Fractionation of stable zinc isotopes in the field-grown zinc hyperaccumulator Noccaea caerulescens and the zinc-tolerant plant Silene vulgaris.

Stable Zn isotope signatures offer a potential tool for tracing Zn uptake and transfer mechanisms within plant-soil systems. Zinc isotopic compositions were determined in the Zn hyperaccumulator Noccaea caerulescens collected at a Zn-contaminated site (Viviez), a serpentine site (Vosges), and a noncontaminated site (Sainte Eulalie) in France. Meanwhile, a Zn-tolerant plant ( Silene vulgaris ) was also collected at Viviez for comparison. While δ(66)Zn was substantially differentiated among N. caerulescens from the three localities, they all exhibited an enrichment in heavy Zn isotopes of 0.40-0.72‰ from soil to root, followed by a depletion in heavy Zn from root to shoot (-0.10 to -0.50‰). The enrichment of heavy Zn in roots is ascribed to the transport systems responsible for Zn absorption into root symplast and root-to-shoot translocation, while the depletion in heavy Zn in shoots is likely to be mediated by a diffusive process and an efficient translocation driven by energy-required transporters (e.g., NcHMA4). The mass balance yielded a bulk Zn isotopic composition between plant and soil (Δ(66)Zn(plant-soil)) of -0.01‰ to 0.63‰ in N. caerulescens , indicative of high- and/or low-affinity transport systems operating in the three ecotypes. In S. vulgaris , however, there was no significant isotope fractionation between whole plant and rhizosphere soil and between root and shoot, suggesting that this species appears to have a particular Zn homeostasis. We confirm that quantifying stable Zn isotopes is useful for understanding Zn accumulation mechanisms in plants.

Tracing and quantifying anthropogenic mercury sources in soils of northern france using isotopic signatures.

The mercury (Hg) isotopic composition was investigated in topsoils from two case studies in north of France. The Hg isotope composition was first determined in agricultural topsoils contaminated by a close by Pb-Zn smelter. The Hg isotopic composition was also measured in topsoils from an urban area in northeastern France (Metz). In both cases, no significant mass independent isotope fractionation could be found in the soils. However, the soil isotopic composition (δ(202)Hg) was enriched in the heavier isotopes as the Hg concentration increased in the soils. A linear relationship between the δ(202)Hg in soils and 1/[Hg] indicated a mixing between a contamination source and the Hg derived from the geogenic background soils. Such findings demonstrate that the contamination signature was preserved in the soils and that the deposition of anthropogenic Hg was predominant compared to reactions leading to isotope fractionation such as biotic and abiotic reduction of Hg(II) and resulting in Hg mobility or evasion from the soils. It was therefore possible, for the first time in the case of Hg, to evaluate the contribution of the contamination source relative to the background Hg source in urban topsoils using relative isotope abundances.

Isotope tracing of atmospheric mercury sources in an urban area of northeastern France.

Mercury (Hg) isotope composition was investigated in lichens over a territory of 900 km(2) in the northeast of France over a period of nine years (2001-2009). The studied area was divided into four geographical areas: a rural area, a suburban area, an urban area, and an industrial area. In addition, lichens were sampled directly at the bottom of chimneys, within the industrial area. While mercury concentrations in lichens did not correlate with the sampling area, mercury isotope compositions revealed both mass dependent and mass independent fractionation globally characteristic of each geographical area. Odd isotope deficits measured in lichens were smallest in samples close to industries, with Delta(199)Hg of -0.15 +/- 0.03 per thousand, where Hg is thought to originate mainly from direct anthropogenic inputs. Samples from the rural area displayed the largest anomalies with Delta(199)Hg of -0.50 +/- 0.03 per thousand. Samples from the two other areas had intermediate Delta(199)Hg values. Mercury isotopic anomalies in lichens were interpreted to result from mixing between the atmospheric reservoir and direct anthropogenic sources. Furthermore, the combination of mass-dependent and mass independent fractionation was used to characterize the different geographical areas and discriminate the end-members (industrial, urban, and local/regional atmospheric pool) involved in the mixing of mercury sources.

Variation in the isotopic composition of zinc in the natural environment and the use of zinc isotopes in biogeosciences: a review.

Zinc (Zn) is a trace element that is, as a building block in various enzymes, of vital importance for all living organisms. Zn concentrations are widely determined in dietary, biological and environmental studies. Recent papers report on the first efforts to use stable Zn isotopes in environmental studies, and initial results point to significant Zn isotope fractionation during various biological and chemical processes, and thus highlight their potential as valuable biogeochemical tracers. In this article, we discuss the state-of-the-art analytical methods for isotopic analysis of Zn and the procedures used to obtain accurate Zn isotope ratio results. We then review recent applications of Zn isotope measurements in environmental and life sciences, emphasizing the mechanisms and causes responsible for observed natural variation in the isotopic composition of Zn. We first discuss the Zn isotope variability in extraterrestrial and geological samples. We then focus on biological processes inducing Zn isotope fractionation in plants, animals and humans, and we assess the potential of Zn isotope ratio determination for elucidating sources of atmospheric particles and contamination. Finally, we discuss possible impediments and limitations of the application of Zn isotopes in (geo-) environmental studies and provide an outlook regarding future directions of Zn isotope research.

Ocean to continent transfer of atmospheric Se as revealed by epiphytic lichens.

There is still a long-term debate concerning the relative contributions of naturally emitted and anthropogenic Se at the regional and local scales. Here, Se and heavy metal concentrations are reported for epiphytic lichens collected in coastal and inland areas from the USA, Canada and France for assessing atmospheric Se source. Correlations found between Se and Cl in lichens confirmed the major marine biogenic source for atmospheric Se. Continental samples do not show systematic relationships between Se and other metal (Pb, Cu, In ...) contents, even for lichens collected in the vicinity of smelters or close to urban areas. Our results suggest that, although anthropogenic Se may be present, the marine biogenic Se source is a major contributor to atmospheric Se for our sampling locations. The contribution of naturally emitted atmospheric Se may be significant in urban and industrial areas and should be taken into account for further studies.

Odd isotope deficits in atmospheric Hg measured in lichens.

Redox reactions govern mercury (Hg) concentrations in the atmosphere because fluxes (emissions and deposition), and residence times, are largely controlled by Hg speciation. Recent work on aquatic Hg photoreduction suggested that this reaction produces non-mass dependent fractionation (NMF) and that residual aquatic Hg(II)is characterized by positive delta199Hg and delta201Hg anomalies. Here, we show that atmospheric Hg accumulated in lichens is characterized by NMF with negative delta199Hg and delta201Hg values (-0.3 to -1 per thousand), making the atmosphere and the aquatic environment complementary reservoirs regarding photoreduction and NMF of Hg isotopes. Because few other reactions than aquatic Hg photoreduction induce NMF, photochemical reduction appears to be a key pathway in the global Hg cycle. Based on a NMF isotope mass balance, direct anthropogenic emissions may account for only 50 +/- 10% of atmospheric Hg deposition in an urban area of NE France. Furthermore, isotopic anomalies found in several polluted soils and sediments strongly suggests that an important part of Hg in these samples was affected by photoreactions and has cycled through the atmosphere before being stored in the geological environment. Thus, mercury isotopic anomalies measured in environmental samples may be used to trace and quantify the contribution of source emissions.

Isotopic composition of Zn and Pb atmospheric depositions in an urban/Periurban area of northeastern France.

Epiphytic lichens, ambient PM-10, and bus air-filter aerosols collected in a city and the surrounding area were used to monitor urban atmospheric metal deposition in the Metz area, NE France. According to the measured Pb and Zn concentrations, high-enrichment factors (EF) were calculated for lichens collected in 2001 and 2003, suggesting an anthropogenic origin for those metals. Pb and Zn concentrations in lichens and other samples are correlated, probably indicative of the level of pollution recorded. However, different trends and scatters in the relationship suggest decoupling of Zn and Pb sources in this area. The lead isotopic composition of lichens varies largely from downtown, near traffic roads and highways, to suburbs but indicate an overall stability of sources between 2001 and 2003, although some minor variations were noted. Remobilization of Pb from leaded gasoline is still significant. The Zn isotopic composition measured in all lichens yielded fairly homogeneous delta66Zn ranging from -0.2% per hundred to 0.5% per hundred relative to ZnJMC solution. Most lichen samples are indistinguishable from urban aerosols (PM-10 and bus air filters, delta66Zn = 0.12 +/- 0.21% per hundred) and from flue gases from the city waste combustor (delta66Zn = 0.13 +/- 0.12% per hundred). No systematic variations of Zn EF and isotopic compositions were observed for and between 2001 and 2003 samples. Some lichens having unradiogenic 206Pb/207Pb ratios displayed high Zn and negative delta66Zn, indicative of a possible traffic source for Zn. A review from the literature on the Zn isotopic composition of terrestrial materials is reported but a few reservoirs seem to have specific compositions. According to the actual precision obtained, Zn isotopes for tracing pollution sources might not be straightforward but might be potentially useful for specific studies.

Selenium speciation in kerogen from two Chinese selenium deposits: environmental implications.

Selenium is an essential trace element for humans, animals, and vegetation. Its occurrence in the environment is characterized by specific chemical and biochemical properties that control its elemental solubility, toxicity, and environmental behavior. The Laerma Se-Au deposit and Yutangba Se deposit are two important Se-bearing deposits found recently in China. In one of these areas (Yutangba), a serious environmental impact happened involving Se poisoning. Previous studies have shown that Se in both deposits is closely related to organic matter, especially kerogen fractions, but detailed relationships between Se and kerogen and Se chemical forms were not reported. In this study, the different speciation of Se is identified by transmission electron microscopy (TEM) and other geochemical techniques (infrared spectra (IS) and X-ray diffraction (XRD)) from kerogen samples extracted from ore rocks of both deposits. The occurrence of organically bound Se in the Laerma deposit and elemental Se nanograins in the Yutangba deposit is observed, indicating the diversity of formation mechanisms and possible chemical forms of Se in Se-rich rocks. The formation of elemental Se associated with organic matter is likely related to redox conditions, whereas organic species are related to the higher sulfur content of kerogen and possibly result from S-Se substitutions. This discovery provides new evidence with which to assess potential Se mobility during weathering of ore-bearing rocks. In an altered rock, the elemental Se in kerogen is more steadily mobilized and is potentially accumulated by vegetation, which may explain the sudden prevalence of Se poisoning in the Yutangba area. In contrast, organically bound Se seems more resistant to chemical alteration compared to other Se species so that its bioavailability may be very restricted.

Lead isotopic composition of fly ash and flue gas residues from municipal solid waste combustors in France: implications for atmospheric lead source tracing.

Fly ash and flue gas residues from eight municipal solid waste combustors (MSWC) in France (1992--93 and 1998/ 2002) were analyzed for their Pb isotopic composition. Fly ashes are more representative of solid residual particles, whereas flue gas residues reflect mostly the composition of gas phases. Both sample types contain hundreds to thousands of micrograms of metals per gram. Leaching experiments showed that metals are present in condensed phases, probably as sulfates and chlorides, and suggest that Cd, Pb, and Zn are highly fractionated from one another during volatilization/condensation processes occurring during combustion. Although all the samples analyzed define a fairly restricted range in Pb isotopic compositions (206Pb/207Pb = 1.148-1.158 and 208Pb/206Pb = 2.101-2.114) compared to other environmental samples, some MSWC produce materials having distinct isotopic compositions, whereas others display very similar ones. Isotopic heterogeneity is also measured between samples from a single MSWC. This is interpreted as resulting from the heterogeneity of the waste source materials. The range of Pb isotopic composition of incinerator materials form a well-defined linear array in the 208Pb/206Pb versus 206Pb/207Pb diagram. This array is compatible with the previously reported European standard pollution (ESP) line and most probably represent the average lead isotopic composition of industrial atmospheric emissions in France, with the following ratios: 206Pb/207Pb = 1.154+/-0.003 and 208Pb/206Pb = 2.107+/-0.003 (1sigma).

GFAAS determination of selenium after separation with thiol cotton in lichens and plants: the importance of adding a mineral matrix before decomposition.

This study reports a preparation technique for the determination of Se concentration in lichens and plants, using matrix separation and preconcentration of samples with thiol cotton. Sample digestions were done using HNO(3)-H(2)O(2)-HF. A graphite furnace atomic absorption method has been used for the determination of Se in the different samples. The method was validated through the analysis of four certified reference materials (lichen, grass and sea lettuce) and of four in-house lichen materials. A limit of determination of 0.02 mug g(-1) in the solid sample and a precision (relative standard deviation) varying from 3 to 15% was found through the course of this study. The most important finding resides in the fact that a mineral matrix must be added to the lichen and plant samples before decomposition to obtain high and constant recoveries.