Isotopic discrimination of zinc in higher plants

* The extent of isotopic discrimination of transition metals in biological processes is poorly understood but potentially has important applications in plant and biogeochemical studies. * Using multicollector inductively coupled plasma (ICP) mass spectrometry, we measured isotopic fractionation of zinc (Zn) during uptake from nutrient solutions by rice (Oryza sativa), lettuce (Lactuca sativa) and tomato (Lycopersicon esculentum) plants. * For all three species, the roots showed a similar extent of heavy Zn enrichment relative to the nutrient solution, probably reflecting preferential adsorption on external root surfaces. By contrast, a plant-species specific enrichment of the light Zn isotope occurred in the shoots, indicative of a biological, membrane-transport controlled uptake into plant cells. The extent of the fractionation in the shoots further depended on the Zn speciation in the nutrient solution. * The observed isotopic depletion in heavy Zn from root to shoot (-0.13 to -0.26 per atomic mass unit) is equivalent to roughly a quarter of the total reported terrestrial variability of Zn isotopic compositions (c. 0.84 per atomic mass unit). Plant uptake therefore represents an important source of isotopic variation in biogeochemical cycling of Zn.     

Temporal and spatial variations in the oxygen-18 content of leaf water in different plant species

Temporal variations in the δ¹⁸ oxygen (δ¹⁸O) content of water transpired by leaves during a simulated diurnal cycle fluctuated around the δ¹⁸O content of the source water. Reconstructed variations in the δ¹⁸O values of leaf water differed markedly from those predicted by conventional models. Even when transpiring leaves were maintained under constant conditions for at least 3 h, strict isotopic steady-state conditions of leaf water (equality of the ¹⁸O/¹⁶O ratios in the input and transpired water) were rarely attained in a variety of plant species (Citrus reticu-lata, Citrus paradisi, Gossypium hirsutum, Helianthus annuns, Musa musaceae and Nicotinia tabacum). Isotopic analysis of water transpired by leaves indicated that leaves approach the isotopic steady state in two stages. The first stage takes 10 to 35 min (with a rate of change of about 3–3%h^?1), while in the second stage further approach to the isotopic steady state is asymptotic (with a rate of change of about 0–4% h^?1), and under conditions of low transpiration leaves can last for many hours. Substantial spatial isotopic heterogeneity was maintained even when leaves were at or near isotopic steady state. An underlying pattern in this isotopic heterogeneity is often discerned with increasing ¹⁸O/¹⁶O ratios from base to tip, and from the centre to the edges of the leaves. It is also shown that tissue water along these spatial isotopic gradients, as well as the average leaf water, can have ¹⁸O/¹⁶O ratios both lower and higher than those predicted by the conventional Craig and Gordon model. We concluded, first, that at any given time during the diurnal cycle of relative humidity the attainment of an isotopic steady state in leaf water cannot be assumed a priori and, secondly, that the isotopic enrichment pattern of leaf water reflects gradual enrichment along the water-flow pathway (e.g. as in a string of pools), rather than a single-step enrichment from source water, as is normally assumed.     

High-precision iron isotope analysis of whole blood,erythrocytes, and serum in adults

BackgroundIron isotopic composition serves as a biological indicator of Fe metabolism in humans. In the process of Fe metabolism, essential carriers of Fe circulate in the blood and pass through storage organs and intestinal absorptive tissues. This study aimed to establish an analytical method for high-precision Fe isotopic measurement, investigate Fe concentration and isotopic composition in different parts of whole blood, and explore the potential of Fe isotopic composition as an indicator for Fe status within individuals.Analytical methodsA total of 23 clinically healthy Taiwanese adults of Han descent were enrolled randomly and Fe isotopic compositions of their whole blood, erythrocytes, and serum were measured. The Fe isotopic analysis was performed by Neptune Plus multiple-collector inductively coupled plasma mass spectrometry with double-spike technique. The precision and reproducibility of the Fe isotopic analysis were monitored by international biological and geological reference materials.Main findingsHigh-precision Fe isotopic measurements were achieved alongside with high consistency in the isotopic data for well-characterized reference materials. The Fe isotopic signatures of whole blood and erythrocytes were resolvable from that of serum, where both whole blood and erythrocytes contained significantly lighter Fe isotopic compositions compared to the case of serum (P = 0.0296 and P = 0.0004, respectively). The δ^56/54Fe value of the serum sample was 0.2‰ heavier on an average than those of whole blood or erythrocytes. This isotopic fractionation observed in different parts of whole blood may indicate redox processes involved in Fe cycling, e.g. erythrocyte production and Fe transportation. Moreover, the δ^56/54Fe values of whole blood and serum significantly correlated with the hemoglobin level (P = 0.0126 and P = 0.0020, respectively), erythrocyte count (P = 0.0014 and P = 0.0005, respectively), and Mentzer index (P = 0.0055 and P = 0.0011, respectively), suggesting the Fe isotopic composition as an indicator of functional Fe status in healthy adults. The relationships between blood Fe isotopic compositions and relevant biodemographic variables were also examined. While the average Fe concentration of whole blood was significantly higher in males than in females (P = 0.0028), females exhibited a heavier Fe isotopic composition compared to that of males in whole blood (P = 0.0010) and serum (P < 0.0001). A significantly inverse correlation of the whole blood δ^56/54Fe value with body mass index of individuals (P = 0.0095) was also observed.ConclusionThe results presented herein reveal that blood Fe isotopic signature is consequentially linked to baseline erythrocyte parameters in individuals and is significantly affected by the gender and body mass index in the adult population. These findings support the role of Fe isotopic composition as an indicator for the variance of Fe metabolism among adult individuals and populations and warrant further study to elucidate the underlying mechanisms.     

The influence of climate and habitat on stable isotope signatures and the isotopic niche of nestling White‐headed Woodpeckers (Dryobates albolarvatus)

The majority of landbird species feed their nestlings arthropods and variation in arthropod populations can impact reproductive outcomes in these species. Arthropod populations in turn are influenced by climate because temperature affects survival and reproduction, and larval development. Thus, climate factors have the potential to influence many bird species during their reproductive phases. In this study, we assessed climate factors that impact the diet of nestling White‐headed Woodpecker (Dryobates albolarvatus), an at‐risk keystone species in much of its range in western North America. To do this, we measured stable isotope signatures (δ¹³C and δ¹⁵N) in 152 nestlings across six years and linked variation in isotopic values to winter (December–February) and spring (June) precipitation and temperature using mixed effects models. We also explored habitat factors that may impact δ¹³C and δ¹⁵N and the relationship between δ¹⁵N and nest productivity. Last, we estimated isotopic niche width for nestlings in different watersheds and years using Bayesian standard ellipses, which allowed us to compare dietary niche width and overlap. We found that colder winter temperatures were associated with an increase in δ¹⁵N and δ¹⁵N levels had a weak positive relationship with nest productivity. We also found that sites with a more diverse tree community were associated with a broader isotopic niche width in nestlings. Our findings suggest that nestling diet is affected by climate, and under future warming climate scenarios, White‐headed Woodpecker nestling diet may shift in favor of lower trophic level prey (prey with lower δ¹⁵N levels). The impact of such changes on woodpecker populations merits further study.     

Role of stable isotopes in life--testing isotopic resonance hypothesis

Stable isotopes of most important biological elements, such as C, H, N and O, affect living organisms. In rapidly growing species, deuterium and to a lesser extent other heavy isotopes reduce the growth rate. At least for deuterium it is known that its depletion also negatively impacts the speed of biological processes. As a rule, living organisms "resist" changes in their isotopic environment, preferring natural isotopic abundances. This preference could be due to evolutionary optimization; an additional effect could be due to the presence of the "isotopic resonance". The isotopic resonance phenomenon has been linked to the choice of earliest amino acids, and thus affected the evolution of genetic code. To test the isotopic resonance hypothesis, literature data were analyzed against quantitative and qualitative predictions of the hypothesis. Four studies provided five independent datasets, each in very good quantitative agreement with the predictions. Thus, the isotopic resonance hypothesis is no longer simply plausible; it can now be deemed likely. Additional testing is needed, however, before full acceptance of this hypothesis.     

Using stable isotopes to trace long-distance dispersal in birds and other taxa

The study of long‐distance dispersal (LDD) in animals may be advanced by recent applications of stable isotope analyses designed to track migratory organisms and to link populations throughout their annual cycle. This approach depends on there being enough isotopic difference in tissues among potential source populations such that individuals can be unequivocally assigned to their source. The isotopic mapping of such populations will be feasible only for species occurring in relatively few disjunct populations. However, the identification of isotopic outliers within known populations will be an extremely useful first step in the forensic application of stable isotopes to identify dispersal in general, and LDD in particular. The use of deuterium isotope analysis (δD) of tissues that can be assigned to its source (e.g. feather moult or its hair growth location) has provided a recent breakthrough in our ability to associate individuals with geographical origins at continental scales. The combination of this stable isotope with others and the ultimate combination of a variety of techniques, including the measurement of trace elements and molecular genetics markers, will undoubtedly improve resolution. The isotopic cataloguing of known history (i.e. philopatric) individuals within populations will be an important step in applying isotope techniques to evaluating LDD in any species. For aquatic insects, the isotopic marking of large numbers of individuals is possible through isotopic enrichment of local food webs using labelled compounds.     

An unbiased method to estimate individual specialisation from multi‐tissue isotopic data

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A thermodynamic theory of microbial growth

Our ability to model the growth of microbes only relies on empirical laws, fundamentally restricting our understanding and predictive capacity in many environmental systems. In particular, the link between energy balances and growth dynamics is still not understood. Here we demonstrate a microbial growth equation relying on an explicit theoretical ground sustained by Boltzmann statistics, thus establishing a relationship between microbial growth rate and available energy. The validity of our equation was then questioned by analyzing the microbial isotopic fractionation phenomenon, which can be viewed as a kinetic consequence of the differences in energy contents of isotopic isomers used for growth. We illustrate how the associated theoretical predictions are actually consistent with recent experimental evidences. Our work links microbial population dynamics to the thermodynamic driving forces of the ecosystem, which opens the door to many biotechnological and ecological developments.     

同位素示踪技术在光合作用研究中的应用

利用同位素示踪技术可以掌握物质在化学反应中运行和变化情况。试论述同位素示踪技术在研究光合作用中的多种应用：提示光合作用中几种元素的转变方向;判断光合作用的反应场所和反应条件;推断光合作用的反应过程;检验产物的运输方向;研究光合作用与呼吸作用的关系。     

铵盐和硝酸盐稳定同位素丰度测定方法及其应用案例

综述了过去几十年来铵盐和硝酸盐稳定同位素丰度测定方法的历史发展变化,分析了各种方法的优缺点,并对新方法作了介绍和推荐.目前铵盐稳定同位素丰度的最新测定方法为次溴酸盐氧化结合羟胺还原法,硝酸盐氮氧同位素丰度主流的测定方法为反硝化细菌法和镉粉叠氮酸还原化学法.这些方法的主要共同特点是以N₂O为分析物,分析精度高,对样品的含氮量需求小,一般只需要10～60 nmol N,适用于低浓度样品.新方法的建立对于国内外开展氮素循环研究将起到极大的推动作用.     

The isotopic composition and insect content of diet predict tissue isotopic values in a South American passerine assemblage

We analyzed the carbon and nitrogen isotopic values of the muscle, liver, and crop contents (“diet”) of 132 individuals of 16 species of Chilean birds. The nitrogen content of diet was tightly correlated with the fraction of gut contents represented by insects relative to plant material. The carbon and nitrogen isotopic values of diet, liver, and muscle were all linearly correlated, implying high temporal consistency in the isotopic value of the diet of these birds. However, δ¹⁵N was not significantly related with the percentage of insects in diet. These results cast doubt on the applicability of the use of ¹⁵N enrichment to diagnose trophic level in, at least some, terrestrial ecosystems. However, the residuals of the relationship relating the isotopic value of bird tissues with those of their diet were weakly negatively correlated with insect intake. We hypothesize that this negative correlation stems from the higher quality of protein found in insects relative to that of plant materials. Finally, our data corroborated a perplexing and controversial negative relationship between tissue to diet isotopic discrimination and the isotopic value of diet. We suggest that this relationship is an example of the commonly observed regression to the mean effect that plagues many scientific studies.     

Patterns of isotopic disequilibria in azooxanthellate coral skeletons

A specimen of Desmophyllum cristagalli, an azooxanthellate (non-photosynthetic) coral was intensively and systematically sampled on all interior and exterior coeval surfaces. Even though the coral grew at an almost-constant temperature of about 2.5 °C, ¹⁸O varied by almost 3 and was up to 3.25 depleted with respect to aragonite–seawater oxygen isotope equilibrium. Contour maps of ¹⁸O show that, although portions of the skeleton approached equilibrium, the location of those areas were unpredictable and were not associated with any readily identifiable characteristics, such as colour, texture or crystalline structure changes. The use of regression lines and intercepts will give the mean temperature experienced by individual corals (Smith et al., 2000, Palaios 15: 25), but the prospect of documenting temperature changes over the lifetime of an individual coral remains problematical. Because of the large and seemingly random degree of isotopic disequilibrium, several isotopic values from coeval skeletal material must be obtained for the determination of a single temperature. Although azooxanthellate corals have been shown to have growth banding, analogous to reef corals, the layers are thin and difficult to see with the naked eye, uneven and often discontinuous, rendering sampling for a `time series' impossible at present. Reasons for the degree of variation in the isotopic patterns remain unclear.     

Stable isotope analysis as a tool to monitor dietary trends in little penguins Eudyptula minor

Long‐term dietary monitoring of seabirds can be used to relate population fluctuations to at‐sea events. Stomach flushing is a conventional dietary monitoring technique, but has a number of disadvantages. Stable isotope analysis (SIA) is a less invasive method that provides unbiased dietary information over a longer period. We evaluated stable isotope analysis as a potential tool for monitoring long‐term little penguin Eudyptula minor diet. We determined diet composition during the chick feeding stage using stomach flushing and SIA at three separate colonies, using spatial variation in diet as a surrogate for potential temporal variation. Bayesian isotopic mixing models were generated for blood and feathers to evaluate their ability to discriminate broad‐scale (fish, squid, crustaceans) and fine‐scale (individual prey species) diet composition. Differences in stable carbon and nitrogen isotope ratios were found between colonies: broad‐scale isotopic mixing models predicted different proportional contributions of broad taxa (fish, cephalopod, crustacean) to diet than was indicated by stomach samples, reflecting the bias incurred by one‐off stomach contents analysis. Fine‐scale isotopic mixing models predicted proportional contributions of prey items with less certainty. Blood isotopic mixing models had narrower confidence intervals than models for feathers, but trends in δ¹⁵N for feathers mirrored those for blood. Our results suggest that relying on stomach contents analysis to detect shifts in prey consumption in little penguins could be very misleading, resulting in a less‐than‐complete idea of total prey consumption. SIA of little penguin tissues could be used to monitor dietary shifts across dissimilar taxa that may affect population numbers, but would fail to detect shifts between fish species.     

Temporal variation in trophic relationships among three congeneric penguin species breeding in sympatry

Penguins are a monophyletic group in which many species are found breeding sympatrically, raising questions regarding how these species coexist successfully. Here, the isotopic niche of three sympatric pygoscelid penguin species was investigated at Powell Island, South Orkney Islands, during two breeding seasons (austral summers 2013–2014 and 2015–2016). Measurements of carbon (δ¹³C) and nitrogen (δ¹⁵N) stable isotope ratios were obtained from blood (adults) or feather (chicks) samples collected from Adélie Pygoscelis adeliae, chinstrap P. antarctica, and gentoo P. papua penguins. Isotopic niche regions (a proxy for the realized trophic niches) were computed to provide estimates of the trophic niche width of the studied species during the breeding season. The isotopic niche regions of adults of all three species were similar, but gentoo chicks had noticeably wider isotopic niches than the chicks of the other two species. Moderate to strong overlap in isotopic niche among species was found during each breeding season and for both age groups, suggesting that the potential for competition for shared food sources was similar during the two study years, although the actual level of competition could not be determined owing to the lack of data on resource abundance. Clear interannual shifts in isotopic niche were seen in all three species, though of lower amplitude for adult chinstrap penguins. These shifts were due to variation in carbon, but not nitrogen, isotopic ratios, which could indicate either a change in isotopic signature of their prey or a switch to an alternative food web. The main conclusions of this study are that (1) there is a partial overlap in the isotopic niches of these three congeneric species and that (2) they responded similarly to changes that likely occurred at the base of their food chain between the 2 years of the study.     

Tracing site‐specific isotopic signatures along a Blue Tit Cyanistes caeruleus food chain

Food chains culminating with temperate insectivorous passerines are well described, yet whether trophic webs can be site‐specific remains a largely unexplored question. In the case of site‐ or habitat‐specificity of food webs, stable isotope signatures of bird feathers may enable assignment of unmarked individuals to a site or a habitat of origin. We address this question in landscapes that include contrasting forest habitat patches with either deciduous Downy Oak Quercus humilis or evergreen Holm Oak Quercus ilex as dominant tree species. First, we examine the spatial variation across habitats and sites in the stable isotope ratios of carbon (δ¹³C) and nitrogen (δ¹⁵N) along the oak leaf–Tortrix moth Tortrix viridana caterpillar–Blue Tit Cyanistes caeruleus food chain. Secondly, we assess whether the isotopic signatures allow for correct assignment of individual birds to their site or habitat of origin. At the scale of the landscape, stable isotope values enabled identification of the different components of the Blue Tit food chain: from oak leaves to Blue Tit nestlings and yearling birds. However, isotopic signatures were site‐specific (i.e. geographical) more than habitat‐specific (i.e. deciduous vs. evergreen oaks). Discriminant analyses correctly assigned 85% of nestlings and 83% of resident yearling birds, indicating a pronounced effect of site on Blue Tit feather isotopic signatures. We thereby demonstrate that isotopes reflect a stronger association of locally born birds to the local features of their habitat than that of un‐ringed yearling birds, whose plumage may have grown while in a wider geographical area. This study provides evidence of site‐specific isotopic signatures from oak leaves to Blue Tit feathers at a fine spatial scale.     

The application of δ¹⁸O and δD for understanding water pools and fluxes in a Typha marsh

The δ¹⁸O and δD composition of water pools (leaf, root, standing water and soil water) and fluxes [transpiration (T), evaporation (E)] were used to understand ecohydrological processes in a managed Typha latifolia L. freshwater marsh. We observed isotopic steady‐state T and deep rooting in Typha. The isotopic mass balance of marsh standing water showed that E accounted for 3% of the total water loss, T accounted for 17% and subsurface drainage (D) accounted for the majority (80%). There was a vertical gradient in water vapour content and isotopic composition within and above the canopy sufficient for constructing an isotopic mass balance of water vapour during some sampling periods. During these periods, the proportion of T in evapotranspiration (T/ET) was between 56 ± 17% and 96 ± 67%, and the estimated error was relatively high (>37%) because of non‐local, background sources in vapour. Independent estimates of T/ET using eddy covariance measurements yielded similar mean values during the Typha growing season. The various T/ET estimates agreed that T was the dominant source of marsh vapour loss in the growing season. The isotopic mass balance of water vapour yielded reasonable results, but the mass balance of standing water provided more definitive estimates of water losses.     

生态系统光合与呼吸拆分的同位素理论、方法和应用进展

生态系统光合和呼吸是构成净生态系统CO₂交换量(NEE)的重要组分。涡度相关技术可直接观测生态系统NEE,并通过建立温度回归或光响应曲线等函数将NEE统计拆分为生态系统光合和呼吸,但是存在自相关和高估白天呼吸等问题。稳定同位素红外光谱技术的进步使高时间分辨率大气CO₂及其稳定碳同位素组成(δ¹³C)的连续观测成为可能,与涡度相关技术观测的NEE数据相结合,可实现昼夜和季节尺度生态系统光合和呼吸拆分。本文系统阐述了生态系统光合与呼吸的同位素通量拆分方法的基本理论与假设,阐述了同位素通量观测技术的发展及其应用进展,综述了同位素通量拆分理论解析生态系统光合与呼吸过程的新机制认识,最后总结并展望了同位素通量拆分理论的不确定性以及开展多种拆分方法综合比较的必要性。     

Rhizosphere carbon flow measurement and implications: from isotopes to reporter genes

Despite the fundamental importance of rhizosphere C-flow in managed and natural systems, reliable measurement/resolution of C-flow and assessment of its consequences have largely remained elusive to soil biologists. Techniques involving both radioactive (¹⁴C) and stable (¹³C) isotopes of carbon have made some progress in terms of studying rhizosphere C-flow. Pulse-chase techniques have been used effectively to study dynamics of C-transfer to the rhizosphere and rhizosphere microbial biomass. The information obtained through pulse-chase is strongly dependent on the chase period following the labelling event. Continuous labelling is primarily used to determine plant inputs to soil over an extended time period and includes all kinds of C input – from root turnover, root respiration, root exudation, production of mucilage, etc. One of the main constraints to both approaches is that distinguishing root from microbial respiration is difficult, if not impossible. ¹³C techniques have gone some way towards resolving this difficulty, although ¹³C signatures in the plant–soil system are not easy to interpret and detailed resolution of carbon flow through different components of the rhizosphere biomass is unlikely to be achieved in such an inherently `noisy' system. Recent developments in molecular biology now provide a new opportunity to resolve rhizosphere C-flow and its implications. Reporter gene systems where, for example, rhizobacteria are marked with lux and unstable gfp reporters, overcome the difficulty of distinguishing root and microbial C fluxes and complement the isotopic and more traditional approaches. Reporter systems have now begun to resolve the competitive C sink strengths of different components of the rhizosphere microbial community and assess how a rhizobacterial inoculum may change C-flow in applications such as disease control and rhizoremediation of contaminated land. Fusion of reporter genes to nutrient (N and P) starvation genes in rhizobacteria has also enabled in situ characterisation of nutrient depletion around the root and assessment of the impact of changes in C-flow (such as those induced by climate change) on nutrient depletion dynamics. The availability of an integrated approach involving isotopic, molecular biological and other techniques now offers an exciting new era where reliable measurement and resolution of rhizosphere C-flow (and its consequences) can contribute to our understanding of ecosystem function and to management of crop-microbe interactions.     

Methyl chloride isotopic signatures from Irish forest soils and a comparison between abiotic and biogenic methyl halide soil fluxes

Forest soils demonstrate in a microcosm the difficulties that are faced in quantifying methyl halide budgets. Carbon isotopic analyses have been proposed as a potential tool to address these concerns and in this study we have measured significant enrichment of the methyl chloride ¹³C/¹²C isotopic ratio (from ?40.2 ± 0.8‰ to ?33.4 ± 7.4‰) after 9 min chamber emplacement on local Irish forest soils. This enrichment occurred independent of direction of methyl chloride fluxes. Measurements from soil cores in a flow‐through system (FTS) are comparable with chamber‐based isotopic measurements and indicate that methyl chloride produced abiotically from organic soil horizons has an isotopic ¹³C signature of ?53 ± 49‰, significantly less depleted than previously reported. Average net methyl chloride, methyl bromide and methyl iodide fluxes from soils (77.8 ± 2.1, 1.25 ± 3.63 and 0.35 ± 2.00 μg MeX m^?2 day^?1, respectively) are in line with previously reported values; however, a better understanding of spatial and temporal variability is needed for budget quantification. Methyl halide fluxes from FTS soil cores demonstrate that, on a per gram basis, most consumption occurs through biologically driven processes in the O horizon, with progressively smaller contributions in deeper horizons. Sporadic biogenic production was observed in shallow soil horizons only. Abiotic production was at most one‐tenth the net biological reaction rate in the O horizon and did not appear to be significantly different from zero in lower horizons. Modelled emissions based upon observed and reported rates for production, consumption and diffusion within the soil atmosphere system are unable to replicate all observed isotopic signatures from chamber fluxes.     

The isotopic composition of anthropogenic boron and its potential impact on the environment

The present study investigates the isotopic composition of anthropogenic boron (B) and its potential affects on the environment. The isotopic ratios of B in synthetic products from the main ores in the world have been measured by negative thermal ionization mass spectrometry. The data show that the isotopic compositions of Na-borate products and washing powders overlap with those of natural Na-borate minerals. In contrast, the¹¹B/¹⁰B ratios of synthetic Ca-borate and Na/Ca borate products are significantly lower (by 15 permil) and overlap with those of the natural Ca-borate minerals. Consequently, the original isotopic signature of natural borate minerals is not modified during the manufacturing process of synthetic products. The B isotopic composition of domestic wastewater from Israel and Riverside, California suggests that B in sewage is derived from Na-borate components used in detergents. Since B, like other inorganic ions, is not removed during conventional sewage treatment, it accumulates in domestic wastewater. Although the B concentration in pristine groundwaters is generally low (<0.05 mg/L), contaminant sources (e.g., wastewater) are relatively enriched in B (0.5–1 mg/L). The isotopically distinguished signature of borate compounds is used to trace groundwater contamination.