Organic contamination detection for isotopic analysis of water by laser spectroscopy.

RATIONALE: Hydrogen and oxygen stable isotope ratios (δ2 H, δ17 O, and δ18 O values) are commonly used tracers of water. These ratios can be measured by isotope ratio infrared spectroscopy (IRIS). However, IRIS approaches are prone to errors induced by organic compounds present in plant, soil, and natural water samples. A novel approach using 17 O-excess values has shown promise for flagging spectrally contaminated plant samples during IRIS analysis. A systematic assessment of this flagging system is needed to prove it useful. METHODS: Errors induced by methanol and ethanol water mixtures on measured IRIS and isotope ratio mass spectrometry (IRMS) results were evaluated. For IRIS analyses both liquid- and vapour-mode (via direct vapour equilibration) methods are used. The δ2 H, δ17 O, and δ18 O values were measured and compared with known reference values to determine the errors induced by methanol and ethanol contamination. In addition, the 17 O-excess contamination detection approach was tested. This is a post-processing detection tool for both liquid and vapour IRIS triple-isotope analyses, utilizing calculated 17 O-excess values to flag contaminated samples. RESULTS: Organic contamination induced significant errors in IRIS results, not seen in IRMS results. Methanol caused larger errors than ethanol. Results from vapour-IRIS analyses had larger errors than those from liquid-IRIS analyses. The 17 O-excess approach identified methanol driven error in liquid- and vapour-mode IRIS samples at levels where isotope results became unacceptably erroneous. For ethanol contaminated samples, a mix of erroneous and correct flagging occurred with the 17 O-excess method. Our results indicate that methanol is the more problematic contaminant for data corruption. The 17 O-excess method was therefore useful for data quality control. CONCLUSIONS: Organic contamination caused significant errors in IRIS stable isotope results. These errors were larger during vapour analyses than during liquid IRIS analyses, and larger for methanol than ethanol contamination. The 17 O-excess method is highly sensitive for detecting narrowband (methanol) contamination error in vapour and liquid analysis modes in IRIS.

Retraction Note: Global analysis of streamflow response to forest management.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Editorial Expression of Concern: Global analysis of streamflow response to forest management.

An Addendum to this paper has been published and can be accessed via a link at the top of the paper.

Author Correction: Global analysis of streamflow response to forest management.

An Amendment to this paper has been published and can be accessed via a link at the top of the paper.

Global analysis of streamflow response to forest management.

Predicting the responses of streamflow to changes in forest management is fundamental to the sustainable regulation of water resources. However, studies of changes in forest cover have yielded unclear and largely unpredictable results. Here we compile a comprehensive and spatially distributed database of forest-management studies worldwide, to assess the factors that control streamflow response to forest planting and removal. We introduce a vegetation-to-bedrock model that includes seven key landscape factors in order to explain the impacts of forest removal and planting on water yield. We show that the amount of water stored in a landscape is the most important factor in predicting streamflow response to forest removal, whereas the loss of water through evaporation and transpiration is the most important factor in predicting streamflow response to forest planting. Our findings affect model parameterizations in climate change mitigation schemes (involving, for example, afforestation or deforestation) in different geologic and climate regions around the world, and inform practices for the sustainable management of water resources.

17 O-excess as a detector for co-extracted organics in vapor analyses of plant isotope signatures.

RATIONALE: The stable isotope compositions of hydrogen and oxygen in water (δ2 H and δ18 O values) have been widely used to investigate plant water sources, but traditional isotopic measurements of plant waters are expensive and labor intensive. Recent work with direct vapor equilibration (DVE) on laser spectroscopy has shown potential to side step limitations imposed by traditional methods. Here, we evaluate DVE analysis of plants with a focus on spectral contamination introduced by organic compounds. We present 17 O-excess as a way of quantifying organic compound interference in DVE. METHODS: We performed isotopic analysis using the δ2 H, δ18 O and δ17 O values of water on an Off-Axis Integrated Cavity Output Spectroscopy (IWA-45EP OA-ICOS) instrument in vapor mode. We used a set of methanol (MeOH) and ethanol (EtOH) solutions to assess errors in isotope measurements. We evaluated how organic compounds affect the 17 O-excess. DVE was used to measure the isotopic signatures in natural plant material from Pinus banksiana, Picea mariana, and Larix laricina, and soil from boreal forest for comparison with solutions. RESULTS: The 17 O-excess was sensitive to the presence of organic compounds in water. 17 O-excess changed proportionally to the concentration of MeOH per volume of water, resulting in positive values, while EtOH solutions resulted in smaller changes in the 17 O-excess. Soil samples did not show any spectral contamination. Plant samples were spectrally contaminated on the narrow-band and were enriched in 1 H and 16 O compared with source water. L. laricina was the only species that did not show any evidence of spectral contamination. Xylem samples that were spectrally contaminated had positive 17 O-excess values. CONCLUSIONS: 17 O-excess can be a useful tool to identify spectral contamination and improve DVE plant and soil analysis in the laboratory and in situ. The 17 O-excess flagged the presence of MeOH and EtOH. Adding measurement of δ17 O values to traditional measurement of δ2 H and δ18 O values may shed new light on plant water analysis for source mixing dynamics using DVE.

A comparison of extraction systems for plant water stable isotope analysis.

RATIONALE: The stable isotope ratios of water (δ2 H and δ18 O values) have been widely used to trace water in plants in a variety of physiological, ecohydrological, biogeochemical and hydrological studies. In such work, the analyte must first be extracted from samples, prior to isotopic analysis. While cryogenic vacuum distillation is currently the most widely used method reported in the literature, a variety of extraction-collection-analysis methods exist. A formal inter-method comparison on plant tissues has yet to be carried out. METHODS: We performed an inter-method comparison of six plant water extraction techniques: direct vapour equilibration, microwave extraction, two unique versions of cryogenic vacuum distillation, centrifugation, and high-pressure mechanical squeezing. These methods were applied to four isotopically unique plant portions (head, stem, leaf, and root crown) of spring wheat (Triticum aestivum L.). Extracted plant water was analyzed via spectrometric (OA-ICOS) and mass-based (IRMS) analysis systems when possible. Spring wheat was grown under controlled conditions with irrigation inputs of a known isotopic composition. RESULTS: The tested methods of extraction yielded markedly different isotopic signatures. Centrifugation, microwave extraction, direct vapour equilibration, and high-pressure mechanical squeezing produced water more enriched in 2 H and 18 O content. Both cryogenic vacuum distillation systems and the high-pressure mechanical squeezing method produced water more depleted in 2 H and 18 O content, depending upon the plant portion extracted. The various methods also produced differing concentrations of co-extracted organic compounds, depending on the mode of extraction. Overall, the direct vapor equilibration method outperformed all other methods. CONCLUSIONS: Despite its popularity, cryogenic vacuum distillation was outperformed by the direct vapor equilibration method in terms of limited co-extraction of volatile organic compounds, rapid sample throughput, and near instantaneous returned stable isotope results. More research is now needed with other plant species, especially woody plants, to see how far the findings from this study could be extended.

A sprinkling experiment to quantify celerity-velocity differences at the hillslope scale.

Few studies have quantified the differences between celerity and velocity of hillslope water flow and explained the processes that control these differences. Here, we asses these differences by combining a 24-day hillslope sprinkling experiment with a spatially explicit hydrologic model analysis. We focused our work on Watershed 10 at the H. J. Andrews Experimental Forest in western Oregon. Celerities estimated from wetting front arrival times were generally much faster than average vertical velocities of δ2H. In the model analysis, this was consistent with an identifiable effective porosity (fraction of total porosity available for mass transfer) parameter, indicating that subsurface mixing was controlled by an immobile soil fraction, resulting in the attenuation of the δ2H input signal in lateral subsurface flow. In addition to the immobile soil fraction, exfiltrating deep groundwater that mixed with lateral subsurface flow captured at the experimental hillslope trench caused further reduction in the δ2H input signal. Finally, our results suggest that soil depth variability played a significant role in the celerity-velocity responses. Deeper upslope soils damped the δ2H input signal, while a shallow soil near the trench controlled the δ2H peak in lateral subsurface flow response. Simulated exit time and residence time distributions with our hillslope hydrologic model showed that water captured at the trench did not represent the entire modeled hillslope domain; the exit time distribution for lateral subsurface flow captured at the trench showed more early time weighting.

Spatial and temporal patterns of soil water storage and vegetation water use in humid northern catchments.

Using stable isotope data from soil and vegetation xylem samples across a range of landscape positions, this study provides preliminary insights into spatial patterns and temporal dynamics of soil-plant water interactions in a humid, low-energy northern environment. Our analysis showed that evaporative fractionation affected the isotopic signatures in soil water at shallow depths but was less marked than previously observed in other environments. By comparing the temporal dynamics of stable isotopes in soil water mainly held at suctions around and below field capacity, we found that these waters are not clearly separated. The study inferred that vegetation water sources at all sites were relatively constant, and most likely to be in the upper profile close to the soil/atmosphere interface. The data analyses also suggested that both vegetation type and landscape position, including soil type, may have a strong influence on local water uptake patterns, although more work is needed to explicitly identify water sources and understand the effect of plant physiological processes on xylem isotopic water signatures.

Prevalence and magnitude of groundwater use by vegetation: a global stable isotope meta-analysis.

The role of groundwater as a resource in sustaining terrestrial vegetation is widely recognized. But the global prevalence and magnitude of groundwater use by vegetation is unknown. Here we perform a meta-analysis of plant xylem water stable isotope (δ2H and δ18O, n = 7367) information from 138 published papers - representing 251 genera, and 414 species of angiosperms (n = 376) and gymnosperms (n = 38). We show that the prevalence of groundwater use by vegetation (defined as the number of samples out of a universe of plant samples reported to have groundwater contribution to xylem water) is 37% (95% confidence interval, 28-46%). This is across 162 sites and 12 terrestrial biomes (89% of heterogeneity explained; Q-value = 1235; P < 0.0001). However, the magnitude of groundwater source contribution to the xylem water mixture (defined as the proportion of groundwater contribution in xylem water) is limited to 23% (95% CI, 20-26%; 95% prediction interval, 3-77%). Spatial analysis shows that the magnitude of groundwater source contribution increases with aridity. Our results suggest that while groundwater influence is globally prevalent, its proportional contribution to the total terrestrial transpiration is limited.

The role of stable isotopes in understanding rainfall interception processes: A review.

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects a suite of processes modifying rainfall. Factors that affect isotopic composition of canopy water include fractionation, exchange between liquid and vapor, and selective transmittance of temporally varying rainfall along varying canopy flowpaths. Despite frequent attribution of canopy effects on isotopic composition of throughfall to evaporative fractionation, data suggest exchange and selection are more likely the dominant factors. Temporal variability in canopy effects is generally consistent with either exchange or selection, but spatial variability is generally more consistent with selection. However, most investigations to date have not collected data sufficient to unambiguously identify controlling processes. Using isotopic data for improved understanding of physical processes and water routing in the canopy requires recognizing how these factors and processes lead to patterns of isotopic variability, and then applying this understanding towards focused data collection and analysis.

Global separation of plant transpiration from groundwater and streamflow.

Current land surface models assume that groundwater, streamflow and plant transpiration are all sourced and mediated by the same well mixed water reservoir--the soil. However, recent work in Oregon and Mexico has shown evidence of ecohydrological separation, whereby different subsurface compartmentalized pools of water supply either plant transpiration fluxes or the combined fluxes of groundwater and streamflow. These findings have not yet been widely tested. Here we use hydrogen and oxygen isotopic data ((2)H/(1)H (δ(2)H) and (18)O/(16)O (δ(18)O)) from 47 globally distributed sites to show that ecohydrological separation is widespread across different biomes. Precipitation, stream water and groundwater from each site plot approximately along the δ(2)H/δ(18)O slope of local precipitation inputs. But soil and plant xylem waters extracted from the 47 sites all plot below the local stream water and groundwater on the meteoric water line, suggesting that plants use soil water that does not itself contribute to groundwater recharge or streamflow. Our results further show that, at 80% of the sites, the precipitation that supplies groundwater recharge and streamflow is different from the water that supplies parts of soil water recharge and plant transpiration. The ubiquity of subsurface water compartmentalization found here, and the segregation of storm types relative to hydrological and ecological fluxes, may be used to improve numerical simulations of runoff generation, stream water transit time and evaporation-transpiration partitioning. Future land surface model parameterizations should be closely examined for how vegetation, groundwater recharge and streamflow are assumed to be coupled.

Testing the hydrological landscape unit classification system and other terrain analysis measures for predicting low-flow nitrate and chloride in watersheds.

Elevated nitrate concentrations in streamwater are a major environmental management problem. While land use exerts a large control on stream nitrate, hydrology often plays an equally important role. To date, predictions of low-flow nitrate in ungauged watersheds have been poor because of the difficulty in describing the uniqueness of watershed hydrology over large areas. Clearly, hydrologic response varies depending on the states and stocks of water, flow pathways, and residence times. How to capture the dominant hydrological controls that combine with land use to define streamwater nitrate concentration is a major research challenge. This paper tests the new Hydrologic Landscape Regions (HLRs) watershed classification scheme of Wolock and others (Environmental Management 34:S71-S88, 2004) to address the question: Can HLRs be used as a way to predict low-flow nitrate? We also test a number of other indexes including inverse-distance weighting of land use and the well-known topographic index (TI) to address the question: How do other terrain and land use measures compare to HLR in terms of their ability to predict low-flow nitrate concentration? We test this for 76 watersheds in western Oregon using the U.S. Environmental Protection Agency's Environmental Monitoring and Assessment Program and Regional Environmental Monitoring and Assessment Program data. We found that HLRs did not significantly improve nitrate predictions beyond the standard TI and land-use metrics. Using TI and inverse-distance weighting did not improve nitrate predictions; the best models were the percentage land use-elevation models. We did, however, see an improvement of chloride predictions using HLRs, TI, and inverse-distance weighting; adding HLRs and TI significantly improved model predictions and the best models used inverse-distance weighting and elevation. One interesting result of this study is elevation consistently predicted nitrate better than TI or the hydrologic classification scheme.