sorption reactions are ubiquitous in Earth’s surface environments, it is important to evaluate their influence on the isotopic distribution of Zn before it can be used to track and quantify contributions of various sources and/or biogeochemical processes involving this element. Our results show that Zn isotopes are fractionated upon sorption on Fe-oxyhydroxides with an enrichment of the heavy isotopes present on the solid’s surface. This fractionation appears to proceed through an equilibrium mechanism and yields different (Δ^66/64Zn)_{sorbed-aqueous} values for Zn sorption on goethite [(Δ^66/64Zn)_{sorbed-aqueous} around +0.29‰] and Fh2L [(Δ^66/64Zn)_{sorbed-aqueous} around +0.53‰]. These different magnitudes of Zn fractionation are related to structural differences between Zn complexes existing on the surface of goethite (octahedrally coordinated Zn by oxygen atoms) and Fh2L (tetrahedrally coordinated Zn by oxygen atoms), as evidenced by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and CD-MUSIC modeling. These results show the importance of accounting for reactions at the Fe-oxyhydroxide/water interface when dealing with the isotopic distribution of Zn at the Earth’s surface. Considering the large range of other possible sorbents (Mn or Al oxides, phyllosilicates, carbonates, biologic surfaces, etc.) and the importance of reactions at sorbent/water interfaces for other non-traditional stable isotopes (i.e. Cr, Fe, Ni and Cu) that are increasingly used in environmental studies, these results emphasize the need for further experimental studies that are needed to quantify the isotopic fractionation of these elements possibly accompanying their sorption.     

Trace elements in primitive meteorites—VI. Abundance patterns of thirteen trace elements and interelement relationships in unequilibrated ordinary chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 13 different unequilibrated ordinary chondrites (UOC), i.e. those having chemicallyinhomogeneous silicates. This study together with prior data completes our coverage of this group of 23 primitive chondrites. Four elements are quite variable in UOC (Cd—20 x, In—30 x, Bi—300 x and Tl—1300 x), the others varying by 2–8 x. Three highly-depleted elements—Bi, In and Tl—are richer by 5–35 x in unequilibrated chondrites than in their equilibrated congeners. All 3 elements vary directly in characteristic fashion with disequilibrium parameters for olivine and pyroxene in UOC and generally with petrologic type 3 > 4 > 5 > 6. The data do not provide unambiguous evidence for nebular fractionation of siderophile elements. Examination of statistically-significant interelement relationships among various ordinary chondrite populations involving 34 elements reveals patterns distinct from those of other chondritic groups. These patterns reflect nebular metal-silicate fractionation which preceded or accompanied thermal fractionation. The results point to significant differences in the formation of primitive carbonaceous, enstatite and ordinary chondrites.     

Magnesium isotopic composition of the Earth and chondrites

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ²⁵Mg and ±0.07‰ on δ²⁶Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL).Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ²⁵Mg = −0.13 ± 0.05 (2SD) and δ²⁶Mg = −0.26 ± 0.07 (2SD) for global oceanic basalts (n = 110) and δ²⁵Mg = −0.13 ± 0.03 (2SD) and δ²⁶Mg = −0.25 ± 0.04 (2SD) for global peridotite xenoliths (n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ²⁵Mg = −0.15 ± 0.04 (2SD) and δ²⁶Mg = −0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes.Collectively, the Mg isotopic composition of the Earth’s mantle, based on oceanic basalts and peridotites, is estimated to be −0.13 ± 0.04 for δ²⁵Mg and −0.25 ± 0.07 for δ²⁶Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.     

Thermal metamorphism of primitive meteorites—III. Ten trace elements in Krymka L3 chondrite heated at 400–1000°C

Ten trace elements were determined by neutron activation analysis in Krymka (L3) chondrite samples heated for 1 week, at 100°C increments, from 400 to 1000°C in a low-pressure environment (initially 10^?5 atm H₂). As in other samples studied. Co seems unaffected by heating; ~50% of Cs and Ga are lost only at 1000°C and losses of other elements increase with temperature to extremes of ～ 25% for Se and 95–99% for Ag, Bi, In, Te, T1 and Zn. Where comparison is possible, ‘open-system’ losses are generally in the order Krymka (L3) > Abee (E4) > Allende (C3). Treating elemental mobilization as representing a kinetic process involving diffusion from spherical grains of uniform size Ag, Bi, In, Te, Tl and Zn are lost from a single host phase or by a single process. This differs from trends shown by many of these elements in Abee and Allende and terrestrial basalt BCR-1. Loss of Tl apparently involves a process with a low activation energy, perhaps desorption. Loss of other elements apparently reflects diffusion-controlled process(es).Trace element contents, patterns of statistically significant interelement relationships, factor analysis and two-element correlation diagrams for unheated and heated Krymka and ‘as-received’ L3-6 chondrites are very different. Thus, significant open-system metamorphism during the genesis of L-group chondrites are not supported by these data. This contrasts sharply with the picture for enstatite chondrites, indicating substantial differences in the origin of various chondritic groups.     

Atmospheric deposition and isotope biogeochemistry of zinc in ombrotrophic peat

Zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in Finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record. The peat deposits were located in Hietajärvi, a background site well away from any point pollution source and representing ‘background’ conditions, in Outokumpu, next to a mining site, and in Harjavalta, next to a smelter. Measured total concentrations, calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat. Significant isotopic variability was found in all three peat bogs, with heavier zinc in the deeper and lighter zinc in the upper sections. Isotope ratios and concentrations correlated in the two peats located next to dominant point sources, i.e. the smelting and mining site, suggesting that zinc isotopes trace pollution sources. Concentration and isotope peaks were offset from the period of mining and smelting activity, supporting migration of zinc down the profile. The δ⁶⁶Zn_JMC (where δ⁶⁶Zn = [(⁶⁶Zn/⁶⁴Zn)_sample/(⁶⁶Zn/⁶⁴Zn)_JMC-standard − 1] × 10³) of the top section sample at the remote Hietajärvi site was 0.9‰ and we suggest this represents the regional background isotope signature of atmospheric zinc. The deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source, indicating that post depositional processes affected the isotopic records. The large variations encountered (up to 1.05‰ for δ⁶⁶Zn) and Rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern.We propose that zinc isotopes are amenable to identify different atmospheric zinc sources, including zinc derived from anthropogenic activities such as mining and smelting, but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords.     

Zn isotopes in the suspended load of the Seine River, France: Isotopic variations and source determination

We report Zn isotopic ratios (δ⁶⁶Zn) of river suspended particulate matter (SPM) and floodplain deposits (FD) from the Seine basin, France, with a precision ?0.05‰. A decrease in δ⁶⁶Zn from 0.30‰ to 0.08‰ is observed in SPM from the upstream to downstream parts of the fluvial system, associated with an increase in Zn concentration from 100 ppm to 400 ppm. The Zn/Al of SPM at the river mouth is up to five times greater than the Zn/Al of the natural background, and by normalizing to the later value we define a Zn enrichment factor. Suspended sediments from a temporal series of samples collected in Paris display a similar variation in δ⁶⁶Zn of between 0.08‰ and 0.26‰, while showing an inverse relationship between the Zn enrichment factor and δ⁶⁶Zn. The amount of Zn transported as suspended load varies from 10% to 90%, as a function of increasing discharge. The δ⁶⁶Zn of SPM and the dissolved load are correlated, suggesting that adsorption processes are probably not the dominant process by which the Zn enrichment of SPM takes place. Instead, we interpret our data as reflecting the mixture of two main populations of suspended particles with distinct δ⁶⁶Zn. The first is characteristic of natural silicate particles transported by erosion processes to the river, while the second likely represents anthropogenic particles derived from wastewater treatment plants or combined sewer overflows. Based on isotopic ratios, we calculate that 70% of Zn in SPM of the Seine River in Paris is of anthropogenic origin.     

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).     

Cadmium stable isotope cosmochemistry

Cadmium stable isotope compositions are reported for a comprehensive suite of carbonaceous, ordinary, enstatite, and Rumuruti chondrites as well as achondrites and lunar samples (soils, breccias, pristine anorthosite). The Cd isotope analyses were performed by multiple collector ICP-MS with an external reproducibility of ±0.43‰ (2 sd) for δ^114/110Cd. None of the samples shows evidence of nucleosynthetic anomalies and cosmogenic isotope effects from neutron-capture by ¹¹³Cd were only observed for two lunar samples.The Cd stable isotope compositions of type 1, 2, and some type 3 carbonaceous chondrites, EH4 enstatite chondrites, eucrites, and the Earth are essentially identical at δ^114/110Cd ≈ 0.0 ± 0.4. This suggests that the portion of the solar nebula from which the inner solar system bodies accreted was homogeneous with respect to its Cd isotope composition. It also indicates that the primary volatile element depletion of the inner solar system did not involve partial kinetic Rayleigh evaporation or condensation. Furthermore no resolvable Cd isotope effects were generated during the accretion and initial differentiation of the planetary bodies.In contrast, the analyses reveal large Cd isotope effects for ordinary and some enstatite chondrites, which display δ^114/110Cd values between about −8 and +16. Smaller fractionations are observed for the Rumuruti and some type 3 to 5 carbonaceous chondrites. These Cd isotope variations are thought to reflect secondary depletion or redistribution of Cd, due to open system thermal metamorphism on the meteorite parent bodies.One CAI and chondrule separates from the Allende meteorite have unexpectedly high Cd concentrations and fractionated light Cd isotope compositions with δ^114/110Cd ≈ −1 to −4. These characteristics may have been established by the interaction of originally Cd-poor materials with a volatile-rich gas prior to the final accretion of the Allende parent body. The general Cd enrichment of the lunar soil and regolith mainly reflects early volcanic activity. However, decreasing Cd abundances in lunar soils correlate well with an enrichment of the heavy Cd isotopes. This relationship is best explained by suppressed Rayleigh fractionation in response to space weathering.     

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits,Cantabria, Spain

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ⁶⁶Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ³⁴S?=?+6.6 and stage 2 has δ³⁴S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light ⁶⁶Zn-depleted signatures with δ⁶⁶Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ³⁴S values from +10.7 to +15.7 per mil without any relationship between the δ⁶⁶Zn and δ³⁴S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH₂S?>?mZn²⁺ as a result of change in pH, T, and Zn predominant species. The light δ⁶⁶Zn accompanied by heavy δ³⁴S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ⁶⁶Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.     

Ion-exchange fractionation of copper and zinc isotopes

Whether transition element isotopes can be fractionated at equilibrium in nature is still uncertain. Standard solutions of Cu and Zn were eluted on an anion-exchange resin, and the isotopic compositions of Cu (with respect to Zn) of the eluted fractions were measured by multiple-collector inductively coupled plasma mass spectrometry. It was found that for pure Cu solutions, the elution curves are consistent with a ⁶³Cu/⁶⁵Cu mass fractionation coefficient of 0.46‰ in 7 mol/L HCl and 0.67‰ in 3 mol/L HCl between the resin and the solution. Batch fractionation experiments confirm that equilibrium fractionation of Cu between resin and 7 mol/L HCl is ∼0.4‰ and therefore indicates that there is no need to invoke kinetic fractionation during the elution. Zn isotope fractionation is an order of magnitude smaller, with a ⁶⁶Zn/⁶⁸Zn fractionation factor of 0.02‰ in 12 mol/L HCl. Cu isotope fractionation results determined from a chalcopyrite solution in 7 mol/L HCl give a fractionation factor of 0.58‰, which indicates that Fe may interfere with Cu fractionation.Comparison of Cu and Zn results suggests that the extent of Cu isotopic fractionation may signal the presence of so far unidentified polynuclear complexes in solution. In contrast, we see no compelling reason to ascribe isotope fractionation to the coexistence of different oxidation states. We further suggest that published evidence for iron isotopic fractionation in nature and in laboratory experiments may indicate the distortion of low-spin Fe tetrahedral complexes.The isotope geochemistry of transition elements may shed new light on their coordination chemistry. Their isotopic fractionation in the natural environment may be interpreted using models of thermodynamic fractionation.     

Development of Cu and Zn Isotope MC-ICP-MS Measurements: Application to Suspended Particulate Matter and Sediments from the Scheldt Estuary

The present study evaluates several critical issues related to precision and accuracy of Cu and Zn isotopic measurements with application to estuarine particulate materials. Calibration of reference materials (such as the IRMM 3702 Zn) against the JMC Zn and NIST Cu reference materials were performed in wet and/or dry plasma modes (Aridus I and DSN‐100) on a Nu Plasma MC‐ICP‐MS. Different mass bias correction methods were compared. More than 100 analyses of certified reference materials suggested that the sample‐calibrator bracketing correction and the empirical external normalisation methods provide the most reliable corrections, with long term external precisions of 0.06 and 0.07‰ (2SD), respectively. Investigation of the effect of variable analyte to spike concentration ratios on Zn and Cu isotopic determinations indicated that the accuracy of Cu measurements in dry plasma is very sensitive to the relative Cu and Zn concentrations, with deviations of δ⁶⁵Cu from ?0.4‰ (Cu/Zn = 4) to +0.4‰ (Cu/Zn = 0.2). A quantitative assessment (with instrumental mass bias corrections) of spectral and non‐spectral interferences (Ti, Cr, Co, Fe, Ca, Mg, Na) was performed. Titanium and Cr were the most severe interfering constituents, contributing to inaccuracies of ?5.1‰ and +0.60‰ on δ^68/64Zn, respectively (for 500 μg l^?1 Cu and Zn standard solutions spiked with 1000 μg l^?1 of Ti or Cr). Preliminary isotopic results were obtained on contrasting sediment matrices from the Scheldt estuary. Significant isotopic fractionation of zinc (from 0.21‰ to 1.13‰ for δ⁶⁶Zn) and copper (from ?0.38‰ to 0.23‰ for δ⁶⁵Cu), suggest a control by physical mixing of continental and marine water masses, characterized by distinct Cu and Zn isotopic signatures. These results provide a stepping‐stone to further evaluate the use of Cu and Zn isotopes as biogeochemical tracers in estuarine environments.