RESUMO
Anthropogenic Pb is widespread in the environment including remote places. However, its presence in Canadian Arctic seawater is thought to be negligible based on low dissolved Pb (dPb) concentrations and proxy data. Here, we measured dPb isotopes in Arctic seawater with very low dPb concentrations (average â¼5 pmol â kg-1) and show that anthropogenic Pb is pervasive and often dominant in the western Arctic Ocean. Pb isotopes further reveal that historic aerosol Pb from Europe and Russia (Eurasia) deposited to the Arctic during the 20th century, and subsequently remobilized, is a significant source of dPb, particularly in water layers with relatively higher dPb concentrations (up to 16 pmol â kg-1). The 20th century Eurasian Pb is present predominantly in the upper 1,000 m near the shelf but is also detected in older deep water (2,000 to 2,500 m). These findings highlight the importance of the remobilization of anthropogenic Pb associated with previously deposited aerosols, especially those that were emitted during the peak of Pb emissions in the 20th century. This remobilization might be further enhanced because of accelerated melting of permafrost and ice along with increased coastal erosion in the Arctic. Additionally, the detection of 20th century Eurasian Pb in deep water helps constrain ventilation ages. Overall, this study shows that Pb isotopes in Arctic seawater are useful as a gauge of changing particulate and contaminant sources, such as those resulting from increased remobilization (e.g., coastal erosion) and potentially also those associated with increased human activities (e.g., mining and shipping).
Assuntos
Atividades Humanas , Água do Mar , Regiões Árticas , Canadá , Geografia , Humanos , Chumbo/análise , Água do Mar/químicaRESUMO
To evaluate metallurgical processing as a source of Zn and Cd isotopic fractionation and to potentially trace their distribution in the environment, high-precision MC-ICP-MS Zn, Cd and Pb isotope ratio measurements were made for samples from the integrated Zn-Pb smelting and refining complex in Trail, B.C., Canada. Significant fractionation of Zn and Cd isotopes during processing of ZnS and PbS ore concentrates is demonstrated by the total variation in delta(66/64)Zn and delta(114/110)Cd values of 0.42 per thousand and 1.04 per thousand, respectively, among all smelter samples. No significant difference is observed between the isotopic compositions of the Zn ore concentrates (delta(66/64)Zn=0.09 to 0.17 per thousand; delta(114/110)Cd=-0.13 to 0.18 per thousand) and the roasting product, calcine (delta(66/64)Zn=0.17 per thousand; delta(114/110)Cd=0.05 per thousand), due to approximately 100% recovery from roasting. The overall Zn recovery from metallurgical processing is approximately 98%, thus the refined Zn metal (delta(66/64)Zn=0.22 per thousand) is not significantly fractionated relative to the starting materials despite significantly fractionated fume (delta(66/64)Zn=0.43 per thousand) and effluent (delta(66/64)Zn=0.41 to 0.51 per thousand). Calculated Cd recovery from metallurgical processing is 72-92%, with the majority of the unrecovered Cd lost during Pb operations (delta(114/110)Cd=-0.38 per thousand). The refined Cd metal is heavy (delta(114/110)Cd=0.39 to 0.52 per thousand) relative to the starting materials. In addition, significant fractionation of Cd isotopes is evidenced by the relatively light and heavy isotopic compositions of the fume (delta(114/110)Cd=-0.52 per thousand) and effluent (delta(114/110)Cd=0.31 to 0.46 per thousand). In contrast to Zn and Cd, Pb isotopes are homogenized by mixing during processing. The total variation observed in the Pb isotopic compositions of smelter samples is attributed to mixing of ore sources with different radiogenic signatures.
Assuntos
Fracionamento Químico/métodos , Monitoramento Ambiental/métodos , Metais Pesados/análise , Poluentes do Solo/análise , Cádmio/análise , Canadá , Poluição Ambiental/análise , Resíduos Industriais , Isótopos , Chumbo/análise , Metalurgia , Zinco/análiseRESUMO
Resin-derived contaminants added to samples during column chemistry are shown to cause matrix effects that lead to inaccuracy in multi-collector inductively coupled plasma mass spectrometry measurement of small natural variations in Cd and Zn isotopic compositions. These matrix effects were evaluated by comparing pure Cd and Zn standards and standards doped with bulk column blank from the anion exchange chromatography procedure. Doped standards exhibit signal enhancements (Cd, Ag, Zn and Cu), instrumental mass bias changes and inaccurate isotopic compositions relative to undoped standards, all of which are attributed to the combined presence of resin-derived organics and inorganics. The matrix effect associated with the inorganic component of the column blanks was evaluated separately by doping standards with metals at the trace levels detected in the column blanks. Mass bias effects introduced by the inorganic column blank matrix are smaller than for the bulk column blank matrix but can still lead to significant changes in ion signal intensity, instrumental mass bias and isotopic ratios. Chemical treatment with refluxed HNO(3) or HClO(4)/HNO(3) removes resin-derived organic components resulting in matrix effects similar in magnitude to those associated with the inorganic component of the column blank. Mass bias correction using combined external normalization-SSB does not correct for these matrix effects because the instrumental mass biases experienced by Cd and Zn are decoupled from those of Ag and Cu, respectively. Our results demonstrate that ion exchange chromatography and associated resin-derived contaminants can be a source of error in MC-ICP-MS measurement of heavy stable element isotopic compositions.