Regional and global perspectives of honey as a record of lead in the environment.

Honey from Apis mellifera is a useful and inexpensive biomonitor for mapping metal distributions in urban centers. The sampling resolution of a biomonitoring survey (e.g., city versus global scale) determines which geochemical processes are reflected in the results. This study presents Pb isotopic compositions and metal concentrations in honey from around the world, sampled at varying resolutions: honey from Canada (n = 21), the United States (n = 111), Belgium (n = 25), and New Zealand (n = 10), with additional samples from Afghanistan, Brazil, Cuba, Germany, Liberia, Taiwan, and Turkey. Honey was sampled at high resolution in two uniquely different land-use settings (New York Metro Area and the Hawaiian island of Kaua'i), at regional-scale resolution in eastern North America (including the Great Lakes region), and Pb isotopic compositions of all samples were compared on a global scale. At high sampling resolution, metal concentrations in honey reveal spatially significant concentration gradients: in New York City, metals associated with human activity and city infrastructure (e.g., Pb, Sb, Ti, V) are more concentrated in honey collected within the city compared to honey from upstate New York, and metal concentrations in honey from Kaua'i suggest polluting effects of nearby agricultural operations. At lower resolution (regional and global scales), lead isotopic compositions of honey are more useful than metal concentrations in revealing large-scale Pb processes (e.g., the enduring legacy of global leaded gasoline use throughout the twentieth century) and the continental origin of the honey. Lead isotopic compositions of honey collected from N. America (especially from the eastern USA) are more radiogenic (206Pb/207Pb: 1.132-1.253, 208Pb/206Pb: 2.001-2.129) compared to European honey, and honey from New Zealand, which has the least radiogenic isotopic compositions measured in this study (206Pb/207Pb: 1.077-1.160, 208Pb/206Pb: 2.090-2.187). Thus, biomonitoring using honey at different resolutions reflects differing processes and, to some extent, a honey terroir defined by the Pb isotopic composition. The data presented here provide important (and current) global context for future studies that utilize Pb isotopes in honey. Moreover, this study exhibits community science in action, as most of the honey was collected by collaborators around the world, working directly with local apiarists and hobby beekeepers.

Tracing Molybdenum Attenuation in Mining Environments Using Molybdenum Stable Isotopes.

Molybdenum contamination is a concern in mining regions worldwide. Better understanding of processes controlling Mo mobility in mine wastes is critical for assessing potential impacts and developing water-quality management strategies associated with this element. Here, we used Mo stable isotope (δ98/95Mo) analyses to investigate geochemical controls on Mo mobility within a tailings management facility (TMF) featuring oxic and anoxic environments. These isotopic analyses were integrated with X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and aqueous chemical data. Dissolved Mo concentrations were inversely correlated with δ98/95Mo values such that enrichment of heavy Mo isotopes in solution reflected attenuation processes. Inner-sphere complexation of Mo(VI) with ferrihydrite was the primary driver of Mo removal and was accompanied by a ca. 1‰ isotope fractionation. Limited Mo attenuation and isotope fractionation were observed in Fe(II)- and Mo-rich anoxic TMF seepage, while attenuation and isotope fractionation were greatest during discharge and oxidation of this seepage after discharge into a pond where Fe-(oxyhydr)oxide precipitation promoted Mo sorption. Overall, this study highlights the role of sorption onto Fe-(oxyhydr)oxides in attenuating Mo in oxic environments, a process which can be traced by Mo isotope analyses.

Metal and Pb isotope characterization of particulates encountered by foraging honeybees in Metro Vancouver.

Honeybees and their products are useful biomonitors of metal distribution in urban centres. This study investigates particulate sources that foraging honeybees encounter in Metro Vancouver. Metal concentrations and lead (Pb) isotope compositions were measured in topsoil (top 2 cm, n = 14) colocated with existing research hives and in particulate matter ≤10 µm (PM10, n = 27) collected throughout Metro Vancouver (British Columbia, Canada) during honeybee foraging hours over the course of one year (2018-2019). Topsoil served as a proxy for resuspended/coarse PM and, together with PM10, covered the size range of particulates collected by foraging bees both actively (pollen) and passively (dusts). Particulate matter ≤ 2.5 µm (PM2.5, n = 7) was collected on Whistler Mountain during two transpacific events (in spring 2014) to estimate the possible effect of transpacific particulate input on the Pb isotope composition of Western Canada aerosols. Metal concentrations and Pb isotopes in topsoil and PM from this study and bees and hive products from previous studies (collected in 2014-2019) reveal similar spatial trends: there were elevated amounts of some metals associated with anthropogenic activity (e.g., Pb, Zn, Sb) and less radiogenic Pb isotope compositions in most samples collected nearer to the city centre in comparison to samples collected in more suburban or rural areas. Bees and hive products have a smoothing effect on the spatiotemporal variability of the data; metal concentrations and Pb isotope compositions vary less in hive products than in PM, presumably because bees interact with multiple environmental domains while foraging. Wildfire smoke and transpacific input are phenomena that cause measurable shifts in Pb isotope compositions of PM, but not in hive matrices. The findings highlight important considerations to make (i.e., the smoothing effect) when linking public health data and decisions with environmental data from hive products in urban centres.

Evaluating Spatiotemporal Resolution of Trace Element Concentrations and Pb Isotopic Compositions of Honeybees and Hive Products as Biomonitors for Urban Metal Distribution.

Assessing metal distributions in cities is an important aspect of urban environmental quality management. Western honeybees (Apis mellifera) and their products are biomonitors that can elucidate small-scale metal distribution within a city. We compare range and variations in trace element (TE) concentrations and lead (Pb) isotopic compositions of honey, bee tissue, bee pollen, and propolis collected throughout Metro Vancouver (BC, Canada). Honey, bee, and bee pollen results have similar TE and isotopic trends; samples collected in urban and industrialized areas exhibit elevated concentrations of anthropogenically influenced TE (e.g., Pb, Zn, V, and Ti) and a less radiogenic Pb isotopic composition (i.e., lower 206Pb/207Pb and elevated 208Pb/206Pb) relative to their suburban and rural counterparts. For example, 206Pb/207Pb, 208Pb/206Pb in honey range from 1.126, 2.131 and 1.184, 2.063; extremes measured in honey from urban and suburban/rural areas, respectively. Except for propolis, measured and interpolated (kriged) results in all materials reflect the immediate zoning or land use setting near the hive, providing kilometer-scale geospatial resolution, suitable for monitoring urban systems. Statistical analysis reveals that no systematic variations or intra- or inter-annual trends exist in TE concentrations or Pb isotopic compositions, including among sampling and field methods (i.e., old vs. new hive equipment and honey from the brood nest box vs. honey super). The results of this systematic study using honeybees and hive products in Metro Vancouver provide a robust, current baseline for future comparison of local land use and environmental policy change.

Evaluation of zinc, cadmium and lead isotope fractionation during smelting and refining.

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.

Matrix effects on the multi-collector inductively coupled plasma mass spectrometric analysis of high-precision cadmium and zinc isotope ratios.

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.

Iron isotopic fractionation in industrial emissions and urban aerosols.

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM-EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO(3)) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08 per thousand

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.