Use of Stable Isotopes to Identify Sources of Mercury in Sediments: A Review and Uncertainty Analysis

Mass-dependent and mass-independent mercury isotope fractionation potentially generates unique source signatures that can be used to apportion contributions to sediment contamination. This article reviews findings from previous investigations that have used mercury isotopes to identify sources. It also discusses a mass balance mercury isotope fractionation model that simulates changes in isotopic source signatures in aquatic systems caused by natural biogeochemical cycling. According to the model, the extent of source signature alteration depends on chemical speciation, with more labile forms exhibiting greater isotopic fractionation. Apportionment is tractable when differences between δ²⁰²Hg of sources are larger than potential changes in isotopic signatures following the release of mercury into the environment.     

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 (CaCO₃) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08‰ < δ⁵⁶Fe < +0.80‰) of enriched ores processed by the manufacturer (−0.16‰ < δ⁵⁶Fe < +1.19‰). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3–4 μm aggregates. In the close urban area, 5 km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (δ⁵⁶Fe = 0.14 ± 0.11‰) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.     

Relationships between stable isotopes and metal contaminants in feathers are spurious and biologically uninformative

Stable isotopes of carbon (δ¹³C) and nitrogen (δ¹⁵N) are used frequently in ecotoxicological investigations of birds to relate contaminant levels to trophic position (δ¹⁵N) or foraging location (δ¹³C) and many researchers using avian feathers in such investigations use δ¹³C or δ¹⁵N as a predictor of contaminant concentrations. Contaminants, especially mercury, however, are integrated into feathers over different time periods than are stable isotopes, resulting in spurious relationships that have no biological meaning. I show the fundamental principles behind the conclusion that relating δ¹³C or δ¹⁵N to contaminant concentrations in feathers is not appropriate in light of the number of recent studies that have employed this approach, and make recommendations for those wishing to investigate the relationship between contaminants and stable isotope ratios.     

Atmospheric pollutants in alpine peat bogs record a detailed chronology of industrial and agricultural development on the Australian continent

Two peat bogs from remote alpine sites in Australia were found to contain detailed and coherent histories of atmospheric metal pollution for Pb, Zn, Cu, Mo, Ag, As, Cd, Sb, Zn, In, Cr, Ni, Tl and V. Dramatic increases in metal deposition in the post-1850 AD portion of the cores coincide with the onset of mining in Australia. Using both Pb isotopes and metals, pollutants were ascribed to the main atmospheric pollution emitting sources in Australia, namely mining and smelting, coal combustion and agriculture. Results imply mining and metal production are the major source of atmospheric metal pollution, although coal combustion may account for up to 30% of metal pollutants. A novel finding of this study is the increase in the otherwise near-constant Y/Ho ratio after 1900 AD. We link this change to widespread and increased application of marine phosphate fertiliser in Australia's main agricultural area (the Murray Darling Basin).     

Lead (Pb) isotopic fingerprinting and its applications in lead pollution studies in China: A review

As the most widely scattered toxic metal in the world, the sources of lead (Pb) observed in contamination investigation are often difficult to identify. This review presents an overview of the principles, analysis, and applications of Pb isotopic fingerprinting in tracing the origins and transport pathways of Pb in the environment. It also summarizes the history and current status of lead pollution in China, and illustrates the power of Pb isotopic fingerprinting with examples of its recent applications in investigating the effectiveness of leaded gasoline phase-out on atmospheric lead pollution, and the sources of Pb found in various environmental media (plants, sediments, and aquatic organisms) in China. The limitations of Pb isotopic fingerprinting technique are discussed and a perspective on its development is also presented. Further methodological developments and more widespread instrument availability are expected to make isotopic fingerprinting one of the key tools in lead pollution investigation.     

Diet shifts during egg laying: Implications for measuring contaminants in bird eggs

We combined stable isotope tracers of blood plasma, blood cells and egg contents with faecal analysis during pre-breeding and egg laying phases in two dipper species Cinclus cinclus and Cinclus mexicanus to determine the occurrence of dietary shifts during egg production and to assess consequences for egg contaminant loads. In both species, changes in δ¹³C (C. cinclus) or δ¹⁵N (C. mexicanus) in female plasma relative to red blood cells indicated a dietary shift during laying that was not observed in males. Eurasian dippers increased prey consumption as breeding approached, shifting from primarily trichopteran insect larvae to ephemeropterans and plecopterans. In American dippers, egg-laying females switched to feeding at a higher trophic level by consuming more fish. Eggs derived from higher trophic level diets contained more mercury (American dipper), polychlorinated biphenyls and some organochlorines, especially DDT metabolites. The results demonstrate how dietary changes during egg laying accompany the demands for egg production with consequences for contaminant deposition in avian eggs.     

Variations of sulfur isotope ratios in a single lichen thallus: A potential historical archive for sulfur pollution

Utilizing the analytical capability to measure S isotope ratios of small quantities of S in biological material without any chemical pretreatment, the variation of δ³⁴S within a lichen thallus was investigated using old and young segments of fruticose lichen thalli (Alectoria sarmentosa) from an oil refinery area in Come-By-Chance and two coastal areas, Newfoundland, Canada. Old segments of lichen samples from the oil refinery area showed significantly higher δ³⁴S values (1.0-2.5‰) than their corresponding young segments. Lichen samples from two coastal areas showed no noticeable differences in δ³⁴S values between old and young segments. These results demonstrate that lichen thalli record temporal changes in the isotopic composition of atmospheric S and hence constitute a historical archive of atmospheric S pollution.     

岩溶流域不同水体硝酸盐的来源解析

为解析岩溶流域不同水体中硝酸盐的来源和转化过程,运用δ~(15)N-NO~-_3、δ~(18)O-NO~-_3和δ~(18)O-H_2O多同位素示踪技术和水化学分析方法,对地表水和地下水的硝酸盐时空分布特征、来源及转化过程进行分析,并利用SIAR模型,计算不同端元对水体硝酸盐的贡献比例.结果表明,研究区水体溶解性无机氮以NO~-_3-N和NH~+_4-N两种形态为主,地下水样品中的NO~-_3-N浓度在平水期和枯水期的超标率分别为7.89%和16.67%.时间上,枯水期水体硝酸盐平均浓度高于平水期.空间上,旱地集中区(凯伦河至松柏山水库坝前区域)地下水硝酸盐浓度明显高于水田集中区(干河区域),旱地和建设用地集中区(凯伦河区域)地表水硝酸盐浓度普遍较高.水体硝酸盐转化过程以硝化作用为主,土壤有机氮、粪便污水和化肥为水体硝酸盐的主要来源,对地表水硝酸盐的贡献比例分别为36.7%、 34.7%和28.6%,对地下水硝酸盐的贡献比例分别为39.9%、 34.9%和25.2%.     

柴达木盆地东部降水氢氧同位素特征与水汽来源

稳定性氢氧同位素可以作为示踪剂来判断大气降水的水汽来源.本研究选择柴达木盆地南部的格尔木和东北部的德令哈两个区域,在分析这两个地区2010年6~9月降水同位素组成特征、时间变化以及降水中δD与δ18O关系的基础上,探讨柴达木盆地降水的水汽来源.结果表明:1格尔木和德令哈地区6~9月大气降水线分别为,格尔木:δD=7.840δ18O-4.566(R2=0.918,P0.001),德令哈:δD=7.833δ18O+8.606(R2=0.986,P0.001).两地区6~9月大气降水线的斜率和截距均低于全球大气降水线,而格尔木地区的截距仅为-4.566,反映出格尔木极其干旱的气候特点.2格尔木降水的δ18O在7月初较高,表现出一定的重同位素富集;在7月中下旬至9月初,δ18O较低;9月中下旬更低.德令哈降水的δ18O在6~8月相对较高,9月中下旬较低.3格尔木和德令哈地区水汽来源有一定的差异,格尔木地区可能是西南季风能够到达青藏高原的北部边界,德令哈地区水汽来源主要为局地蒸发.     

双河洞流域氢氧同位素特征及其指示意义

为了探究喀斯特区域地表水与地下水的相互转化关系及水-岩作用特征,以双河洞流域为研究对象,分别在2018年12月和2019年6月对流域地表水与地下水进行监测采样。运用数理统计、Piper三线图、回归分析等方法对水样的氢氧同位素组成和水化学特征进行分析。结果表明：(1)旱季和雨季流域内地表水、地下水优势阳离子以Ca²⁺和Mg²⁺为主,优势阴离子以HCO^-₃为主;水化学类型为Ca²⁺·Mg²⁺-HCO^-₃型。(2)流域内氢氧同位素具有季节变化特征,表现为雨季高、旱季低;流域沿程有着复杂的转换关系,池武溪上游以地下水补给地表水为主,池武溪中游至下游地表水与地下水交替补给。(3)流域氘盈余值呈现出旱季低雨季高的季节差异,在水-岩作用的影响下与当地大气降水的氘盈余值变化特征相反,而且水-岩作用强烈的区域与流域洞穴密集分布的特点相对应。