Cd Isotopic Compositions Research Articles

Cadmium isotope fractionation during coal combustion: Insights from two U.S. coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of ∼70% amorphous Al-Si-rich glasses and ∼30% mineral phases of quartz (SiO2) and mullite (Ai6Si2O13). The Cd isotope compositions (δ114Cd, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from −0.51 to +0.47‰) are distinctively heavier than those of BA samples (−0.75 to −0.52‰) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+1.10 to +7.09‰), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (−0.43 to +1.18‰). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.

Cadmium cycling in the water column of the Kuroshio-Oyashio Extension region: Insights from dissolved and particulate isotopic composition

We measured dissolved and particulate Cd isotopic composition in the water column of a meridional transect across the Kuroshio-Oyashio Extension region in a Japanese GEOTRACES cruise to investigate the relative influence of physical and biogeochemical processes on Cd cycling in the Northwestern Pacific Ocean. Located at 30–50°N along 165°E, the transect across the extension region possesses dramatic hydrographic contrast. Cold surface water and a relatively narrow and shallow thermocline characterizes the Oyashio Extension region in contrast to a relatively warm and highly stratified surface water and thermocline in the Kuroshio Extension region. The contrasting hydrographic distinction at the study site provides us with an ideal platform to investigate the spatial variations of Cd isotope fractionation systems in the ocean. Particulate samples demonstrated biologically preferential uptake of light Cd isotopes, and the fractionation effect varied dramatically in the surface water of the two regions, with relatively large fractionation factors in the Oyashio region. Based on the relationship of dissolved Cd concentrations and isotopic composition, we found that a closed system fractionation model can reasonably explain the relationship in the Kuroshio region. However, using dissolved Cd isotopic data, either a closed system or steady-state open system fractionation model may explain the relationship in the surface water of the Oyashio region. Particulate δ114/110Cd data further supports that the surface water of the Oyashio region matches a steady-state open system model more closely. Contrary to the surface water, the distribution of potential density exhibits comparable patterns with Cd elemental and isotopic composition in the thermocline and deep water in the two extension regions, showing that physical processes are the dominant forcing controlling Cd cycling in the deep waters. The results demonstrate that Cd isotope fractionation can match either a closed or open system Rayleigh fractionation model, depending on the relative contribution of physical and biogeochemical processes on its cycling.

Cadmium isotopic evidence for the evolution of marine primary productivity and the biological extinction event during the Permian-Triassic crisis from the Meishan section, South China

Abstract Cadmium (Cd) isotopic compositions in seawater are important parameters for tracing the biogeochemical cycling of Cd in modern oceans and may be used as a direct proxy for nutrient utilization by phytoplankton and an indirect proxy for primary productivity. In this study, we measured the stable Cd isotope ratios (δ114Cd) of marine sedimentary carbonates from the Meishan section in Changxing County of Zhejiang Province, South China, the Global Stratotype Section and Point (GSSP) of the Permian-Triassic Boundary (PTB). The results suggest that the inferred marine primary productivity recorded in the marine carbonates from the Late Permian (i.e., before the mass extinction) was high and relatively stable (the δ114/110Cd values of carbonates range from +0.31‰ to +0.60‰; after correction for salinity-controlled fractionation into inorganic calcite, the δ114/110Cd values of palaeo-seawater range from +0.47‰ to +0.79‰). During the mass extinctions, the δ114/110Cd values of carbonates abruptly decreased at the beginning of each episode of mass extinction, suggesting that the primary productivity of the palaeo-ocean declined before each episode of extinction events at the PTB. We suggest that the mass extinction events at the PTB in the Meishan section could be a ripple effect due to the destruction of primary producers at the base of the food chain in the palaeo-ocean ecosystem.

Cd isotope fractionation during sulfide mineral weathering in the Fule Zn-Pb-Cd deposit, Yunnan Province, Southwest China

Zinc (Zn)-Lead (Pb) deposits are generally rich in cadmium (Cd), and the weathering of sulfide minerals in such deposits results in large releases of Cd into the environment. From an environmental and public health standpoint, understanding Cd sources and cycling is critical to identifying potential hazards to humans. In this study, the Cd isotope compositions (expressed as δ114/110Cd) of secondary minerals such as anglesite (−0.57±0.03‰; 2S.D.), granular smithsonite (0.04±0.14‰; 2S.D.), layered smithsonite (0.15±0.40‰; 2S.D.), hydrozincite (0.26±0.01‰; 2S.D.) and clay minerals (−0.01±0.06‰; 2S.D.) from the Fule Zn-Pb-Cd deposit, Southwest China, are investigated to better understand the Cd sources and cycling in this area.Combined with our previous study (Zhu et al., 2017), the work herein elucidates the patterns of Cd isotopic fractionation during the formation processes of such secondary minerals and traces the weathering of these minerals into the ecosystem. The δ114/110Cd values of secondary minerals exhibit the following decreasing trend: hydrozincite>large granular smithsonite>small granular smithsonite>anglesite. Although different amounts of Cd were lost during the formation of equally sized samples, no or minor variations in Cd isotopic composition were observed. However, significant isotopic differences were observed between different size fractions. These results demonstrate that the particle size of secondary minerals and weathering products of sulfide significantly influence Cd isotope composition and fractionation during natural weathering. This systematic fractionation provides an initial foundation for the use of Cd isotopes as environmental tracers in ecosystems and in the global Cd isotope budget.

Variable Tl, Pb, and Cd concentrations and isotope compositions of enstatite and ordinary chondrites—Evidence for volatile element mobilization and decay of extinct 205Pb

AbstractNew Tl, Pb, and Cd concentration and Tl, Pb isotope data are presented for enstatite as well as L‐ and LL‐type ordinary chondrites, with additional Cd stable isotope results for the former. All three chondrite suites have Tl and Cd contents that vary by more than 1–2 orders of magnitude but Pb concentrations are more uniform, as a result of terrestrial Pb contamination. Model calculations based on Pb isotope compositions indicate that for more than half of the samples, more than 50% of the measured Pb contents are due to addition of modern terrestrial Pb. In part, this is responsible for the relatively young and imprecise Pb‐Pb ages determined for EH, L, and LL chondrites, which are hence only of limited chronological utility. In contrast, four particularly pristine EL chondrites define a precise Pb‐Pb cooling age of 4559 ± 6 Ma. The enstatite chondrites (ECs) have highly variable ε114/110Cd of between about +3 and +70 due to stable isotope fractionation from thermal and shock metamorphism. Furthermore, nearly all enstatite meteorites display ε205Tl values from −3.3 to +0.8, while a single anomalous sample is highly fractionated in both Tl and Cd isotopes. The majority of the ECs thereby define a correlation of ε205Tl with ε114/110Cd, which suggests that at least some of the Tl isotope variability reflects stable isotope fractionation rather than radiogenic ingrowth of 205Tl from 205Pb decay. Considering L chondrites, most ε205Tl values range between −4 and +1, while two outliers with ε205Tl ≤ −10 are indicative of stable isotope fractionation. Considering only those L chondrites which are least likely to feature Pb contamination or stable Tl isotope effects, the results are in accord with the former presence of live 205Pb on the parent body, with an initial 205Pb/204Pb = (1.5 ± 1.4) × 10−4, which suggests late equilibration of the Pb‐Tl system 26–113 Ma after carbonaceous chondrites (CCs). The LL chondrites display highly variable ε205Tl values from −12.5 to +14.9, also indicative of stable isotope effects. However, the data for three pristine LL3/LL4 chondrites display an excellent correlation between ε205Tl and 204Pb/203Tl. This defines an initial 205Pb/204Pb of (1.4 ± 0.3) × 10−4, equivalent to a 205Pb‐205Tl cooling age of 55 + 12/−24 Ma (31–67 Ma) after CCs.

Isotope Tracing of Long-Term Cadmium Fluxes in an Agricultural Soil.

Globally widespread phosphate fertilizer applications have resulted in long-term increases in the concentration of cadmium (Cd) in soils. The accumulation of this biotoxic, and bioaccumulative metal presents problems for the management of soil-plant-animal systems, because the magnitude and direction of removal fluxes (e.g., crop uptake, leaching) have been difficult to estimate. Here, Cd isotopic compositions (δ114/110Cd) of archived fertilizer and soil samples from a 66 year-long agricultural field trial in Winchmore, New Zealand, were used to constrain the Cd soil mass balance between 1959 and 2015 AD, informing future soil Cd accumulation trajectories. The isotopic partitioning of soil Cd sources in this system was aided by a change in phosphate source rocks in 1998 AD, and a corresponding shift in fertilizer isotope composition. The dominant influence of mixing between isotopically distinct Cd end-members was confirmed by a Bayesian modeling approach. Furthermore, isotope mass balance modeling revealed that Cd removal processes most likely increased in magnitude substantially between 2000 and 2015 AD, implying an increase in Cd bioaccumulation and/or leaching over that interval. Natural-abundance stable isotopes are introduced here as a powerful tool for tracing the fate of Cd in agricultural soils, and potentially the wider environment.

Fine-scale spatial and interannual cadmium isotope variability in the subarctic northeast Pacific

We present dissolved cadmium (Cd) concentrations, [Cd], and stable isotope compositions, ε112/110Cd, in high-resolution depth profiles from five stations along the Line P transect in the subarctic northeast Pacific Ocean. In addition to profiles collected in 2012, subsurface isopycnal samples and surface samples were collected in 2013 and 2014 respectively, providing both temporal and spatial coverage. Surface waters are characterized by Cd depletion relative to phosphate (PO43−) compared to deepwater Cd:PO43−, and high inferred remineralization ratios in the nutricline (0.45nmolμmol−1) are observed, consistent with Cd enrichment relative to phosphorus (P) in surface-derived biogenic particles. The correlation between Cd and PO43− weakens at depths where oxygen is highly depleted as shown by local minima in dissolved [Cd] and the tracer Cd⁎. The decoupling, which is driven by a deficit of Cd relative to PO43−, appears consistent with the recent hypothesis of dissolved Cd removal in oxygen-depleted regions by insoluble metal sulfide formation.Dissolved ε112/110Cd indicates a biologically driven fractionation in surface waters with more positive (heavy) values in the upper water column and lower (light) values in deeper waters. The highest ε112/110Cd observed in our sample set (5.19±0.23) is comparable to observations from the Southern Ocean but is significantly lighter than maximum reported surface values from the subtropical North Pacific of ε112/110Cd≥15. A global compilation of low [Cd] surface water shows similar differences in maximum ε112/110Cd. A surface water intercalibration should be prioritized to help determine if these differences at low [Cd] reflect true physical or biological variability or are due to analytical artefacts. Surface samples from the 2012 sampling campaign fit a closed-system Rayleigh fractionation model; however, surface waters sampled in 2014 had much lower [Cd] with relatively constant ε112/110Cd that cannot be explained by a closed-system Rayleigh model. These results correspond with a warm water surface anomaly found along Line P in 2014 and demonstrate that there is interannual variability in the biogeochemical cycling of Cd and its isotopes in the subarctic North Pacific. In contrast to other ocean basins where vertical variability in ε112/110Cd is observed at depth, deep and intermediate waters in the North Pacific have a near-uniform ε112/110Cd value (mean of 1.14±0.37, n=43, 2SD) representative of nearly all samples at or below 1000 m depth. Imprinted upon this nearly homogeneous intermediate and deep North Pacific ε112/110Cd signature are fine-scale spatial trends, with heavier values observed toward the coastal end of Line P than the oceanic end at intermediate depths, and with slightly heavier values in subtropical North Pacific deep water compared to the subarctic North Pacific. The nearly constant Cd isotopic composition of North Pacific deep waters is consistent with the inflow of Circumpolar Deep Water at depth in the Pacific basin, along with deep remineralization, and supports the potential of ε112/110Cd as a tracer of global deepwater circulation.

Non-Rayleigh control of upper-ocean Cd isotope fractionation in the western South Atlantic

We present seawater Cd isotopic compositions in five depth profiles and a continuous surface water transect, from 50°S to the Equator, in the western South Atlantic, sampled during GEOTRACES cruise 74JC057 (GA02 section, Leg 3), and investigate the mechanisms governing Cd isotope cycling in the upper and deep ocean.The depth profiles generally display high ε112/110Cd at the surface and decrease with increasing depth toward values typical of Antarctic Bottom Water (AABW). However, at stations north of the Subantarctic Front, the decrease in ε112/110Cd is interrupted by a shift to values intermediate between those of surface and bottom waters, which occurs at depths occupied by North Atlantic Deep Water (NADW). This pattern is associated with variations in Cd concentration from low surface values to a maximum at mid-depths and is attributed to preferential utilization of light Cd by phytoplankton in the surface ocean. Our new results show that in this region Cd-deficient waters do not display the extreme, highly fractionated ε112/110Cd reported in some earlier studies from other oceanic regions. Instead, in the surface and subsurface southwest (SW) Atlantic, when [Cd] drops below 0.1 nmol kg−1, ε112/110Cd are relatively homogeneous and cluster around a value of +3.7, in agreement with the mean value of 3.8±3.3 (2SD, n=164) obtained from a statistical evaluation of the global ocean Cd isotope dataset. We suggest that Cd-deficient surface waters may acquire their Cd isotope signature via sorption of Cd onto organic ligands, colloids or bacterial/picoplankton extracellular functional groups. Alternatively, we show that an open system, steady-state model is in good accord with the observed Cd isotope systematics in the upper ocean north of the Southern Ocean. The distribution of ε112/110Cd in intermediate and deep waters is consistent with the water mass distribution, with the north–south variations reflecting changes in the mixing proportion of NADW and either AABW or AAIW depending on the depth. Overall, the SW Atlantic Cd isotope dataset demonstrates that the large-scale ocean circulation exerts the primary control on ε112/110Cd cycling in the global deep ocean.

The Cd isotope composition of atmospheric aerosols from the Tropical Atlantic Ocean

AbstractStable isotope compositions can potentially be used to trace atmospheric Cd inputs to the surface ocean and anthropogenic Cd emissions to the atmosphere. Both of these applications may provide valuable insights into the effects of anthropogenic activities on the cycling of Cd in the environment. However, a lack of constraints for the Cd isotope compositions of atmospheric aerosols is currently hindering such studies. Here we present stable Cd isotope data for aerosols collected over the Tropical Atlantic Ocean. The samples feature variable proportions of mineral dust‐derived and anthropogenic Cd, yet exhibit similar isotope compositions, thus negating the distinction of these Cd sources by using isotopic signatures in this region. Isotopic variability between these two atmospheric Cd sources may be identified in other areas, and thus warrants further investigation. Regardless, these data provide important initial constraints on the isotope composition of atmospheric Cd inputs to the ocean.

Cadmium isotope fractionation in the Fule Mississippi Valley-type deposit, Southwest China

High-precision cadmium (Cd) isotope compositions are reported for sphalerite, galena, and smithsonite from the Fule Zn–Pb–Cd deposit, a typical Mississippi Valley-type deposit in Southwest China. Dark sphalerite has lighter δ114/110Cd values (0.06 to 0.46 ‰) than light sphalerite (0.43 to 0.70 ‰), and the Cd in galena is primarily in the form of sphalerite micro-inclusions with δ114/110Cd of −0.35 to 0.39 ‰. From early to late stages, δ114/110Cd values of smithsonite regularly increase from 0.19 to 0.42 ‰, whereas Cd/Zn ratios decrease from 252 to 136; the δ114/110Cd variation pattern of supergene smithsonite reflects kinetic Rayleigh fractionation during low-temperature processes. From the bottom to the top of the orebody, the dark sphalerite has different patterns in δ114/110Cd values, Cd/Zn ratios, δ34S values, and Fe concentrations compared to the light sphalerite, indicating that dark and light sphalerite formed by different processes. The varying patterns of δ144/110Cd values and Cd/Zn ratios within light sphalerite are similar to those of layered smithsonite, and the δ144/110Cd values have a positive correlation with δ34S values, indicating that Cd isotope fractionation in the light sphalerite was due to kinetic Rayleigh fractionation. Instead, in dark sphalerite, the δ144/110Cd values have a negative correlation with δ34S values and a positive correlation with the Cd/Zn ratio. Thus, it can be concluded that dark sphalerite could be modeled in terms of two-component mixing (basement fluid and host-rock fluid), which is in agreement with previous explanations for the negative correlation between δ66Zn and δ34S in some typical Zn–Pb deposits. We propose that the significant variation in Cd isotope composition observed in the Fule Zn–Pb–Cd deposit confirms that Cd isotopes can be used for tracing fluid evolution and ore formation.

Fractionation of Stable Cadmium Isotopes in the Cadmium Tolerant Ricinus communis and Hyperaccumulator Solanum nigrum.

Cadmium (Cd) isotopes provide new insights into Cd uptake, transport and storage mechanisms in plants. Therefore, the present study adopted the Cd-tolerant Ricinus communis and Cd-hyperaccumulator Solanum nigrum, which were cultured under controlled conditions in a nutrient solution with variable Cd supply, to test the isotopic fractionation of Cd during plant uptake. The Cd isotope compositions of nutrient solutions and organs of the plants were measured by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS). The mass balance of Cd isotope yields isotope fractionations between plant and Cd source (δ114/110Cdorgans-solution) of −0.70‰ to −0.22‰ in Ricinus communis and −0.51‰ to −0.33‰ in Solanum nigrum. Moreover, Cd isotope fractionation during Cd transport from stem to leaf differs between the Cd-tolerant and -hyperaccumulator species. Based on these results, the processes (diffusion, adsorption, uptake or complexation), which may induce Cd isotope fractionation in plants, have been discussed. Overall, the present study indicates potential applications of Cd isotopes for investigating plant physiology.

Cadmium and sulfur isotopic compositions of the Tianbaoshan Zn–Pb–Cd deposit, Sichuan Province, China

Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78m. Sphalerite has δ114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ34SCDT values ranging from 0.2 to 5.0‰. Although δ34SCDT and δ114/110Cd values in sphalerites have no regular spatial variations, the δ34SCDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130°C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ34S∑S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0±3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit.

Improvements in Cd stable isotope analysis achieved through use of liquid-liquid extraction to remove organic residues from Cd separates obtained by extraction chromatography.

Organic compounds released from resins that are commonly employed for trace element separations are known to have a detrimental impact on the quality of isotopic analyses by MC-ICP-MS. A recent study highlighted that such effects can be particularly problematic for Cd stable isotope measurements (M. Gault-Ringold and C. H. Stirling, J. Anal. At. Spectrom., 2012, 27, 449-459). In this case, the final stage of sample purification commonly applies extraction chromatography with Eichrom TRU resin, which employs particles coated with octylphenyl-N,N-di-isobutyl carbamoylphosphine oxide (CMPO) dissolved in tri-n-butyl phosphate (TBP). During chromatography, it appears that some of these compounds are eluted alongside Cd and cannot be removed by evaporation due to their high boiling points. When aliquots of the zero-ε reference material were processed through the purification procedure, refluxed in concentrated HNO3 and analyzed at minimum dilution (in 1 ml 0.1 M HNO3), they yielded Cd isotopic compositions (ε114/110Cd = 4.6 ± 3.4, 2SD, n = 4) that differed significantly from the expected value, despite the use of a double spike technique to correct for instrumental mass fractionation. This result was accompanied by a 35% reduction in instrumental sensitivity for Cd. With increasing dilution of the organic resin residue, both of these effects are reduced and they are insignificant when the eluted Cd is dissolved in ≥3 ml 0.1 M HNO3. Our results, furthermore, indicate that the isotopic artefacts are most likely related to anomalous mass bias behavior. Previous studies have shown that perchloric acid can be effective at avoiding such effects (Gault-Ringold and Stirling, 2012; K. C. Crocket, M. Lambelet, T. van de Flierdt, M. Rehkämper and L. F. Robinson, Chem. Geol., 2014, 374-375, 128-140), presumably by oxidizing the resin-derived organics, but there are numerous disadvantages to its use. Here we show that liquid-liquid extraction with n-heptane removes the organic compounds, dramatically improving quality of the Cd isotope data for samples that are analyzed at or close to minimum dilution factors. This technique is quick, simple and may be of use prior to analysis of other isotope systems where similar resins are employed.

Isotopic Geochemistry of Cadmium: A Review

AbstractCadmium (Cd) is a scarce, but not an extremely rare element in the Earth's crust (crustal average: 0.2 ppm Cd). Geochemically, Cd exhibits thiophile, lithophile, and volatile behavior in different geologic processes. Biologically, it is a nutrient‐like element that is closely related to P and Zn and is toxic element to organisms. Presently, Cd isotopes have been successfully utilized to trace Cd sources and nutrient cycling in marine systems in addition to unearthing other geochemical processes. Using published studies and our recent work, this survey summarizes the chemical preparation and mass spectrometry of Cd isotopes. It also reviews Cd isotopic compositions and fractionation mechanisms in nature as well as experiments.

Cadmium isotope fractionation of materials derived from various industrial processes

Our study represents ϵ114/110 Cd NIST3108 values of materials resulting from anthropogenic activities such as coal burning, smelting, refining, metal coating, and the glass industry. Additionally, primary sources (ore samples, pigment, coal) processed in the industrial premises were studied. Two sphalerites, galena, coal and pigment samples exhibited ϵ114/110 CdNIST3108 values of 1.0±0.2, 0.2±0.2, 1.3±0.1, −2.3±0.2 and −0.1±0.3, respectively. In general, all studied industrial processes were accompanied by Cd isotope fractionation. Most of the industrial materials studied were clearly distinguishable from the samples used as a primary source based on ϵ114/110 Cd NIST3108 values. The heaviest ϵ114/110 CdNIST3108 value of 58.6±0.9 was found for slag resulting from coal combustion, and the lightest ϵ114/110 CdNIST3108 value of −23±2.5 was observed for waste material after Pb refinement. It is evident that ϵ114/110 Cd NIST3108 values depend on technological processes, and in case of incomplete Cd transfer from source to final waste material, every industrial activity creates differences in Cd isotope composition. Our results show that Cd isotope analysis is a promising tool to track the origins of industrial waste products.

Cd isotopic composition in the suspended and sinking particles of the surface water of the South China Sea: The effects of biotic activities

We determined the Cd isotopic composition of size-fractionated phytoplankton, zooplankton and sinking particles collected in the top 160 m of a deep water time series station in the South China Sea (SCS) to investigate the fractionation effects of major biotic activities. The isotopic composition (εCd114/110=[(Cd114/Cd110)sample/(Cd114/Cd110)NIST 3108−1]×104) ranged from −2.5 to +7.0, from −9.3 to +6.7, from −1.2 to +4.5, and from −0.2 to +3.2ε in the plankton of size fractions 10–60, 60–150, >150, and >100 μm, respectively. The composition in the two smallest fractions, dominated by phytoplankton, was lower than the ambient seawater value (+8 to +9ε), indicating that the phytoplankton preferentially take up relatively light Cd isotopes. The insignificant difference between the composition of phytoplankton and zooplankton suggests that the fractionation effect through zooplankton grazing may be relatively small. The composition in the sinking particles at 30 m, ranging from +8.1 to +12.8ε, was significantly heavier than the composition in the suspended particles and the composition increased with depth, ranging from +11.5 to +20.8ε at 100 m, and from +16.0 to +18.0ε at 160 m. The increasing isotopic value with depth indicates that the processes of microbial degradation and/or zooplankton repackaging preferentially decomposed relatively light Cd in the sinking particles. The comparable isotopic composition between sinking particles and dissolved Cd indicates that the fractionation effects of major biotic activities, including phytoplankton uptake, microbial degradation and zooplankton repackaging, take place at similar magnitudes and result in insignificant net biological fractionation effects of Cd in the mixed layer.

Cadmium isotope fractionation within the soil profile complicates source identification in relation to Pb–Zn mining and smelting processes

Many cadmium species are among the most toxic of environmental contaminants. Because Cd in many forms is mobile in the environment, identifying its sources is a crucial aspect of remedial intervention. Data from the literature suggest that Cd isotopes could be a useful tool for such identification, but no data about Cd isotopes through entire soil profiles has yet been published. We compared in this paper the Cd isotope composition of three forest and two meadow soil profiles affected by different contamination sources near the Olkusz Pb–Zn smelter in southern Poland together with the main industrial source of possible contamination at that location. In the contaminated forest soil profile, the upper soils reflected the heaviest Cd isotope compositions, while the deeper soil humus layer had the lightest Cd isotope compositions. We found that the overall Cd isotope heterogeneity in industrial wastes was overlapped by the overall Cd isotope fractionation within the forest soil profile near the smelter (ε114/110CdNIST3108 values of 5.14 compared to 11.8, respectively). Both meadow soil profiles had approximately a Cd isotope composition corresponding to the processed ore (Olkusz sphalerite).

Tracing sources of pollution in soils from the Jinding Pb–Zn mining district in China using cadmium and lead isotopes

Systematic variations in the Cd and Pb isotope ratios in polluted topsoils surrounding the Jinding Pb–Zn mine in China were measured so that the sources of the metals could be traced. The average δ114/110Cd value and 206Pb/207Pb isotope ratio in background soils from the region were +0.41‰ and 1.1902, respectively, whereas the contaminated soil samples had different values, with the δ114/110Cd values varying between −0.59‰ and +0.33‰ and the 206Pb/207Pb isotope ratios varying between 1.1764 and 1.1896. We also measured the Cd and Pb isotopic compositions in oxide ores, sulfide ores, and slags, and found that binary mixing between ores and background soils could explain almost all of the variations in the Cd and Pb isotope ratios in the contaminated soils. This suggests that Cd and Pb pollution in the soils was mainly caused by the deposition of dust emitted during anthropogenic activities (mining and refining). The Pb and Cd isotope ratios clearly showed that contamination in soils in the northeastern part of the area was caused by surface mines and zinc smelters and their slagheaps, while contamination in soils in the southwestern part of the area also came from tailing ponds and underground mines. The main area of soil polluted by dust from Pb–Zn mining processes roughly extended for up to 5km from the mine itself.

The isotopic composition of dissolved cadmium in the water column of the West Philippine Sea

The dissolved concentration and isotopic compositions of cadmium (Cd) in the seawater of the West Philippine Sea were determined. In general, Cd isotopic composition in the water column decreased with depth, with e114/110Cd (e114/110Cd = [(114Cd/110Cd)sample / (114Cd/110Cd)NIST 3108 - 1]×10000) ranging from +7.2 to +10.1 in the top 60 m, from +4.8 to +5.1 between 100 and 150 m, peaking at +8.2 at 200 m, decreasing from +4.5 to +3.3 from 400 to 1000 m, and remaining constant at +3.0 from 1000 m and deeper. Different to a Rayleigh fractionation model, the isotopic composition and log scale concentrations of Cd do not exhibit a linear relationship. However, from the deep water to thermocline, the variations in Cd concentration and e114/110Cd are relevant to the variations of temperature and salinity, indicating that water mixing is the dominant processes determining the concentration and isotopic composition in the interval. At 200 m where North Pacific Tropic Water dominates the water mass, the elevated e114/110Cd could be linked to the composition in the upper portions of the water mass. In the top 150 m, the e114/110Cd varies similarly to the phytoplankton community structures, implying that Cd uptake by various phytoplankton species may be associated with the isotopic variation. However, the effects of atmospheric inputs to the e114/110Cd in the surface water cannot be excluded. A box model calculation is used to constrain the contributions of various processes to the Cd isotopes of surface water, and the results indicate that the Cd concentration and isotopic composition in most of the water body of the region are controlled by physical mixing, while the effects of biological fractionation and atmospheric inputs are limited in the euphotic zone.

Cadmium isotope fractionation during adsorption to Mn oxyhydroxide at low and high ionic strength

We report results of experiments conducted to quantify the sense and magnitude of cadmium stable isotope fractionation during sorption to synthetic birnessite (Mn oxyhydroxide) and to constrain the molecular mechanism responsible for fractionation in this system. Ferromanganese crusts have recently been proposed as a possible archive of the cadmium isotopic composition of seawater over the last few tens of millions of years (Horner et al., 2010), and this archive can potentially yield information about biological use of Cd by diatoms over the Cenozoic Era. Cd isotopes may also be useful for determining the extent to which sorption to mineral substrates attenuates Cd transport in contaminated aquifers. At low ionic strength, we found a small fractionation effect (Δ114/112Cdfluid–solid=+0.12±0.06‰, 1sd; equivalent to +2.4 in terms of ε114/110Cd) that was constant as a function of the fraction of total Cd sorbed, indicating a reversible equilibrium isotope effect. At high ionic strength we observed a fractionation averaging (Δ114/112Cdfluid–solid=+0.27±0.07‰ (1sd; equivalent to +5.4 in terms of ε114/110Cd). A time series conducted at high ionic strength revealed that the magnitude of isotopic fractionation decreases gradually over time, from Δ114/112Cdfluid–solid of nearly +0.4‰ after 1h to +0.2‰ after 24h and +0.1‰ after 912h. Furthermore, the percentage of Cd sorbed to birnessite increases over this interval from 27% to 58%. We hypothesize that this shift results from either changes over time in the structure and crystallinity of birnessite and/or a change in the molecular mechanism of sorption of cadmium on birnessite. Our result is encouraging for application of Cd isotopes in ferromanganese crusts to reconstruction of the Cd isotopic composition of coexisting seawater, given the very slow accumulation rates of such sediments.