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Geology topics

C. Kendall

Publications and source records attributed to C. Kendall.

At least 37 records · Page 2Linked to original sources

Global patterns of the isotopic composition of soil and plant nitrogen

We compiled new and published data on the natural abundance N isotope composition (δ 15 N values) of soil and plant organic matter from around the world. Across a broad range of climate and ecosystem types, we found that soil and plant δ 15 N values systematically decreased with increasing mean annual precipitation (MAP) and decreasing mean annual temperature (MAT). Because most undisturbed soils are near N steady state, the observations suggest that an increasing fraction of ecosystem N losses are 15 N-depleted forms (NO 3 , N 2 O, etc.) with decreasing MAP and increasing MAT. Wetter and colder ecosystems appear to be more efficient in conserving and recycling mineral N. Globally, plant δ 15 N values are more negative than soils, but the difference (δ 15 N plant -δ 15 N soil ) increases with decreasing MAT (and secondarily increasing MAP), suggesting a systematic change in the source of plant-available N (organic/NH 4 + versus NO 3 − ) with climate. Nitrogen isotopes reflect time integrated measures of the controls on N storage that are critical for predictions of how these ecosystems will respond to human-mediated disturbances of the global N cycle.

Global Biogeochemical Cycles

A multiisotope C and N modeling analysis of soil organic matter turnover and transport as a function of soil depth in a California annual grassland soil chronosequence

We examine soil organic matter (SOM) turnover and transport using C and N isotopes in soil profiles sampled circa 1949, 1978, and 1998 (a period spanning pulse thermonuclear 14 C enrichment of the atmosphere) along a 3‐million‐year annual grassland soil chronosequence. Temporal differences in soil Δ 14 C profiles indicate that inputs of recently living organic matter (OM) occur primarily in the upper 20–30 cm but suggest that OM inputs can occur below the primary rooting zone. A three‐pool SOM model with downward transport captures most observed variation in Δ 14 C, percentages of C and N, δ 13 C, and δ 15 N, supporting the commonly accepted concept of three distinct SOM pools. The model suggests that the importance of the decadal SOM pool in N dynamics is greatest in young and old soils. Altered hydrology and possibly low pH and/or P dynamics in highly developed old soils cause changes in soil C and N turnover and transport of importance for soil biogeochemistry models.

Global Biogeochemical Cycles

The role of bedrock topography on subsurface storm flow

We conducted a detailed study of subsurface flow and water table response coupled with digital terrain analysis (DTA) of surface and subsurface features at the hillslope scale in Panola Mountain Research Watershed (PMRW), Georgia. Subsurface storm flow contributions of macropore and matrix flow in different sections along an artificial trench face were highly variable in terms of timing, peak flow, recession characteristics, and total flow volume. The trench flow characteristics showed linkages with the spatial tensiometer response defining water table development upslope. DTA of the ground surface did not capture the observed spatial patterns of trench flow or tensiometric response. However, bedrock surface topographic indices significantly improved the estimation of spatial variation of flow at the trench. Point‐scale tensiometric data were also more highly correlated with the bedrock surface‐based indices. These relationships were further assessed for temporal changes throughout a rainstorm. Linkages between the bedrock indices and the trench flow and spatial water table responses improved during the wetter periods of the rainstorm, when the hillslope became more hydrologically connected. Our results clearly demonstrate that in developing a conceptual framework for understanding the mechanisms of runoff generation, local bedrock topography may be highly significant at the hillslope scale in some catchments where the bedrock surface acts as a relatively impermeable boundary.

Water Resources Research

Oxygen isotope corrections for online δ34S analysis

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

Rapid Communications in Mass Spectrometry

Controls on old and new water contributions to stream flow at some nested catchments in Vermont, USA

Factors controlling the partitioning of old and new water contributions to stream flow were investigated for three events in four catchments (three of which were nested) at Sleepers River Research Watershed in Danville, Vermont. In the 1993 snowmelt period, two-component isotopic hydrograph separations showed that new water (meltwater) inputs to the stream ranged widely from 41 to 74%, and increased with catchment size (41 to 11 125 ha) (with one exception) and with open land cover (0-73%). Peak dissolved organic carbon concentrations and relative alkalinity dilution in stream water ranked in the same order among catchments as the new water fractions, suggesting that new water followed shallow flow paths. During the 1994 snowmelt, despite similar timing and magnitude of melt inputs, the new-water contribution to stream flow ranged only from 30 to 36% in the four catchments. We conclude that the uncommonly high and variable new water fractions in streamwater during the 1993 melt were caused by direct runoff of meltwater over frozen ground, which was prevalent in open land areas during the 1993 winter. In a high-intensity summer rainstorm in 1993, new water fractions were smaller relative to the 1993 snowmelt, ranging from 28 to 46%, but they ranked in the identical catchment order. Reconciliation of the contrasting patterns of new-old water partitioning in the three events appears to require an explanation that invokes multiple processes and effects, including: 1 topographically controlled increase in surface-saturated area with increasing catchment size; 2 direct runoff over frozen ground; 3 low infiltration in agriculturally compacted soils; 4 differences in soil transmissivity, which may be more relevant under dry antecedent conditions. These data highlight some of the difficulties faced by catchment hydrologists in formulating a theory of runoff generation at varying basin scales. Copyright ?? 2002 John Wiley and Sons, Ltd.

Hydrological Processes

Isotope variations in a Sierra Nevada snowpack and their relation to meltwater

Isotopic variations in melting snow are poorly understood. We made weekly measurements at the Central Sierra Snow Laboratory, California, of snow temperature, density, water equivalent and liquid water volume to examine how physical changes within the snowpackgovern meltwater δ 18 O. Snowpack samples were extracted at 0.1 m intervals from ground level to the top of the snowpack profile between December 1991 and April 1992. Approximately 800 mm of precipitation fell during the study period with δ 18 O values between −21.35 and −4.25‰. Corresponding snowpack δ 18 O ranged from −22.25 to −6.25‰. The coefficient of variation of δ 18 O in snowpack levels decreased from −0.37 to −0.07 from winter to spring, indicating isotopic snowpack homogenization. Meltwater δ 18 O ranged from −15.30 to −8.05‰, with variations of up to 2.95‰ observed within a single snowmeltepisode, highlighting the need for frequent sampling. Early snowmelt originated in the lower snowpack with higher δ 18 O through ground heat flux and rainfall. After the snowpack became isothermal, infiltrating snowmelt displaced the higher δ 18 O liquid in the lower snowpack through a piston flow process. Fractionation analysis using a two-component mixing model on the isothermal snowpack indicated that δ 18 O in the initial and final half of major snowmelt was 1.30‰ lower and 1.45‰ higher, respectively, than the value from simple mixing. Mean snowpack δ 18 O on individual profiling days showed a steady increase from −15.15 to −12.05‰ due to removal of lower δ 18 O snowmelt and addition of higher δ 18 O rainfall. Results suggest that direct sampling of snowmelt and snow cores should be undertaken to quantify tracer input compositions adequately. The snowmelt sequence also suggests that regimes of early lower δ 18 O and later higher δ 18 O melt may be modeled and used in catchment tracing studies.

Journal of Hydrology

Levels of mercury in alligators (Alligator mississippiensis) collected along a transect through the Florida Everglades

As part of a multi-agency study of alligator health, 28 American alligators (Alligator mississippiensis) were captured along a transect through the Florida Everglades in 1999. Liver and tail muscle tissues were sampled and analyzed on a wet weight basis for total mercury (THg) using cold-vapor atomic absorption spectrophotometry. All tissues had detectable concentrations of THg that ranged from 0.6 to 17 mg/kg in liver and from 0.1 to 1.8 mg/kg in tail muscle. THg was more concentrated in liver tissue than tail muscle, but levels were highly correlated between tissues. THg concentrations in tissue differed significantly among locations, with animals from Everglades National Park (ENP) having mean concentrations of THg in liver (10.4 mg/kg) and tail muscle (1.2 mg/kg) that were two-fold higher than basin-wide averages (4.9 and 0.64 mg/kg, respectively). The reasons for higher contamination of ENP alligators were unclear and could not be explained by differences in sex, length, weight or animal age. While ??15N values were positively correlated with THg concentrations in tail muscle, spatial patterns in isotopic composition did not explain the elevated THg levels in ENP alligators. Therefore, it appears that ENP alligators were more highly exposed to mercury in their environment than individuals in other areas. Comparisons to a previous survey by Yanochko et al. [Arch Environ Contam Toxicol 32 (1997) 323] suggest that mercury levels have declined in some Everglades alligators since 1994. ?? 2002 Elsevier Science B.V. All rights reserved.

Science of the Total Environment

A look inside 'black box' hydrograph separation models: A study at the hydrohill catchment

Runoff sources and dominant flowpaths are still poorly understood in most catchments; consequently, most hydrograph separations are essentially 'black box' models where only external information is used. The well-instrumented 490 m2 Hydrohill artificial grassland catchment located near Nanjing (China) was used to examine internal catchment processes. Since groundwater levels never reach the soil surface at this site, two physically distinct flowpaths can unambiguously be defined: surface and subsurface runoff. This study combines hydrometric, isotopic and geochemical approaches to investigating the relations between the chloride, silica, and oxygen isotopic compositions of subsurface waters and rainfall. During a 120 mm storm over a 24 h period in 1989, 55% of event water input infiltrated and added to soil water storage; the remainder ran off as infiltration-excess overland flow. Only about 3-5% of the pre-event water was displaced out of the catchment by in-storm rainfall. About 80% of the total flow was quickflow, and 10% of the total flow was pre-event water, mostly derived from saturated flow from deeper soils. Rain water with high ??18O values from the beginning of the storm appeared to be preferentially stored in shallow soils. Groundwater at the end of the storm shows a wide range of isotopic and chemical compositions, primarily reflecting the heterogeneous distribution of the new and mixed pore waters. High chloride and silica concentrations in quickflow runoff derived from event water indicate that these species are not suitable conservative tracers of either water sources or flowpaths in this catchment. Determining the proportion of event water alone does not constrain the possible hydrologic mechanisms sufficiently to distinguish subsurface and surface flowpaths uniquely, even in this highly controlled artificial catchment. We reconcile these findings with a perceptual model of stormflow sources and flowpaths that explicitly accounts for water, isotopic, and chemical mass balance. Copyright ?? 2001 John Wiley & Sons, Ltd.

Hydrological Processes

Soil N and 15N variation with time in a California annual grassland ecosystem

The %N and ??15N values of soils and plants were measured along a chronosequence spanning 3 to 3000 Ky in a California annual grassland. Total soil N decreased with increasing soil age (1.1 to 0.4 kg N m-2) while the mean ?? 15N values of the soil N increased by several ??? from the youngest to oldest sites (+3.5 to +6.2 ???). The ?? 15N values of plants varied along the gradient, reflecting changing soil N pools and differences in the form of N uptake. The decline in total N storage with time is hypothesized to be due to a shift from N to P limitation with increasing soil age. The general increase in ?? 15N values with time is interpreted using a N mass balance model, and appears to reflect a shift toward an increasing proportional losses of inorganic mineral forms of N (vs. organic forms) with increasing soil age. We develop a quantitative index of this trend (mineral vs. organic forms of N loss) using mass balance considerations and parameters. The %N and ?? 15N values along the California age gradient were compared to the published data for a comparably aged chronosequence in Hawaii. Most striking in this comparison is the observation that the California soil and plant ?? 15N values are several ??? greater than those on comparably aged Hawaiian sites. Multiple explanations are plausible, but assuming the sites have a similar range in ?? 15N values of atmospheric inputs, the isotopic differences suggest that N may be, at least seasonally, in greater excess in the strongly seasonal, semi-arid, California grassland. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta

The role of event water, a rapid shallow flow component, and catchment size in summer stormflow

Seven nested headwater catchments (8 to 161 ha) were monitored during five summer rain events to evaluate storm runoff components and the effect of catchment size on water sources. Two-component isotopic hydrograph separation showed that event-water contributions near the time of peakflow ranged from 49% to 62% in the 7 catchments during the highest intensity event. The proportion of event water in stormflow was greater than could be accounted for by direct precipitation onto saturated areas. DOC concentrations in stormflow were strongly correlated with stream 18O composition. Bivariate mixing diagrams indicated that the large event water contributions were likely derived from flow through the soil O-horizon. Results from two-tracer, three-component hydrograph separations showed that the throughfall and O-horizon soil-water components together could account for the estimated contributions of event water to stormflow. End-member mixing analysis confirmed these results. Estimated event-water contributions were inversely related to catchment size, but the relation was significant for only the event with greatest rainfall intensity. Our results suggest that perched, shallow subsurface flow provides a substantial contribution to summer stormflow in these small catchments, but the relative contribution of this component decreases with catchment size.Seven nested headwater catchments (8 to 161 ha) were monitored during five summer rain events to evaluate storm runoff components and the effect of catchment size on water sources. Two-component isotopic hydrograph separation showed that event-water contributions near the time of peakflow ranged from 49% to 62% in the 7 catchments during the highest intensity event. The proportion of event water in stormflow was greater than could be accounted for by direct precipitation onto saturated areas. DOC concentrations in stormflow were strongly correlated with stream 18O composition. Bivariate mixing diagrams indicated that the large event water contributions were likely derived from flow through the soil O-horizon. Results from two-tracer, three-component hydrograph separations showed that the throughfall and O-horizon soil-water components together could account for the estimated contributions of event water to stormflow. End-member mixing analysis confirmed these results. Estimated event-water contributions were inversely related to catchment size, but the relation was significant for only the event with greatest rainfall intensity. Our results suggest that perched, shallow subsurface flow provides a substantial contribution to summer stormflow in these small catchments, but the relative contribution of this component decreases with catchment size.

Journal of Hydrology

Carbon isotopic constraints on the contribution of plant material to the natural precursors of trihalomethanes

The δ 13 C values of individual trihalomethanes (THM) formed on reaction of chlorine with dissolved organic carbon (DOC) leached from maize (corn; Zea maize L. ) and Scirpus acutus (an aquatic bulrush), and with DOC extracted from agricultural drainage waters were determined using purge and trap introduction into a gas chromatograph-combustion-isotope ratio monitoring mass spectrometer. We observed a 16.8‰ difference between the δ 13 C values of THM produced from the maize and Scirpus leachates, similar to the isotopic difference between the whole plant materials. Both maize and Scirpus formed THM 12‰ lower in 13 C than whole plant material. We suggest that the low value of the THM relative to the whole plant material is evidence of distinct pools of THM-forming DOC, representing different biochemical types or chemical structures, and possessing different environmental reactivity.

Organic Geochemistry

A method for nitrate collection for δ 15 N and δ 18 O analysis from waters with low nitrate concentrations

Recently, methods have been developed to analyze NO3- for δ15N and δ18O, improving our ability to identify NO3- sources and transformations. However, none of the existing methods are suited for waters with low NO3- concentrations (0.7-10 µM). We describe an improved method for collecting and recovering NO3- on exchange columns. To overcome the lengthy collection loading times imposed by the large sample volumes (7-70 L), the sample was prefiltered (0.45 µm) with a large surface area filter. Switching to AG2X anion resin and using a coarser mesh size (100-200) than previous methods also enhanced sample flow. Placement of a cation column in front of the anion column minimized clogging of the anion column by dissolved organic carbon (DOC) accumulation. This also served to minimize transfer of unwanted oxygen atoms from DOC to the 18O portion of the NO3- sample, thereby contaminating the sample and shifting δ18O. The cat-AG2X method is suited for on-site sample collection, making it possible to collect and recover NO3- from low ionic strength waters with modest DOC concentrations (80-800 µM), relieves the investigator of transporting large volumes of water back to the laboratory, and offers a means of sampling rain, snow, snowmelt, and stream samples from access-limited sites.

Canadian Journal of Fisheries and Aquatic Sciences

Geochemistry of Florida Bay sediments: Nutrient history at five sites in eastern and central Florida Bay

Recent seagrass dieoff and massive microalgal blooms have focused attention on the health of the Florida Bay ecosystem. Changes in nutrient input and the nutrient dynamics of Florida Bay are hypothesized to be linked to these problems, but crucial baseline information is still lacking. Efforts to restore Florida Bay to its natural condition will require information on the nutrient history of the bay. The purpose of this study was to examine distributions of organic C, total N, and total P in carbonate sediments from sites of continuous and known sedimentation rate (210Pb and 137Cs dated), in eastern and central Florida Bay. These sediments provide a record of historical changes in the C, N, and P load to the eastern and central bay. Analyses were conducted on sediments from cores collected at five sites, and on buried seagrass fragments at two sites. At three of the sites, sediments from seagrass-covered and adjacent barren areas were examined to determine differences in sedimentary geochemistry. Stable isotope analyses (??13C and ??15N) of sedimentary organic C and total N and of buried seagrass fragments were also carried out at two sites to examine possible changes in nutrient sources to the estuary. Results were consistent with recent increases in N and P in eastern Florida Bay, beginning in the early to mid 1980's. The timing of the increase in nutrient load observed in the sediment data directly preceded the first observations of massive microalgal blooms and seagrass dieoff in Florida Bay in 1987. The observed nutrification was greater for P than N, and was most pronounced at the most northeasterly site sampled (Pass Key). Isotope data (??15N) suggested that an increase in algal production accompanied the increase in N load at the Pass Key site. Along record of organic C, total N, and total P distributions from Whipray Basin in central Florida Bay showed historical peaks (mid 1700's and late 1800's) in organic C and total N, but not total P; these enrichments were nearly equivalent to recent inputs to the estuary. Barren areas were observed to have generally lower concentrations of organic C, total N, and total P in near surface sediments compared to seagrass-covered areas, but had generally similar concentrations in deeper sediments. This suggested that barren areas adjacent to seagrass-covered sites were places where relict sediment was physically transported and covered seagrass beds. This dataset provides an historical view of changes in nutrient inputs to Florida Bay, and baseline information needed for nutrient modeling of the bay.

Journal of Coastal Research

The role of near-stream riparian zones in the hydrology of steep upland catchments

Surface and subsurface waters were monitored and sampled at various topographic positions in a 40.5-ha headwater catchment to test several hypotheses of runoff generation and stream chemical and isotopic evolution during snowmelt. Transmissivity feedback was observed on the hillslopes during the melt period. Groundwater levels and stream DOC were highly correlated with stream discharge. Hysteresis in the groundwater-streamflow relation suggests that localized water flux from the riparian areas controlled the rising limb and main peak response of the melt hydrograph, whilst hillslope drainage controlled the timing and volume of the falling limb. Lateral flow from upslope positions was detected in the riparian zone.

IAHS-AISH Publication

Identification of internal flow dynamics in two experimental catchments

Identification of the internal flow dynamics in catchments is difficult because of the lack of information in precipitation -stream discharge time series alone. Two experimental catchments, Hydrohill and Nandadish, near Nanjing in China, have been set up to monitor internal flows reaching the catchment stream at various depths, from the surface runoff to the bedrock. With analysis of the precipitation against these internal discharges, it is possible to quantify the time constants and volumes associated with various flowpaths in both catchments.

Nanjing

Kinetic and mineralogic controls on the evolution of groundwater chemistry and 87Sr/86Sr in a sandy silicate aquifer, northern Wisconsin, USA

Substantial flowpath-related variability of 87Sr/86Sr is observed in groundwaters collected from the Trout Lake watershed of northern Wisconsin. In the extensive shallow aquifer composed of sandy glacial outwash, groundwater is recharged either by seepage from lakes or by precipitation that infiltrates the inter-lake uplands. 87Sr/86Sr of groundwater derived mainly as seepage from a precipitation-dominated lake near the head of the watershed decreases with progressive water chemical evolution along its flowpath due primarily to enhanced dissolution of relatively unradiogenic plagioclase. In contrast, 87Sr/86Sr of groundwater derived mainly from precipitation that infiltrates upland areas is substantially greater than that of precipitation collected from the watershed, due to suppression of plagioclase dissolution together with preferential leaching of Sr from radiogenic phases such as K-feldspar and biotite. The results of a column experiment that simulated the effects of changing residence time of water in the aquifer sand indicate that mobile waters obtain relatively unradiogenic Sr, whereas stagnant waters obtain relatively radiogenic Sr. Nearly the entire range of strontium-isotope composition observed in groundwaters from the watershed was measured in the experimental product waters. The constant mobility of water along groundwater recharge flowpaths emanating from the lakes promotes the dissolution of relatively unradiogenic plagioclase, perhaps due to effective dispersal of clay mineral nuclei resulting from dissolution reactions. In contrast, episodic stagnation in the unsaturated zone along the upland recharge flowpaths suppresses plagioclase dissolution, perhaps due to accumulation of clay mineral nuclei on its reactive surfaces. Differences in redox conditions along these contrasting flowpaths probably enhance the observed differences in strontium isotope behavior. This study demonstrates that factors other than the calculated state of mineral saturation must be considered when attempting to simulate chemical evolution along flowpaths, and that reaction models must be able to incorporate changing contributions from reacting minerals in the calculations.

Geochimica et Cosmochimica Acta

Testing and validating environmental models

Generally accepted standards for testing and validating ecosystem models would benefit both modellers and model users. Universally applicable test procedures are difficult to prescribe, given the diversity of modelling approaches and the many uses for models. However, the generally accepted scientific principles of documentation and disclosure provide a useful framework for devising general standards for model evaluation. Adequately documenting model tests requires explicit performance criteria, and explicit benchmarks against which model performance is compared. A model's validity, reliability, and accuracy can be most meaningfully judged by explicit comparison against the available alternatives. In contrast, current practice is often characterized by vague, subjective claims that model predictions show 'acceptable' agreement with data; such claims provide little basis for choosing among alternative models. Strict model tests (those that invalid models are unlikely to pass) are the only ones capable of convincing rational skeptics that a model is probably valid. However, 'false positive' rates as low as 10% can substantially erode the power of validation tests, making them insufficiently strict to convince rational skeptics. Validation tests are often undermined by excessive parameter calibration and overuse of ad hoc model features. Tests are often also divorced from the conditions under which a model will be used, particularly when it is designed to forecast beyond the range of historical experience. In such situations, data from laboratory and field manipulation experiments can provide particularly effective tests, because one can create experimental conditions quite different from historical data, and because experimental data can provide a more precisely defined 'target' for the model to hit. We present a simple demonstration showing that the two most common methods for comparing model predictions to environmental time series (plotting model time series against data time series, and plotting predicted versus observed values) have little diagnostic power. We propose that it may be more useful to statistically extract the relationships of primary interest from the time series, and test the model directly against them.

Science of the Total Environment