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To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ18O and δ2H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at-site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap's surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of standards. Copyright © 2010 John Wiley & Sons, Ltd.

We assessed species-specific coverage (km2) of a submerged aquatic vegetation (SAV) community in the fresh and upper oligohaline Potomac Estuary from 1985 to 2001 using a method combining field observations of species-proportional coverage data with congruent remotely sensed coverage and density (percent canopy cover) data. Biomass (estimated by density-weighted coverage) of individual species was calculated. Under improving water quality conditions, exotic SAV species did not displace native SAV; rather, the percent of natives increased over time. While coverage-based diversity did fluctuate and increased, richness-based community turnover rates were not significantly different from zero. SAV diversity was negatively related to nitrogen concentration. Differences in functional traits, such as reproductive potential, between the dominant native and exotic species may explain some interannual patterns in SAV. Biomass of native, as well as exotic, SAV species varied with factors affecting water column light attenuation. We also show a positive response by a higher trophic level, waterfowl, to SAV communities dominated by exotic SAV from 1959 to 2001. Submerged vascular macrophytes, commonly referred to as submerged aquatic vegetation (SAV) in the Chesapeake Bay, provide necessary habitat and/or food for invertebrates, fish, and waterfowl (Rozas and Odum 1988; Perry and Deller 1996), but the quality of this habitat is threatened by the stress of diminishing water quality and invasion by exotic species. Despite the global prevalence of these stressors on SAV (Litav and Agame 1976; Phillips et al. 1978; Kozhova and Izhboldina 1993), there is a lack of long-term and quantitative data with which to characterize the behavior of a SAV community subject both to such stresses and to restorative efforts to improve water quality. The tidal Potomac River and Potomac Estuary are part of the Chesapeake Bay watershed (Fig. 1), and large public expenditures have been made to protect its living resources, including SAV. Several episodes of high SAV abundance in the upper tidal Potomac River have been documented. A dense community of SAV reported in 1916 (Potamogeton crispus L. [curly pondweed] and other Potamogeton spp., Ceratophyllum demersum L. [coontail], and Vallisneria americana Michaux [wild celery]) remained abundant until the late 1930s, but disappeared by 1952 as wastewater contributions increased (Carter et al. 1985). From the 1950s to the 1970s, algal blooms became massive and persistent. The exotic species Myriophyllum spicatum L. (milfoil)

The mid-to-late Pleistocene Devils Hole δ18O record has been extended from 60,000 to 4500 yr ago. The new δ18O time series, in conjunction with the one previously published, is shown to be a proxy of Pacific Ocean sea surface temperature (SST) off the coast of California. During marine oxygen isotope stages (MIS) 2 and 6, the Devil Hole and SST time series exhibit a steady warming that began 5000 to > 10,000 yr prior to the last and penultimate deglaciations. Several possible proximate causes for this early warming are evaluated. The magnitude of the peak δ18O or SST during the last interglacial (LIG) is significantly greater (1 per mill and 2 to 3°C, respectively) than the peak value of these parameters for the Holocene; in contrast, benthic δ18O records of ice volume show only a few tenths per mill difference in the peak value for these interglacials. Statistical analysis provides an estimate of the large shared information (variation) between the Devils Hole and Eastern Pacific SST time series from ∼ 41 to ∼ 2°N and enforces the concept of a common forcing among all of these records. The extended Devils Hole record adds to evidence of the importance of uplands bordering the eastern Pacific as a source of archives for reconstructing Pacific climate variability.

We developed an algorithm for calculating habitat suitability for seagrasses and related submerged aquatic vegetation (SAV) at coastal sites where monitoring data are available for five water quality variables that govern light availability at the leaf surface. We developed independent estimates of the minimum light required for SAV survival both as a percentage of surface light passing though the water column to the depth of SAV growth (PLW min) and as a percentage of light reaching reaching leaves through the epiphyte layer (PLL min). Value were computed by applying, as inputs to this algorithm, statistically dervived values for water quality variables that correspond to thresholds for SAV presence in Chesapeake Bay. These estimates ofPLW min andPLL min compared well with the values established from a literature review. Calcultations account for tidal range, and total light attenuation is partitioned into water column and epiphyte contributions. Water column attenuation is further partitioned into effects of chlorophylla (chla), total suspended solids (TSS) and other substances. We used this algorithm to predict potential SAV presence throughout the Bay where calculated light available at plant leaves exceededPLL min. Predictions closely matched results of aerial photographic monitoring surveys of SAV distribution. Correspondence between predictions and observations was particularly strong in the mesohaline and polythaline regions, which contain 75–80% of all potential SAV sites in this estuary. The method also allows for independent assessment of effects of physical and chemical factors other than light in limiting SAV growth and survival. Although this algorithm was developed with data from Chesapeake Bay, its general structure allows it to be calibrated and used as a quantitative tool for applying water quality data to define suitability of specific sites as habitats for SAV survival in diverse coastal environments worldwide.

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 +/- 20 micro g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H(3)PO(4)/CaCO(3)) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H(3)PO(4)/CaCO(3) reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 degrees C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was

Reanalysis and additional dating of the Devils Hole δ18O paleotemperature record confirm that the last interglaciation in the Great Basin (the continental analog of marine isotopic substage 5e) lasted ∼22,000 yr, consistent with the Vostok paleotemperature record which suggests a duration of ∼19,000 yr for this event in Antarctica. The three preceding interglaciations in the Devils Hole record (analogs of marine isotopic substages 7e, 9c, and 11c) range from 20,000 to 26,000 yr in duration. A ∼20,000-yr duration for the last interglaciation is consistent with TIMS uranium-series dated sea-level high stands. Thus, the widely held view that interglaciations were of 11,000- to 13,000-yr duration and constituted only about 10% of mid-to-late Pleistocene climatic cycles needs reexamination. The warmest portion of each interglaciation in the Devils Hole time series is marked by a δ18O plateau, signifying apparent climatic stability for periods of 10,000- to 15,000-yr duration.

The record of carbon-13 (delta(13)C) variations in DH-11 vein calcite core from Devils Hole, Nevada, shows four prominent minima near glacial terminations (glacial-interglacial transitions) V to II. The delta(13)C time series is inversely correlated with the DH-11 oxygen isotope ratio time series and leads it by as much as 7000 years. The delta(13)C variations likely record fluctuations in the delta(13)C of dissolved inorganic carbon of water recharging the aquifer. How such variations are transported 80 kilometers to Devils Hole without obliteration by water-rock reaction remains an enigma. The record may reflect (i) global variations in the delta(13)C of atmospheric CO(2) and, hence, the delta(13)C of continental biomass or (ii) variations in extent and density of vegetation in the southern Great Basin. In the latter case, delta(13)C minima at 414, 334, 246, and 133 thousand years ago mark times of maximum vegetation.

Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction f(E). We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction f(E) should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction f(E) can be calculated that are arguably protein-type specific and, as such, f(E) could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of standards.

[1] With a new automated precipitation collector we measured a remarkable decrease of 51‰ in the hydrogen isotope ratio (δ2H) of precipitation over a 60-minute period during the landfall of an extratropical cyclone along the California coast on 21 March 2005. The rapid drop in δ2H occurred as precipitation generation transitioned from a shallow to a much deeper cloud layer, in accord with synoptic-scale ascent and deep “seeder-feeder” precipitation. Such unexpected δ2H variations can substantially impact widely used isotope-hydrograph methods. From extreme δ2H values of −26 and −78‰, we calculate precipitation temperatures of 9.7 and −4.2°C using an adiabatic condensation isotope model, in good agreement with temperatures estimated from surface observations and radar data. This model indicates that 60 percent of the moisture was precipitated during ascent as temperature decreased from 15°C at the ocean surface to −4°C above the measurement site.

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 +/- 20 micro g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H(3)PO(4)/CaCO(3)) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H(3)PO(4)/CaCO(3) reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 degrees C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was/=0.1 and/=0.2 per mill or per thousand, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for delta(18)O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings.

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400+/-20 micrograms) of calcium carbonate. This new method streamlines the classical phosphoric acid - calcium carbonate (H3PO4 - CaCO3) reaction method by making use of a Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. To obtain reproducible and accurate results, optimal conditions for the H3PO4 - CaCO3 reaction had to be determined. At the acid-carbonate reaction temperature suggested by the equipment manufacturer, the oxygen isotope ratio results were unsatisfactory (standard deviation (sigma) greater than 1.5 per mill)), probably because of a secondary reaction. When the acid-carbonate reaction temperature was lowered to 26 deg C and the reaction time was increased to 24 hours, the precision of the carbon and oxygen isotope ratios for duplicate analyses improved to 0. 1 and 0.2 per mill, respectively. The method was tested by analyzing calcite from Devils Hole, Nevada, which was formed by precipitation from ground water onto the walls of a sub-aqueous cavern during the last 500,000 years. Isotope-ratio varies previously had been obtained by the classical method for Devils Hole core DH-11. The DH-11 core had been recently re-sampled, and isotope-ratio varies were obtained using this new method. The results were comparable to those obtained by the classical method. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, a cutting error that was then independently confirmed. The reproducibility of the isotopic varies is demonstrated by a correlation of approximately 0.96 for both isotopes, after correcting for an alignment offset. This result indicates that the new method is a viable alternative to the classical method.

The detailed and well-dated 500,000-year record of 818O variations found in vein calcite core DH-11 taken from Devils Hole in Nevada (Winograd and others, 1992) provides several challenges to the Milankovitch theory for the occurrence of Quaternary glaciations. A recent discussion paper (Imbrie and others, 1993) has dismissed the relevance of this well-dated core for determining the timing of global climatic fluctuations and, moreover, asserts that the Devils Hole record provides support for the Milankovitch theory. Upon analysis of the arguments found in this discussion, we find nothing to dissuade us from the original conclusion that the Devils Hole chronology does present a serious challenge to the Milankovitch theory.

Oxygen-18 (delta(18)O) variations in a 36-centimeter-long core (DH-11) of vein calcite from Devils Hole, Nevada, yield an uninterrupted 500,000-year paleotemperature record that closely mimics all major features in the Vostok (Antarctica) paleotemperature and marine delta(18)O ice-volume records. The chronology for this continental record is based on 21 replicated mass-spectrometric uranium-series dates. Between the middle and latest Pleistocene, the duration of the last four glacial cycles recorded in the calcite increased from 80,000 to 130,000 years; this variation suggests that major climate changes were aperiodic. The timing of specific climatic events indicates that orbitally controlled variations in solar insolation were not a major factor in triggering deglaciations. Interglacial climates lasted about 20,000 years. Collectively, these observations are inconsistent with the Milankovitch hypothesis for the origin of the Pleistocene glacial cycles but they are consistent with the thesis that these cycles originated from internal nonlinear feedbacks within the atmosphere-ice sheet-ocean system.

The Devils Hole calcite vein contains a long-term climatic record, but requires accurate chronologic control for its interpretation. Mass-spectrometric U-series ages for samples from core DH-11 yielded (230)Th ages with precisions ranging from less than 1,000 years (2sigma) for samples younger than approximately 140 ka (thousands of years ago) to less than 50,000 years for the oldest samples ( approximately 566 ka). The (234)U/(238)U ages could be determined to a precision of approximately 20,000 years for all ages. Calcite accumulated continuously from 566 ka until approximately 60 ka at an average rate of 0.7 millimeter per 10(3) years. The precise agreement between replicte analyses and the concordance of the (230)Th/(238)U (234)U/(238)U ages for the oldest samples indicate that the DH-11 samples were closed systems and validate the dating technique in general.

Water science finds itself at an interesting and critical crossroads. Sophisticated atmospheric modeling, remote sensing, and Internet-based exchange of data enable exciting new synergies to develop among scientists, policy-makers, and the private sector. Paradoxically we find it evermore difficult to validate products from these high-technology tools and to exploit their full potential due to a severe and sustained decline in available hydrologic data sets.

Weather and water-quality data from 1980 to 1989 were correlated with fluctuations in submersed macrophyte populations in the tidal Potomac River near Washington, D.C., to elucidate causal relationships and explain population dynamics. Both reaches were unvegetated in 1980 when mean growing-season Secchi depths were 0.65 were associated with increases in plant coverage. Changes in mean seasonal Secchi depth were related to changes in mean seasonal TSS and chlorophyll a concentration; mean Secchi depths >0.65 generally occur when seasonal mean TSS is

Hydrologic processes are generally held to be persistent and not secularly independent. Impetus for this view was given by Hurst in his work which dealt with properties of the rescaled range of many types of long geophysical records, in particular dendrochronologic records, in addition to hydrologic records. Mandelbrot introduced an infinite memory stationary process, the fractional Gaussian noise process (F), as an explanation for Hurst's observations. This is in contrast to other explanations which have been predicated on the implicit non-stationarity of the process underlying the construction of the records. In this work, we introduce a stationary finite memory process which arises naturally from a physical concept and show that it can accommodate the persistence structures observed for dendrochronological records more successfully than an F or any other of a family of related processes examined herein. Further, some question arises as to the empirical plausibility of an F process. Dendrochronologic records are used because they are widely held to be surrogates for records of average hydrologic phenomena and the length of these records allows one to explore questions of stochastic process structure which cannot be explored with great validity in the case of generally much shorter hydrologic records.

The geometric mean is often used to express acceptable levels of fecal coliform counts in federal and state water quality criteria or standards. The expected value of the geometric mean is shown to be a function of the sample size and to be very sensitive to the skew as well as to the form of the underlying distribution function. Implications of these findings are discussed with regard to standards. In particular, it is noted that great care must be taken in specifying the minimal sample size to be used.

Water quality indices are treated as random variables; the class of quality ‘averaging’ indices is examined and several statistics are derived. It is seen that the probability density functions of the water quality constituents as well as the structure of the transform functions (rating curves) influence the ability of indices to measure policy performance.

Index terms are those keywords attached to journal articles and geophysical abstracts in press (GAP) that facilitate their categorization and consequently allow for rapid searches of the published literature by topical areas. AGU published an index set in 1973 that became a standard in the geophysical sciences in that other organizations also incorporated this set into their index schemes.