Dual Isotope Approach Research Articles

Silicon and nitrogen cycling in the upwelling area off Peru: A dual isotope approach

We present a comparison of the dissolved stable isotope composition of silicate (δ30Si(OH)4) and nitrate (δ15 inline image) to investigate the biogeochemical processes controlling nutrient cycling in the upwelling area off Peru, where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Besides strong upwelling of nutrient rich waters mainly favoring diatom growth, an anticyclonic eddy influenced the study area. We observe a tight coupling between the silicon (Si) and nitrogen (N) cycles in the study area. Waters on the shelf showed high Si(OH)4 concentrations accompanied by diminished inline image concentration as a consequence of intense remineralization, high Si fluxes from the shelf sediments, and N-loss processes such as anammox/denitrification within the OMZ. Correspondingly, the surface waters show low δ30Si(OH)4 values (+2‰) due to low Si utilization but relatively high δ15 inline image (+13‰) values due to upwelling of waters influenced by N-loss processes. In contrast, as a consequence of the deepening of the thermocline in the eddy center, a pronounced Si(OH)4 depletion led to the highest δ30Si(OH)4 values (+3.7‰) accompanied by high δ15 inline image values (+16‰). In the eddy center, high inline image: Si(OH)4 ratios favored the growth of non-siliceous organisms (Synechococcus). Our data show that upwelling processes and the presence of eddies play important roles controlling the nutrient cycles and therefore also exert a major influence on the phytoplankton communities in the Peruvian Upwelling. Our findings also show that the combined approach of δ30Si(OH)4 and δ15 inline image can improve our understanding of paleo records as it can help to disentangle utilization and N-loss processes.

Effects of mistletoe removal on growth, N and C reserves, and carbon and oxygen isotope composition in Scots pine hosts.

Most mistletoes are xylem-tapping hemiparasites, which derive their resources from the host's xylem solution. Thus, they affect the host's water relations and resource balance. To understand the physiological mechanisms underlying the mistletoe-host relationship, we experimentally removed Viscum album ssp. austriacum (Wiesb.) Vollmann from adult Pinus sylvestris L. host trees growing in a Swiss dry valley. We analyzed the effects of mistletoe removal over time on host tree growth and on concentrations of nonstructural carbohydrates (NSC) and nitrogen (N) in needles, fine roots and sapwood. In addition, we assessed the δ(13)C and δ(18)O in host tree rings. After mistletoe removal, δ(13)C did not change in newly produced tree rings compared with tree rings in control trees (still infected with mistletoe), but δ(18)O values increased. This pattern might be interpreted as a decrease in assimilation (A) and stomatal conductance (gs), but in our study, it most likely points to an inadequacy of the dual isotope approach. Instead, we interpret the unchanged δ(13)C in tree rings upon mistletoe removal as a balanced increase in A and gs that resulted in a constant intrinsic water use efficiency (defined as A/gs). Needle area-based concentrations of N, soluble sugars and NSC, as well as needle length, single needle area, tree ring width and shoot growth, were significantly higher in trees from which mistletoe was removed than in control trees. This finding suggests that mistletoe removal results in increased N availability and carbon gain, which in turn leads to increased growth rates of the hosts. Hence, in areas where mistletoe is common and the population is large, mistletoe management (e.g., removal) may be needed to improve the host vigor, growth rate and productivity, especially for relatively small trees and crop trees in xeric growth conditions.

Interpretation of anthropogenic impacts (agriculture and urbanization) on tropical deltaic river network through the spatio-temporal variation of stable (N, O) isotopes of NO−3

ABSTRACTFor the first time, the dual isotope approach was applied to trace the sources of impacts and to identify the governing biogeochemical processes in a river network in the tropical deltaic region of the Red River (Vietnam). Our long term surveys concluded that water in this river network was severely impacted by anthropogenic activities. Analysis has shown strong spatio-temporal variation of nitrate isotopes; ranges of δ15N– and δ18O– were from −5 to 15 ‰ and from −10 to 10 ‰, respectively. Average values of δ15N– and δ18O– in the dry season, when fertilizer is applied, were 3.54 and 3.15 ‰, respectively. In the rainy season, the values changed to 6.41 and −2.23 ‰, respectively. Denitrification and biological assimilation were active throughout the year, but were especially enhanced during fertilization time. Mineralization of domestic organic matter and consequent nitrification of mineralized were the dominant processes, particularly during the rainy period.

Isotopic composition (δ18O and δD) of the shallow groundwater in the Poyang Lake basin

The article is focused on the identification of evaporation and other natural processes which affect the isotopic composition of shallow groundwater in the Poyang Lake basin, such as water-rock interaction and mixing of the shallow groundwater and surface water. For this purpose the dual isotope approach (δD–H2O and δ18O–H2O) was used. The samples were collected from domestic wells around the Poyang Lake. The value of δD obtained for the shallow groundwater ranges from -21.5 to -42.6∘/∘∘. The δ18O value varies from -3.5 to -7.1∘/∘∘. It was found that the shallow groundwater of the Poyang Lake catchment is of meteoric origin. The influence of evaporation on the isotopic composition of shallow groundwater is negligible and observed mainly during the dry season. The deviation from the local meteoric water line, especially during the rainy season, may be explained by the processes in the water-rock system, but this issue is required further research.

Temperature signal instability of tree-ring δ13C chronology in the northeastern Qinghai–Tibetan Plateau

Tree ring δ13C as a climate proxy is widely used for palaeoclimate research, however, its temporal stability response to the climate change remains unclear under more than one limited factors on tree growth. Here, we used a millennium tree-ring δ13C chronology combining two annual-resolution δ13C chronologies since 1800 from long-lived Qilian juniper (Sabina przewalskii) to assess its instability of the climate signal in the northeastern Qinghai–Tibetan Plateau. Tree-ring δ13C chronologies were strongly correlated with the regional mean April to August temperature from 1956 to 2008, but the associations were absent within the period 1901 to 1955 values in the CRU TS dataset. Comparison of the millennium-long δ13C series with reconstructed Asian temperatures also demonstrated that the δ13C chronology exhibited climate signal temporal instability. Substantial oscillations were revealed using a frequency-dependent analysis and 51-year running correlation analysis from the millennium-long tree-ring δ13C and δ18O series. Dual-isotope approach indicated that stomatal limitations created a statistical significant positive correlation between tree-ring δ13C and δ18O, but photosynthetic rate may be dominant when the correlations were not significant. Our results suggest that tree-ring δ13C series in the northeastern Qinghai–Tibetan Plateau is responded instability to temperature variations in the past 1000years.

Procedure for rapid determination of δ15N and δ18O values of nitrate: development and application to an irrigated rice paddy watershed.

The dual isotope approach using the stable isotope ratios of nitrate nitrogen (δ(15)N(NO3)) and oxygen (δ(18)O(NO3)) is a strong tool for identifying the history of nitrate in various environments. Basically, a rapid procedure for determining δ(15)N(NO3) and δ(18)O(NO3) values is required to analyze many more samples quickly and thus save on the operational costs of isotope-ratio mass spectrometry (IRMS). We developed a new rapid procedure to save time by pre-treating consecutive samples of nitrous oxide microbially converted from nitrate before IRMS determination. By controlling two six-port valves of the pre-treatment system separately, IRMS determination of the current sample and backflush during the next sample pre-treatment period could be conducted simultaneously. A set of 89 samples was analyzed precisely during a 25-h continuous run (17 min per sample), giving the fastest reported processing time, and simultaneously reducing liquid nitrogen and carrier helium gas consumption by 35%. Application of the procedure to an irrigated rice paddy watershed suggested that nitrate concentrations in river waters decreased in a downstream direction, mainly because of the mixing of nitrate from different sources, without distinct evidence of denitrification. Our procedure should help with more detailed studies of nitrate formation processes in watersheds.

Use of dual carbon–chlorine isotope analysis to assess the degradation pathways of 1,1,1-trichloroethane in groundwater

Compound-specific isotope analysis (CSIA) is a powerful tool to track contaminant fate in groundwater. However, the application of CSIA to chlorinated ethanes has received little attention so far. These compounds are toxic and prevalent groundwater contaminants of environmental concern. The high susceptibility of chlorinated ethanes like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in the subsurface. In this study, the use of a dual C–Cl isotope approach to identify the active degradation pathways of 1,1,1-TCA is evaluated for the first time in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. The reaction-specific dual carbon–chlorine (C–Cl) isotope trends determined in a recent laboratory study illustrated the potential of a dual isotope approach to identify contaminant degradation pathways of 1,1,1-TCA. Compared to the dual isotope slopes (Δδ13C/Δδ37Cl) previously determined in the laboratory for dehydrohalogenation/hydrolysis (DH/HY, 0.33 ± 0.04) and oxidation by persulfate (∞), the slope determined from field samples (0.6 ± 0.2, r2 = 0.75) is closer to the one observed for DH/HY, pointing to DH/HY as the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA is the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C–Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field.

Improvement of water and light availability after thinning at a xeric site: which matters more? A dual isotope approach.

Thinning fosters individual tree growth by increasing the availability of water, light and nutrients. At sites where water rather than light is limiting, thinning also enhances soil evaporation and might not be beneficial. Detailed knowledge of the short- to long-term physiological response underlying the growth responses to thinning is crucial for the management of forests already suffering from recurrent drought-induced dieback. We applied a dual isotope approach together with mechanistic isotope models to study the physiological processes underlying long-term growth enhancement of heavily thinned Pinus sylvestris in a xeric forest in Switzerland. This approach allowed us to identify and disentangle thinning-induced changes in stomatal conductance and assimilation rate. At our xeric study site, the increase in stomatal conductance far outweighed the increase in assimilation, implying that growth release in heavily thinned trees is primarily driven by enhanced water availability rather than increased light availability. We conclude that in forests with relatively isohydric species (drought avoiders) that are growing close to their physiological limits, thinning is recommended to maintain a less negative water balance and thus foster tree growth, and ultimately the survival of forest trees under drought.

Identification of nitrate sources in groundwater and potential impact on drinking water reservoir (Goczałkowice reservoir, Poland)

Goczałkowice dammed reservoir (area – 26 km2) is a strategic object for flood control in the Upper Vistula River catchment and one of the most important source of drinking water in the Upper Silesian Industrial Region (Southern Poland). Main aims of the investigation were identification of sources of nitrate and assessment of their significance in potential risk to groundwater quality.In the catchment area monitoring network of 22 piezometers, included 14 nested, have been installed. The significant spatial and seasonal differences in chemical composition between northern and southern part of the catchment were indicated based on the groundwater sampling conducted twice – in autumn 2011 and spring 2012. Maximum observed concentrations of nitrate were identified in northern part of the study area 255 mg/L as a results of inappropriate sewage management and agriculture activity.Results, based on the combines multi-scale hydrogeological and hydrochemical field studies, groundwater flow and transport modelling, dual stable isotope approach and geochemical modelling indicate mainly agriculture and inappropriate sewage water management as a sources of NO3− contamination of groundwater which moreover is affected by geochemical processes. In general, contaminated groundwater does not impact surface water quality. However, due to high concentration of nitrate in northern part a continues measurements of nitrogen compounds should be continued and used for reducing uncertainty of the predictive scenarios of the mass transport modelling in the study area.

A dual-isotope approach to allow conclusive partitioning between three sources.

Stable isotopes have proved to be a transformative tool; their application to distinguish between two sources in a mixture has been a cornerstone of biogeochemical research. However, quantitatively partitioning systems using two stable isotopes (for example, 13C and 12C) has been largely limited to only two sources, and systems of interest often have more than two components, with interactive effects. Here we introduce a dual-isotope approach to allow conclusive partitioning between three sources, using only two stable isotopes. We demonstrate this approach by partitioning soil CO2 emissions derived from microbial mineralization of soil organic carbon (SOC), added pyrogenic organic matter (PyOM) and root respiration. We find that SOC mineralization in the presence of roots is 23% higher (P<0.05) when PyOM is also present. Being able to discern three sources with two isotopes will be of great value not only in biogeochemical research, but may also expand hitherto untapped methodologies in diverse fields.

Decision-tree-model identification of nitrate pollution activities in groundwater: A combination of a dual isotope approach and chemical ions

To develop management practices for agricultural crops to protect against NO3− contamination in groundwater, dominant pollution activities require reliable classification. In this study, we (1) classified potential NO3− pollution activities via an unsupervised learning algorithm based on δ15N- and δ18O-NO3− and physico-chemical properties of groundwater at 55 sampling locations; and (2) determined which water quality parameters could be used to identify the sources of NO3− contamination via a decision tree model. When a combination of δ15N-, δ18O-NO3− and physico-chemical properties of groundwater was used as an input for the k-means clustering algorithm, it allowed for a reliable clustering of the 55 sampling locations into 4 corresponding agricultural activities: well irrigated agriculture (28 sampling locations), sewage irrigated agriculture (16 sampling locations), a combination of sewage irrigated agriculture, farm and industry (5 sampling locations) and a combination of well irrigated agriculture and farm (6 sampling locations). A decision tree model with 97.5% classification success was developed based on SO42− and Cl− variables. The NO3− and the δ15N- and δ18O-NO3− variables demonstrated limitation in developing a decision tree model as multiple N sources and fractionation processes both resulted in difficulties of discriminating NO3− concentrations and isotopic values. Although only the SO42− and Cl− were selected as important discriminating variables, concentration data alone could not identify the specific NO3− sources responsible for groundwater contamination. This is a result of comprehensive analysis. To further reduce NO3− contamination, an integrated approach should be set-up by combining N and O isotopes of NO3− with land-uses and physico-chemical properties, especially in areas with complex agricultural activities.

Identifying the sources of nitrate contamination of groundwater in an agricultural area (Haean basin, Korea) using isotope and microbial community analyses

An integrated study based on hydrogeochemical, microbiological and dual isotopic approaches for nitrate and sulfate was conducted to elucidate sources and biogeochemical reactions governing groundwater contaminants in different seasons and under different land use in a basin of Korea. The land use in the study area is comprised of forests (58.0%), vegetable fields (27.6%), rice paddy fields (11.4%) and others (3.0%). The concentrations of NO3–N and SO42− in groundwater in vegetable fields were highest with 4.2–15.2mgL−1 and 1.6–19.7mgL−1 respectively, whereas under paddy fields NO3–N concentrations ranged from 0 to 10.7mgL−1 and sulfate concentrations were ~15mgL−1. Groundwater with high NO3–N concentrations of >10mgL−1 had δ15N–NO3− values ranging from 5.2 to 5.9‰ and δ18O values of nitrate between 2.7 and 4.6‰ suggesting that the nitrate was mineralized from soil organic matter that was amended by fertilizer additions. Elevated concentrations of SO42− with δ34S–SO42− values between 1 and 6‰ in aquifers in vegetable fields indicated that a mixture of sulfate from atmospheric deposition, mineralization of soil organic matter and from synthetic fertilizers is the source of groundwater sulfate. Elevated δ18O–NO3− and δ18O–SO42− values in samples collected from the paddy fields indicated that denitrification and bacterial sulfate reduction are actively occurring removing sulfate and nitrate from the groundwater. This was supported by high occurrences of denitrifying and sulfate reducing bacteria in groundwater of the paddy fields as evidenced by 16S rRNA pyrosequencing analysis. This study shows that dual isotope techniques combined with microbial data can be a powerful tool for identification of sources and microbial processes affecting NO3− and SO42− in groundwater in areas with intensive agricultural land use.

Isotopic identification of soil and permafrost nitrate sources in an Arctic tundra ecosystem

AbstractThe nitrate (NO3−) dual isotope approach was applied to snowmelt, tundra active layer pore waters, and underlying permafrost in Barrow, Alaska, USA, to distinguish between NO3− derived from atmospheric deposition versus that derived from microbial nitrification. Snowmelt had an atmospheric NO3− signal with δ15N averaging −4.8 ± 1.0‰ (standard error of the mean) and δ18O averaging 70.2 ± 1.7‰. In active layer pore waters, NO3− primarily occurred at concentrations suitable for isotopic analysis in the relatively dry and oxic centers of high‐centered polygons. The average δ15N and δ18O of NO3− from high‐centered polygons were 0.5 ± 1.1‰ and −4.1 ± 0.6‰, respectively. When compared to the δ15N of reduced nitrogen (N) sources, and the δ18O of soil pore waters, it was evident that NO3− in high‐centered polygons was primarily from microbial nitrification. Permafrost NO3− had δ15N ranging from approximately −6‰ to 10‰, similar to atmospheric and microbial NO3−, and highly variable δ18O ranging from approximately −2‰ to 38‰. Permafrost ice wedges contained a significant atmospheric component of NO3−, while permafrost textural ice contained a greater proportion of microbially derived NO3−. Large‐scale permafrost thaw in this environment would release NO3− with a δ18O signature intermediate to that of atmospheric and microbial NO3. Consequently, while atmospheric and microbial sources can be readily distinguished by the NO3− dual isotope technique in tundra environments, attribution of NO3− from thawing permafrost will not be straightforward. The NO3− isotopic signature, however, appears useful in identifying NO3− sources in extant permafrost ice.

Assessing sources of nitrate contamination in the Shiraz urban aquifer (Iran) using the δ15N and δ18O dual-isotope approach

Nitrate () is one of the major threats to the quality of the drinking water taken from the Shiraz aquifer. This aquifer undergoes high anthropogenic pressures from multiple local urban (including uncontrolled sewage systems), agricultural and industrial activities, resulting in concentrations as high as 149 mg L−1, well above the 50 mg L−1 guideline defined by the World Health Organisation. We coupled here classical chemical and dual isotope (δ15N and δ18O of ) approaches trying to characterize sources and potential processes controlling the budget of this pollutant. Chemical data indicate that nitrate in this aquifer is explained by distinct end-members: while mineral fertilizers isotopically show to have no impact, our isotope approach identifies natural soil nitrification and organic (manure and/or septic waste) as the two main contributors. Isotope data suggest that natural denitrification may occur within the aquifer, but this conclusion is not supported by the study of other chemical parameters.

Using dual isotopes to evaluate sources and transformations of nitrate in the West Lake watershed, eastern China

The West Lake is a World Heritage site in the West Lake watershed in eastern China. In this study, the hydrogeological and dual isotopic approaches were integrated to evaluate the seasonal and spatial variations of nitrate (NO3−) in the West Lake watershed, and to characterize NO3− sources and transformations. The results revealed that the geochemical facies of the water samples were dominated by Ca2++Na+–HCO3−+SO42− in the surface water and transfer water, Ca2++Na+–HCO3− and Ca2++Na+–SO42− in the groundwater, which most likely reflect natural reactions and anthropogenic inputs. About 13% of the groundwater samples containing NO3− exceeded the World Health Organization (WHO) standard of 10mgNL−1. NO3− was the dominant form of total nitrogen (TN) and was the main surface water contaminant in the West Lake watershed. The δ15NNO3 and δ18ONO3 values indicated that the dominant NO3− sources in surface water were soil nitrogen (soil N) and chemical fertilizers, while the main NO3− sources in groundwater were soil N from the forest, chemical fertilizers and manure in the tea garden, domestic sewage from the small, old residential area in the forest as well as urban areas. The distribution of NO3− in groundwater was strongly influenced by land use. Results also suggest that there was significant nitrification in surface water and groundwater in the West Lake watershed, and that there were also denitrification processes in groundwater. The annual net fluxes of TN, NO3−, and NH4+ into the West Lake were 2.0×104, 4.0×103, and 1.31×104kg as N, respectively.

Assessment of the sources of nitrate in the Chaohu Lake, China, using a nitrogen and oxygen isotopic approach

Nitrate pollution is an increasingly serious problem in Chaohu Lake, China, with the rapid development of urbanization and industrialization surrounding the lake. The dual isotopic approach was employed to determine the sources of nitrate. Thirty-five and thirty-one water samples were collected in summer and winter, respectively. The concentrations of nitrate in the surface waters and lake waters were lower in summer than that in winter, due to the dilution of the wet deposition in summer. The concentrations of nitrate in the western part of the Chaohu Lake are higher than that in the eastern part, due to the inflow river discharge. The δ15N values of nitrate in winter are higher than that in summer, which is consistent with the seasonal variation of nitrate. The primary nitrate sources in northwestern part of the Chaohu Lake are the input of soil organic nitrogen and sewage/manure effluents, while the soil organic nitrogen is the main source in the southwestern and eastern part of the Chaohu Lake. Meanwhile, the data concerning δ18O–NO3 − values in this study indicate that the nitrification process is one important source for the variability of nitrate in Chaohu Lake. This study can provide useful scientific guidance for the remediation and management of Chaohu Lake.

Where does streamwater come from in low-relief forested watersheds? A dual-isotope approach

Abstract. The time and geographic sources of streamwater in low-relief watersheds are poorly understood. This is partly due to the difficult combination of low runoff coefficients and often damped streamwater isotopic signals precluding traditional hydrograph separation and convolution integral approaches. Here we present a dual-isotope approach involving 18O and 2H of water in a low-angle forested watershed to determine streamwater source components and then build a conceptual model of streamflow generation. We focus on three headwater lowland sub-catchments draining the Savannah River Site in South Carolina, USA. Our results for a 3-year sampling period show that the slopes of the meteoric water lines/evaporation water lines (MWLs/EWLs) of the catchment water sources can be used to extract information on runoff sources in ways not considered before. Our dual-isotope approach was able to identify unique hillslope, riparian and deep groundwater, and streamflow compositions. The streams showed strong evaporative enrichment compared to the local meteoric water line (δ2H = 7.15 · δ18O +9.28‰) with slopes of 2.52, 2.84, and 2.86. Based on the unique and unambiguous slopes of the EWLs of the different water cycle components and the isotopic time series of the individual components, we were able to show how the riparian zone controls baseflow in this system and how the riparian zone "resets" the stable isotope composition of the observed streams in our low-angle, forested watersheds. Although this approach is limited in terms of quantifying mixing percentages between different end-members, our dual-isotope approach enabled the extraction of hydrologically useful information in a region with little change in individual isotope time series.

Tracing the Nitrate Sources of the Yili River in the Taihu Lake Watershed: A Dual Isotope Approach

As the third largest freshwater lake in China, Taihu Lake has experienced severe cyanobacterial blooms and associated water quality degradation in recent decades, threatening the human health and sustainable development of cities in the watershed. The Yili River is a main river of Taihu Lake, contributing about 30% of the total nitrogen load entering the lake. Tracing the nitrate sources of Yili River can inform the origin of eutrophication in Taihu Lake and provide hints for effective control measures. This paper explored the nitrate sources and cycling of the Yili River based on dual nitrogen (δ15N) and oxygen (δ18O) isotopic compositions. Water samples collected during both the wet and dry seasons from different parts of the Yili River permitted the analysis of the seasonal and spatial variations of nitrate concentrations and sources. Results indicated that the wet season has higher nitrate concentrations than the dry season despite the stronger dilution effects, suggesting a greater potential of cyanobacterial blooms in summer. The δ15N-NO3− values were in the range of 4.0‰–14.0‰ in the wet season and 4.8‰–16.9‰ in dry, while the equivalent values of δ18O were 0.5‰–17.8‰ and 3.5‰–15.6‰, respectively. The distribution of δ15N-NO3− and δ18O-NO3− indicated that sewage and manure as well as fertilizer and soil organic matter were the major nitrate sources of the Yili River. Atmospheric deposition was an important nitrate source in the upper part of Yili River but less so in the middle and lower reaches due to increasing anthropogenic contamination. Moreover, there was a positive relationship between δ18O-NO3− and δ15N-NO3− in the wet season, indicating a certain extent of denitrification. In contrast, the δ18O-δ15N relationship in the dry season was significantly negative, suggesting that the δ15N and δ18O values were determined by a mixing of different nitrate sources.

Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane.

This study investigates dual C-Cl isotope fractionation during 1,1,1-TCA transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was performed for the first time, and transformation-associated isotope fractionation ε bulk C and ε bulk Cl values were -4.0 ± 0.2‰ and no chlorine isotope fractionation with PS, -1.6 ± 0.2‰ and -4.7 ± 0.1‰ for HY/DH, -7.8 ± 0.4‰ and -5.2 ± 0.2‰ with Fe(0). Distinctly different dual isotope slopes (Δδ13C/Δδ37Cl): ∞ with PS, 0.33 ± 0.04 for HY/DH and 1.5 ± 0.1 with Fe(0) highlight the potential of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the field. The trend observed with PS agreed with a C-H bond oxidation mechanism in the first reaction step. For HY/DH and Fe(0) pathways, different slopes were obtained although both pathways involve cleavage of a C-Cl bond in their initial reaction step. In contrast to the expected larger primary carbon isotope effects relative to chlorine for C-Cl bond cleavage, ε bulk C < ε bulk Cl was observed for HY/DH and in a similar range for reduction by Fe(0), suggesting the contribution of secondary chlorine isotope effects. Therefore, different magnitude of secondary chlorine isotope effects could at least be partly responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following this dual isotope approach, abiotic transformation processes can unambiguously be identified and quantified.

Moulting and Wintering Grounds of Marsh WarblersAcrocephalus palustris: Evidence from Stable Isotopes and Ring Recoveries

Abstract. We analysed stable carbon (δ13C) and nitrogen (δ15N) isotope ratios in Marsh Warbler Acrocephalus palustris feathers sampled in Europe and Africa to assess non-breeding habitat selection and location of wintering grounds of different breeding populations. Feather δ13C values showed that Marsh Warblers occupy a biome dominated by C4 vegetation during the stopover in northeastern Africa, whereas C3 habitats are used during the complete moult in southern Africa. East European Marsh Warblers differed in their stable isotope profiles from other European regions, suggesting a certain level of population segregation in southern Africa. A dual-isotope assignment approach confirmed this difference and helped us restrict the autumn staging areas to lower elevations of the Ethiopian Highlands west of the Rift valley. Available ring recoveries, however, suggested high levels of population mixing both on migration through East Africa and in the final wintering grounds.