Identification of Multiple Sources of Groundwater Contamination by Dual Isotopes

Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ¹³C and δ³⁷Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.     

Determination of the 13C/12C Isotope Ratio of Organic Compounds for the Biological Degradation of Tetrachloroethene (PCE) and Trichloroethene (TCE)

With the method used here, it was possible to determine the isotope content of both the initial compounds and their metabolites formed due to microbial degradation. The chemical analysis showed that the dominating degradation metabolite for both PCE and TCE degradation was cis-1,2-dichloroethene (cis-1,2-DCE). Apart from this, the formation of TCE, trans-1,2-DCE, 1,1-DCE, chloroethene (VC), ethene and ethane was observed. The isotope analysis showed no measurable fractionation of stable carbon isotopes, for the microbial degradation of PCE and TCE to cis-1,2-DCE. There was a small effect for trans-1,2-DCE and a stronger one for VC as metabolite of TCE.     

Determination of Polycyclic Aromatic Hydrocarbons in Soil by Miniaturized Ultrasonic Extraction and Gas Chromatography‐Mass Selective Detection

A miniaturized ultrasonic extraction procedure was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil by gas chromatography‐mass spectrometry. After determination of the most suitable extraction solvent with 5 min sonication time, several other parameters (sample amount, solvent volume and number of extraction times) were optimized using a 2³ factorial experimental design. Recoveries of PAHs from spiked soil samples were over 90% for three different fortification levels between 50 and 300 μg/kg, and relative standard deviations of the recoveries were in the range of < 1–15%. The limits of detection ranged from 0.002 to 1.87 μg/kg. The performance of the developed procedure was also compared with other traditional Soxhlet, shake flask and large scale ultrasonic extraction procedures on real soil samples, and extraction methods showed comparable efficiencies. The proposed procedure required small volumes of solvent and sample. It was practicable, rapid and easy to use for analysis of PAHs in soils.     

Carbon Isotope Analysis to Evaluate Nanoscale Fe(O) Treatment at a Chlorohydrocarbon Contaminated Site

Remediation of groundwater contaminated by chlorinated hydrocarbons via in situ technologies such as direct injection of nanoscale zero valent iron (ZVI, Fe(O)) particles is increasingly common. However, assessing target compound degradation by abiotic processes is difficult because (1) the injection may displace the contaminant plume so that concentration measurements alone are often inconclusive and (2) biodegradation may also occur, making it challenging to identify and evaluate the abiotic degradation component. In this study, trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA) were treated in a highly heterogeneous hydrogeologic setting. The purpose of this study was to evaluate the potential for compound-specific stable isotope analysis (CSIA) to monitor the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA degradation. Prior to ZVI injection, carbon isotope measurements demonstrated biodegradation of TCE by native microorganisms. This in situ biodegradation was quantified by measuring the enrichment of ¹³C in TCE samples downstream of the suspected source. When ZVI was injected through only two injection wells, no changes in TCE and 1,1,1-TCA isotope signatures were detected compared to preinjection values. In contrast, when ZVI was injected through 11 wells covering a greater portion of the contaminated area, 5 out of 10 monitoring wells showed further enrichment of ¹³C in either TCE or 1,1,1-TCA, indicating additional target compound transformation. The abiotic nature of this TCE transformation was confirmed through temporal trends in carbon isotope values of the putative transformation products cis-dichloroethylene (cis-DCE), ethene and ethane. This demonstrates the usefulness of CSIA in distinguishing abiotic vs. biotic transformation in the field.     

Determination of groundwater discharge rates and water residence time of groundwater‐fed lakes by stable isotopes of water (18O, 2H) and radon (222Rn) mass balances

Lacustrine groundwater discharge (LGD) and the related water residence time are crucial parameters for quantifying lake matter budgets and assessing its vulnerability to contaminant input. Our approach utilizes the stable isotopes of water (δ¹⁸O, δ²H) and the radioisotope radon (²²²Rn) for determining long‐term average and short‐term snapshots in LGD. We conducted isotope balances for the 0.5‐km² Lake Ammelshainer See (Germany) based on measurements of lake isotope inventories and groundwater composition accompanied by good quality and comprehensive long‐term meteorological and isotopic data (precipitation) from nearby monitoring stations. The results from the steady‐state annual isotope balances that rely on only two sampling campaigns are consistent for both δ¹⁸O and δ²H and suggested an overall long‐term average LGD rate that was used to infer the water residence time of the lake. These findings were supported by the good agreement of the simulated LGD‐driven annual cycles of δ¹⁸O and δ²H lake inventories with the observed lake isotope inventories. However, radon mass balances revealed lower values that might be the result of seasonal LGD variability. For obtaining further insights into possible seasonal variability of groundwater–lake interaction, stable water isotope and radon mass balances could be conducted more frequently (e.g., monthly) in order to use the derived groundwater discharge rates as input for time‐variant isotope balances.     

Bound and mobile soil water isotope ratios are affected by soil texture and mineralogy,whereas extraction method influences their measurement

Questions persist about interpreting isotope ratios of bound and mobile soil water pools, particularly relative to clay content and extraction conditions. Interactions between pools and resulting extracted water isotope composition are presumably related to soil texture, yet few studies have manipulated the bound pool to understand its influence on soil water processes. Using a series of drying and spiking experiments, we effectively labelled bound and mobile water pools in soils with varying clay content. Soils were first vacuum dried to remove residual water, which was then replaced with heavy isotope-enriched water prior to oven drying and spiking with heavy isotope-depleted water. Water was extracted via centrifugation or cryogenic vacuum distillation (at four temperatures) and analysed for oxygen and hydrogen isotope ratios via isotope ratio mass spectrometry. Water from centrifuged samples fell along a mixing line between the two added waters but was more enriched in heavy isotopes than the depleted label, demonstrating that despite oven drying, a residual pool remains and mixes with the mobile water. Soils with higher clay + silt content appeared to have a larger bound pool. Water from vacuum distillation samples have a significant temperature effect, with high temperature extractions yielding progressively more heavy isotope-enriched values, suggesting that Rayleigh fractionation occurred at low temperatures in the vacuum line. By distinctly labelling bound and mobile soil water pools, we detected interactions between the two that were dependent on soil texture. Although neither extraction method appeared to completely extract the combined bound and mobile (total water) pool, centrifugation and high temperature cryogenic vacuum distillations were comparable for both δ²H and δ¹⁸O of soil water isotope ratios.     

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation.     

Carbon Isotope Fractionation of PCE and TCE During Dechlorination by Vitamin B12

Reductive dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) by vitamin B12 is an analogue of the microbial reductive dechlorination reaction and is presently being applied as a remediation technique. Stable carbon isotopic analysis, an effective and powerful tool for the investigation and monitoring of contaminant remediation, was used to characterize the isotopic effects of reductive dechlorination of PCE and TCE by vitamin B12 in laboratory microcosms. In laboratory experiments, 10 mg/L vitamin B12 degraded >90% of the initial 20 mg/L PCE with TCE, the primary product of PCE degradation, accounting for between 64% and 72% of the PCE degraded. In experiments with TCE, 147 mg/L vitamin B12 degraded >90% of the initial 20 mg/L TCE with cis -dichloroethene ( c DCE), the primary product of degradation accounting for between 30% and 35% of the TCE degraded. Degradation of both PCE and TCE exhibited first-order kinetics. Strong isotopic fractionation of the reactant PCE and of the reactant TCE was observed over the course of degradation. This fractionation could be described with a Rayleigh model using enrichment factors of −16.5%o and −15.8%o for PCE, and −17.2%o and −16.6%o for TCE. Fractionation was similar in all experiments, with a mean enrichment factor of −16.5%o ± 0.6%o. The occurrence of such large enrichment factors indicates that isotopic analysis can be used to monitor the dechlorination of PCE and TCE by vitamin B12 and remediation of ground water plumes. Evidence indicates that isotopic fractionation is taking place during complexation of the chlorinated ethenes to vitamin B12, as has been suggested for reductive dechlorination by zero valent iron. The differences between e values for this reaction and those observed for anaerobic biodegradation of the chlorinated ethenes suggest that there may be differences in the rate-determining step for these two processes.     

Origin and Evolution of Aquitard Porewater in the Western Coastal Plain of Bohai Bay,China

High‐salinity paleowater from low‐permeability aquitards in coastal areas can be a major threat to groundwater resources; however, such water has rarely been studied. The chemical and isotopic compositions of porewater extracted from a 200‐m‐thick Quaternary sedimentary sequence in the western coastal plain of Bohai Bay, China, were analyzed to investigate the salinity origin and chemical evolution of porewater in aquitards. Porewater samples derived at depths shallower than 32 m are characterized by Cl‐Na type saline water (total dissolved solids [TDS], 10.9–84.3 g/L), whereas those at depths greater than 32 m comprise Cl·SO₄‐Na type brackish water (TDS, 2.2–6.3 g/L). Saline porewater is interpreted as evaporated seawater prior to halite saturation, as evidenced by Cl‐Br relationships. Although substantial dilution of saline porewater with meteoric water is supported by a wider Cl^? range and δ²H‐δ¹⁸O covariance, the original marine waters were not completely flushed out. The deeper brackish porewater is determined to be a mixture of fresher porewater and brine groundwater and had a component of old brine of less than 10%, as indicated by a mixing model defined using δ²H and Cl^? tracers. Porewater δ²H‐δ¹⁸O relationships and negative deuterium excess ranging from ?25.9‰ to ?2.9‰ indicate the existence of an arid climate since Late Pleistocene in Tianjin Plain. The aquitard porewaters were chemically modified through water‐rock interactions due to the long residence time.     

Field Demonstrations Using the Waterloo Ground Water Profiler

Use of direct-push sampling tools fur rapid investigations of contaminated sites has proliferated in the past several years. A direct-push device, referred to as a ground water sampling profiler, was recently developed at the University of Waterloo. This tool differs from oilier direct-push tools in that point samples are collected at multiple depths in the same hole without retrieving, decontaminating, and re-driving the tool alter each sampling event. The collection of point samples, rather than samples from a longer screened interval, allows an exceptional level of detail to be generated about the vertical distribution of contamination from each hole. The benefits of acquiring this level of detail arc contingent on minimization of vertical cross contamination of samples caused by drag down from high concentration zones into underlying low concentration zones. In a detailed study of chlorinated solvent plumes in sandy aquifers, we found that drag down using the profiler is minimal or non-detectable even when the tool is driven through high concentration zones of dissolved chlorinated solvent contamination. Chlorinated solvent concentrations, primarily PCE and TCE at or below a detection limit of 1 μg/L, were obtained directly beneath plumes with maximum concentrations up to thousands of μg/L. Minimal drag down, on the order of a few μg/L to 20 μg/L, may have been observed below chlorinated solvent concentrations of several tens of thousands to hundreds of thousands of μg/L. Drag down through DNAPL zones was not evaluated.     

Numerical Analysis of Thermal Remediation in 3D Field‐Scale Fractured Geologic Media

Thermal methods are promising for remediating fractured geologic media contaminated with volatile organic compounds, and the success of this process depends on the coupled heat transfer, multiphase flow, and thermodynamics. This study analyzed field‐scale removal of trichloroethylene (TCE) and heat transfer behavior in boiling fractured geologic media using the multiple interacting continua method. This method can resolve local gradients in the matrix and is less computationally demanding than alternative methods like discrete fracture‐matrix models. A 2D axisymmetric model was used to simulate a single element of symmetry in a repeated pattern of extraction wells inside a large heated zone and evaluate effects of parameter sensitivity on contaminant recovery. The results showed that the removal of TCE increased with matrix permeability, and the removal rate was more sensitive to matrix permeability than any other parameter. Increasing fracture density promoted TCE removal, especially when the matrix permeability was low (e.g., <10^?17 m²). A 3D model was used to simulate an entire treatment zone and the surrounding groundwater in fractured material, with the interaction between them being considered. Boiling was initiated in the center of the upper part of the heated region and expanded toward the boundaries. This boiling process resulted in a large increase in the TCE removal rate and spread of TCE to the vadose zone and the peripheries of the heated zone. The incorporation of extraction wells helped control the contaminant from migrating to far regions. After 22 d, more than 99.3% of TCE mass was recovered in the simulation.     

A modified light transmission visualization method for DNAPL saturation measurements in 2-D models

In this research, a light transmission visualization (LTV) method was used to quantify dense non-aqueous phase liquids (DNAPL) saturation in two-dimensional (2-D), two fluid phase systems. The method is an expansion of earlier LTV methods and takes into account both absorption and refraction light theories. Based on this method, DNAPL and water saturations can rapidly be obtained point wise across sand-packed 2-D flow chambers without the need to develop a calibration curve. A single point calibration step is, however, needed when dyed DNAPL is used to account for the change in the transmission factor at the dyed DNAPL–water interface. The method was applied to measure, for the first time, undyed DNAPL saturation in small 2-D chambers. Known amounts of DNAPL, modeled by tetrachloroethylene (PCE), were added to the chamber and these amounts were compared to results obtained by this LTV method. Strong correlation existed between results obtained based on this method and the known PCE amounts with an R² value of 0.993. Similar experiments conducted using dyed PCE showed a stronger correlation between results obtained by this LTV method and the known amounts of dyed PCE added to the chamber with an R² value of 0.999. The method was also used to measure dyed PCE saturation in a large 2-D model following sparging experiments. Results obtained from image analyses following each sparging event were compared to results obtained by two independent techniques, namely gas chromatography–mass spectrometry (GC/MS) analyses and carbon column extraction. There was a good agreement between the results obtained by this LTV method and those obtained by the two independent techniques when experiments were carried out under stable light source conditions and errors in mass balance were minor. The method presented here can be expanded to measure fluid contents in three fluid phase systems and provide a non-destructive, non-intrusive tool to investigate changes in DNAPL architecture and flow characteristics in laboratory experiments.     

Numerical simulation of transport and sequential biodegradation of chlorinated aliphatic hydrocarbons using CHAIN_2D

Microbiological degradation of perchloroethylene (PCE) under anaerobic conditions follows a series of chain reactions, in which, sequentially, trichloroethylene (TCE), cis‐dichloroethylene (c‐DCE), vinylchloride (VC) and ethene are generated. First‐order degradation rate constants, partitioning coefficients and mass exchange rates for PCE, TCE, c‐DCE and VC were compiled from the literature. The parameters were used in a case study of pump‐and‐treat remediation of a PCE‐contaminated site near Tilburg, The Netherlands. Transport, non‐equilibrium sorption and biodegradation chain processes at the site were simulated using the CHAIN_2D code without further calibration. The modelled PCE compared reasonably well with observed PCE concentrations in the pumped water. We also performed a scenario analysis by applying several increased reductive dechlorination rates, reflecting different degradation conditions (e.g. addition of yeast extract and citrate). The scenario analysis predicted considerably higher concentrations of the degradation products as a result of enhanced reductive dechlorination of PCE. The predicted levels of the very toxic compound VC were now an order of magnitude above the maximum permissible concentration levels. Copyright © 1999 John Wiley & Sons, Ltd.     

ESTIMATION OF LAKE EVAPORATION FROM A SHALLOW LAKE IN CENTRAL SWEDEN BY OXYGEN-18

Lake evaporation has been estimated for a shallow lake using a combination of water and isotope mass balance, accounting for the isotopic non-steady state of lake water. The main feature of the isotope method is that inflows need not be measured. Knowledge of their isotopic content is sufficient. Oxygen-18 content, i.e. (δ¹⁸O), of lake water, inflows and outflow was measured on a weekly basis, whereas for precipitation it was monitored daily. The discharge from the lake was also recorded daily. Lake water level, relative humidity, air, and lake water surface temperatures were recorded by a logger. The weather data were recorded on a small island in the lake. It was observed that the lake is isotopically well mixed. Furthermore, the atmospheric moisture was not always in isotopic equilibrium with the precipitation. Daily lake evaporation was estimated as an average of six to eight days depending upon the field logistics. Lake evaporation varied from 0.6 to about 5.4 mm/day during the experimental period. It was found that evaporation estimates are very sensitive to small variations in δ¹⁸O of lake evaporate. Induced changes of 10% in δ¹⁸O of lake evaporate caused errors in evaporation estimates of 9–31%, while similar induced changes in δ¹⁸O of inflows caused errors of 8–18%. Thus, an accurate experimental determination of δ¹⁸O of lake evaporate is relatively more important.     

Application of the Response Surface Method for Optimization of Headspace Liquid Phase Microextraction of Trihalomethanes in Drinking Water

An optimized analysis method based on headspace liquid phase microextraction (HS‐LPME) and gas chromatography coupled with mass spectrometry was proposed for the determination of trihalomethanes (THMs) in drinking water. The response surface method (RSM) was used to optimize the extraction of THMs for analysis by HS‐LPME. The temperature, extraction time and NaCl concentration were found to be important extraction parameters. The coefficient of determination (R²) for the model was 94.97%. A high probability value (P < 0.0001) for the regression indicated that the model had a high level of significance. The optimum conditions were seen to be: temperature 42.0°C, NaCl concentration 0.30 g/mL, and extraction time 28 min. The response variable was the summation of the THMs chromatography peak areas and the reproducibility of this was investigated in five replicate experiments under the optimized conditions. The relative standard deviations (RSD%) of the THMs ranged from 8.0–11.6%. The limits of detection (LODs), based on a signal‐to‐noise ratio (S/N) of three ranged from 0.42–0.78 μg/L, and were lower than the maximum limits for THMs in drinking water established by the WHO.     

Major Procedural Discrepancies in Soil Extracted Nitrate Levels and Nitrogen Isotopic Values

Preliminary vadose zone nitrate extraction experiments have revealed the extractant (2N KCl) volume affects the determination of nitrate and its nitrogen isotope ratio. In five cores, extractable NO₃-N concentrations increased an average of 1.7 times after the soil-to-extractant ratio was increased from 1:1 to 1:10. An increased extractant volume resulted in a large positive shift of stable nitrogen values (δ¹⁵N), which averaged +6.2%. An underestimation of available NO₃-N for leaching and transport through the vadose zone and a biased source interpretation from the δ¹⁵N values probably would occur if a procedure which leads to incomplete extraction of nitrate is used.     

Intercomparison of soil pore water extraction methods for stable isotope analysis

Measurements of δ²H and δ¹⁸O composition of pore waters in saturated and unsaturated soil samples are routinely performed in hydrological studies. A variety of in‐situ and lab‐based pore water extraction methods for the analysis of the stable isotopes of water now exist. While some have been used for decades (e.g. cryogenic vacuum extraction) others are relatively new, such as direct vapour equilibration or the microwave extraction technique. Despite their broad range of application, a formal and comprehensive intercomparison of soil water extraction methods for stable isotope analysis is lacking and long overdue. Here we present an intercomparison among five commonly used lab‐based pore water extraction techniques (high pressure mechanical squeezing, centrifugation, direct vapour equilibration, microwave extraction, and cryogenic extraction). We applied these extraction methods to two physicochemically different soil types that were dried and rewetted with water of known isotopic composition at three different water contents. Our results showed that the extraction approach can have a significant effect on pore water isotopic composition as all methods exhibited significant deviations from the spiked reference water, depending secondarily on the soil type and soil water content. Most pronounced, cryogenic water extraction showed large deviations from the spiked reference water, whereas mechanical squeezing and centrifugation provided results closest to the spiked water for both soil types. We also compared results for each extraction method – where liquid water was obtained – on both an OA‐ICOS and IRMS. Differences between these two analytical instruments were negligible for these organic compound‐free waters. We suggest that users of soil water extraction approaches carefully choose an extraction technique that is suitable for the specific research question, adapted to the dominant soil type and water content of the study. Copyright © 2016 John Wiley & Sons, Ltd.     

Evidence for a hypogene paleohydrogeological event at the prospective nuclear waste disposal site Yucca Mountain,Nevada, USA,revealed by the isotope composition of fluid-inclusion water

Secondary calcite residing in open cavities in the unsaturated zone of Yucca Mountain has long been interpreted as the result of downward infiltration of meteoric water through open fractures. In order to obtain information on the isotopic composition (δD and δ¹⁸O) of the mineral-forming water we studied fluid inclusions from this calcite. Water was extracted from inclusions by heated crushing and the δD values were measured using a continuous-flow isotope-ratio mass spectrometry method. The δ¹⁸O values were calculated from the δ¹⁸O values of the host calcite assuming isotopic equilibrium at the temperature of formation determined by fluid-inclusion microthermometry.The δD values measured in all samples range between ? 110 and ? 90‰, similar to Holocene meteoric water. Coupled δ¹⁸O–δD values plot significantly, 2 to 8‰, to the right of the meteoric water line. Among the various processes operating at the topographic surface and/or in the unsaturated zone only two processes, evaporation and water–rock exchange, could alter the isotope composition of percolating water. Our analysis indicates, however, that none of these processes could produce the observed large positive δ¹⁸O-shifts. The latter require isotopic interaction between mineral-forming fluid and host rock at elevated temperature (>100 °C), which is only possible in the deep-seated hydrothermal environment. The stable isotope data are difficult to reconcile with a meteoric origin of the water from which the secondary minerals at Yucca Mountain precipitated; instead they point to the deep-seated provenance of the mineral-forming waters and their introduction into the unsaturated zone from below, i.e. a hypogene origin.     

δ53Cr values of catchment runoff exhibit seasonality regardless of bedrock Cr concentrations: Role of periodically changing chromium export fluxes

One pre-requisite for the construction of a global chromium isotope mass balance is detailed understanding of Cr isotope systematics in the critical zone where redox-processes can modify the isotope signature of geogenic Cr input into the hydrosphere. A Cr isotope inventory of bedrock, soil, and runoff was performed in a Central European headwater catchment underlain by amphibolite, situated in the vicinity of two previously studied catchments underlain by different bedrock types (serpentinite and leucogranite). Fresh bedrock in the amphibolite catchment NAZ contained ~300 mg/kg Cr, serpentinite at PLB contained ~800 mg/kg Cr, and leucogranite at LYS contained ~2 mg/kg Cr. Monthly hydrochemical monitoring at all three sites revealed higher Cr(VI) export fluxes in winter than in summer. NAZ was characterized by a distinct seasonality in the δ⁵³Cr values, with minima during winter/spring snowmelts (−0.35‰) and maxima during dry summers (0.40‰). Similar seasonality in δ⁵³Cr values had been reported from PLB and LYS. Bedrock at all three sites had similar Cr isotope composition close to −0.10‰, a value indistinguishable from the δ⁵³Cr value of bulk silicate Earth (BSE). Positive mean δ⁵³Cr value of NAZ runoff indicated Cr-isotope fractionations during weathering of geogenic Cr(III), combined with adsorption of the resulting Cr(VI) on soil particles during pedogenesis. However, the mass-weighted mean δ⁵³Cr of NAZ runoff was lower (−0.08‰), indistinguishable from the Cr isotope signature of bedrock. The same pattern of lower mass-weighted mean δ⁵³Cr values of runoff, compared to arithmetic mean δ⁵³Cr values of runoff, were observed also at PLB and LYS. We suggest that elevated Cr runoff fluxes in winter remove some of the residual isotopically light Cr that accumulated in the soil during summer. Seasonality in runoff δ⁵³Cr values appears to be a relatively widespread phenomenon, de-coupled from Cr availability for chemical weathering.     

The stable isotopes of natural waters at the Marcell Experimental Forest

We present a new data set from the Marcell Experimental Forest (MEF) that compiles water isotope measurements from multiple research catchments, some of which have been studied since the 1960s. The MEF is located in northern Minnesota, USA, and is home to heavily studied and monitored forests, streams, bogs, and fens. Peat-forming systems (bogs and fens) are an important component of the MEF landscape and have a profound impact on the water cycle in these catchments. Within the last decade, analysis of stable isotopes of water (expressed as δD and δ¹⁸O) has been implemented to characterize the different components of the water budget, and to allow researchers to look at catchment and peatland-specific hydrologic effects in the watershed. This δD and δ¹⁸O data set of natural waters from MEF catchments is primarily composed of measurements from three peatlands (S1, S2, S6) during an 11-year period. More recently collection and analysis were expanded to also include samples from the Spruce and Peatland Responses Under Changing Environments (SPRUCE) project in the S1 bog, peatlands S3, S4, S5, as well as nearby lakes. We establish a local meteoric water line by analyzing the isotopic composition of precipitation, which fills a void in regional meteoric water lines for Minnesota. Furthermore, we establish baseline isotopic composition for bog outlet streams, bog porewater, aquifer groundwater, overland flow, subsurface stormflow, and snowpack, as well as runoff from the SPRUCE experimental chambers. These data are publicly available and will be expanded upon in the future.