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Carol Kendall

Publications and source records attributed to Carol Kendall.

At least 19 recordsLinked to original sources

Stable isotopes provide insight into sources and cycling of N compounds in the Sacramento-San Joaquin Delta, California, USA

River deltas and their diverse array of aquatic environments are increasingly impacted by anthropogenic inputs of nitrogen (N). These inputs can alter the N biogeochemistry of these systems and promote undesirable phenomena including harmful algae blooms and invasive aquatic macrophytes. To examine N sources and biogeochemical processes in the Sacramento-San Joaquin Delta, a river delta located in central California, USA, that is fed primarily by the Sacramento River, we utilized a multi-tracer approach that measured N species concentrations and stable isotope values monthly from April 2011 to November 2012 in samples collected from the channelized mainstem of the Sacramento River, two channelized distributaries of the Sacramento River, and the Cache Slough Complex, a network of Sacramento River tributaries and shallow water wetland habitat. We found that the Sacramento River and its channelized distributaries received N primarily in the form of NH 4 + from treated wastewater effluent and that NH 4 + was lost rapidly while NO 3 − was gained more slowly during subsequent downstream transit, driven by an array of biogeochemical processes whose identities could be constrained via examination of stable isotope values. The Cache Slough Complex, which was characterized by lower net flows and higher water residence times than the Sacramento River and its distributaries, received variable inputs of low conductivity water elevated in NH 4 + from the Sacramento River and higher conductivity water elevated in NO 3 − from landward tributaries. Deviations from expected conservative mixing of these sources were spatially variable but broadly indicative of local inputs of treated wastewater effluent NO 3 − , conversion of Sacramento River NH 4 + to NO 3 − via nitrification, uptake of NH 4 + and NO 3 − by phytoplankton, and remineralization of organic N. These findings highlight both the diversity in N dynamics in anthropogenically impacted river delta environments and the utility of a multi-tracer approach in constraining these processes in such complex systems.

California

Spatial variability of phytoplankton in a shallow tidal freshwater system reveals complex controls on abundance and community structure

Estuaries worldwide are undergoing changes to patterns of aquatic productivity because of human activities that alter flow, impact sediment delivery and thus the light field, and contribute nutrients and contaminants like pesticides and metals. These changes can influence phytoplankton communities, which in turn can alter estuarine food webs. We used multiple approaches-including high-resolution water quality mapping, synoptic sampling, productivity and nitrogen uptake rates, Lagrangian parcel tracking, enclosure experiments and bottle incubations-over a short time period to take a “spatial snapshot” of conditions in the northern region of the San Francisco Estuary (California, USA) to examine how environmental drivers like light availability, nutrients, water residence time, and contaminants affect phytoplankton abundance and community attributes like size distribution, taxonomic structure, and nutrient uptake rates. Zones characterized by longer residence time (15–60 days) had higher chlorophyll-a concentrations (9 ± 4 µg L −1 ) and were comprised primarily of small phytoplankton cells (<5 µm, 74 ± 8%), lower ammonium concentrations (1 ± 0.8 µM), higher nitrate uptake rates, and higher rates of potential carbon productivity. Conversely, zones characterized by shorter residence time (1–14 days) had higher ammonium concentration (13 ± 5 µM) and lower chlorophyll-a concentration (5 ± 1 µg L −1 ) with diatoms making up a larger percent contribution. Longer residence time, however, did not result in the accumulation of large (>5 µm) cells considered important to pelagic food webs. Rather, longer residence time zones had a phytoplankton community comprised primarily of small cells, particularly picocyanobacteria that made up 38 ± 17% of the chlorophyll-a – nearly double the concentration seen in shorter residence time zones (22 ± 7% picocyanobacterial of chlorophyll-a). Our results suggest that water residence time in estuaries may have an effect as large or larger than that experimentally demonstrated for light, contaminants, or nutrients.

California

Unprocessed atmospheric nitrate in waters of the Northern Forest Region in the USA and Canada

Little is known about the regional extent and variability of nitrate from atmospheric deposition that is transported to streams without biological processing in forests. We measured water chemistry and isotopic tracers (δ 18 O and δ 15 N) of nitrate sources across the Northern Forest Region of the U.S. and Canada and reanalyzed data from other studies to determine when, where, and how unprocessed atmospheric nitrate was transported in catchments. These inputs were more widespread and numerous than commonly recognized, but with high spatial and temporal variability. Only 6 of 32 streams had high fractions (>20%) of unprocessed atmospheric nitrate during baseflow. Seventeen had high fractions during stormflow or snowmelt, which corresponded to large fractions in near-surface soil waters or groundwaters, but not deep groundwater. The remaining 10 streams occasionally had some (<20%) unprocessed atmospheric nitrate during stormflow or baseflow. Large, sporadic events may continue to be cryptic due to atmospheric deposition variation among storms and a near complete lack of monitoring for these events. A general lack of observance may bias perceptions of occurrence; sustained monitoring of chronic nitrogen pollution effects on forests with nitrate source apportionments may offer insights needed to advance the science as well as assess regulatory and management schemes.

Environmental Science and Technology

Use of flow cytometry and stable isotope analysis to determine phytoplankton uptake of wastewater derived ammonium in a nutrient-rich river

Anthropogenic alteration of the form and concentration of nitrogen (N) in aquatic ecosystems is widespread. Understanding availability and uptake of different N sources at the base of aquatic food webs is critical to establishment of effective nutrient management programs. Stable isotopes of N ( 14 N, 15 N) are often used to trace the sources of N fueling aquatic primary production, but effective use of this approach requires obtaining a reliable isotopic ratio for phytoplankton. In this study, we tested the use of flow cytometry to isolate phytoplankton from bulk particulate organic matter (POM) in a portion of the Sacramento River, California, during river-scale nutrient manipulation experiments that involved halting wastewater discharges high in ammonium (NH 4 + ). Field samples were collected using a Lagrangian approach, allowing us to measure changes in phytoplankton N source in the presence and absence of wastewater-derived NH 4 + . Comparison of δ 15 N-POM and δ 15 N-phytoplankton ( δ 15 N-PHY) revealed that their δ 15 N values followed broadly similar trends. However, after 3 days of downstream travel in the presence of wastewater treatment plant (WWTP) effluent, δ 15 N-POM and δ 15 N-PHY in the Sacramento River differed by as much as 7 ‰. Using a stable isotope mixing model approach, we estimated that in the presence of effluent between 40 and 90 % of phytoplankton N was derived from NH 4 + after 3 days of downstream transport. An apparent gradual increase over time in the proportion of NH 4 + in the phytoplankton N pool suggests that either very low phytoplankton growth rates resulted in an N turnover time that exceeded the travel time sampled during this study, or a portion of the phytoplankton community continued to access nitrate even in the presence of elevated NH 4 + concentrations.

California

A river-scale Lagrangian experiment examining controls on phytoplankton dynamics in the presence and absence of treated wastewater effluent high in ammonium

Phytoplankton are critical component of the food web in most large rivers and estuaries, and thus identifying dominant controls on phytoplankton abundance and species composition is important to scientists, managers, and policymakers. Recent studies from a variety of systems indicate that ammonium ( NH + 4 ) in treated wastewater effluent decreases primary production and alters phytoplankton species composition. However, these findings are based mainly on laboratory and enclosure studies, which may not adequately represent natural systems. To test effects of effluent high in ammonium on phytoplankton at the ecosystem scale, we conducted whole-river–scale experiments by halting discharges to the Sacramento River from the regional wastewater treatment plant (WWTP), and used a Lagrangian approach to compare changes in phytoplankton abundance and species composition in the presence (+EFF) and absence (−EFF) of effluent. Over 5 d of downstream travel from 20 km above to 50 km below the WWTP, chlorophyll concentrations declined from 15–25 to ∼2.5 μg L −1 , irrespective of effluent addition. Benthic diatoms were dominant in most samples. We found no significant difference in phytoplankton abundance or species composition between +EFF and −EFF conditions. Moreover, greatest declines in chlorophyll occurred upstream of the WWTP where NH + 4 concentrations were low. Grazing by clams and zooplankton could not account for observed losses, suggesting other factors such as hydrodynamics and light limitation were responsible for phytoplankton declines. These results highlight the advantages of conducting ecosystem-scale, Lagrangian-based experiments to understand the dynamic and complex interplay between physical, chemical, and biological factors that control phytoplankton populations.

California

Paleoclimatic reconstruction using the correlation in δ 18 O of hackberry carbonate and environmental water, North America

Celtis sp. (commonly known as &ldquo;hackberry&rdquo;) fruits were collected from 101 North American sites located in 13 states and one Canadian province between the years of 1979&ndash;1994. The biomineralized carbonate endocarp of the hackberry, which is a common botanical fossil found throughout the Quaternary sediments of the Great Plains, was analyzed for its &delta; 18 O value and plotted against the &delta; 18 O value of site environmental water to demonstrate the potential of the hackberry as a paleoclimate indicator. This correlation was reinforced by intensive studies on extracted tissue-water &delta; 18 O value and hackberry endocarp carbonate &delta; 18 O value from three trees in Sterling, Colorado. The observed correlation in the large data set between hackberry endocarp carbonate &delta; 18 O value and environmental water is [endocarp &delta; 18 O=38.56+0.69&times;environmental water &delta; 18 O] ( R =0.88; R 2 =0.78; p value<0.0001). The relation of the hackberry carbonate to temperature in the Great Plains was the following: (average daily-maximum growing season temperature [&deg;C])=6.33+0.67 (&delta; 18 O of endocarp carbonate) ( R =0.73; R 2 =0.54; p value=0.0133). The &delta; 18 O value of early Holocene fossil hackberry carbonate in the Pintwater Cave, southern Nevada, suggested precipitation &delta; 18 O values more positive than today (&sim;&minus;4&permil; early Holocene vs &sim;&minus;9 to &minus;10&permil; today). This shift, combined with paleobotanical data, suggests an influx of summer monsoonal moisture to this region in the early Holocene. Alternatively, the more positive &delta; 18 O values could be viewed as suggestive of warmer temperatures, although the direct use of Great Plains hackberry/temperature relationships to the Great Basin is of debatable value.

Quaternary Research

Bayesian nitrate source apportionment to individual groundwater wells in the Central Valley by use of elemental and isotopic tracers

Groundwater quality is a concern in alluvial aquifers that underlie agricultural areas, such as in the San Joaquin Valley of California. Shallow domestic wells (less than 150 m deep) in agricultural areas are often contaminated by nitrate. Agricultural and rural nitrate sources include dairy manure, synthetic fertilizers, and septic waste. Knowledge of the relative proportion that each of these sources contributes to nitrate concentration in individual wells can aid future regulatory and land management decisions. We show that nitrogen and oxygen isotopes of nitrate, boron isotopes, and iodine concentrations are a useful, novel combination of groundwater tracers to differentiate between manure, fertilizers, septic waste, and natural sources of nitrate. Furthermore, in this work, we develop a new Bayesian mixing model in which these isotopic and elemental tracers were used to estimate the probability distribution of the fractional contributions of manure, fertilizers, septic waste, and natural sources to the nitrate concentration found in an individual well. The approach was applied to 56 nitrate-impacted private domestic wells located in the San Joaquin Valley. Model analysis found that some domestic wells were clearly dominated by the manure source and suggests evidence for majority contributions from either the septic or fertilizer source for other wells. But, predictions of fractional contributions for septic and fertilizer sources were often of similar magnitude, perhaps because modeled uncertainty about the fraction of each was large. For validation of the Bayesian model, fractional estimates were compared to surrounding land use and estimated source contributions were broadly consistent with nearby land use types.

California

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (&delta; 34 S VCDT) of &minus; 0.8&permil;. Bulk deposition on the island of Maui had a &delta; 34 S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7&permil;, and reflected isotopic mixing from three sources: sea-salt (+ 21.1&permil;), marine biogenic emissions (+ 15.6&permil;), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8&permil;). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7&permil;) to relatively high (+ 17.8 to + 19.3&permil;) soil &delta; 34 S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3&permil; and generally decreased with increasing elevation (0&ndash;2000 m), distance from the coast (0&ndash;12 km), and annual rainfall (180&ndash;5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over ecosystem sulfur biogeochemistry across relatively small spatial scales.

Hawaii

Coupled hydrological and biogeochemical processes controlling variability of nitrogen species in streamflow during autumn in an upland forest

Autumn is a season of dynamic change in forest streams of the northeastern United States due to effects of leaf fall on both hydrology and biogeochemistry. Few studies have explored how interactions of biogeochemical transformations, various nitrogen sources, and catchment flow paths affect stream nitrogen variation during autumn. To provide more information on this critical period, we studied (1) the timing, duration, and magnitude of changes to stream nitrate, dissolved organic nitrogen (DON), and ammonium concentrations; (2) changes in nitrate sources and cycling; and (3) source areas of the landscape that most influence stream nitrogen. We collected samples at higher temporal resolution for a longer duration than typical studies of stream nitrogen during autumn. This sampling scheme encompassed the patterns and extremes that occurred during base flow and stormflow events of autumn. Base flow nitrate concentrations decreased by an order of magnitude from 5.4 to 0.7 &micro;mol L &minus;1 during the week when most leaves fell from deciduous trees. Changes to rates of biogeochemical transformations during autumn base flow explained the low nitrate concentrations; in-stream transformations retained up to 72% of the nitrate that entered a stream reach. A decrease of in-stream nitrification coupled with heterotrophic nitrate cycling were primary factors in the seasonal nitrate decline. The period of low nitrate concentrations ended with a storm event in which stream nitrate concentrations increased by 25-fold. In the ensuing weeks, peak stormflow nitrate concentrations progressively decreased over closely spaced, yet similarly sized events. Most stormflow nitrate originated from nitrification in near-stream areas with occasional, large inputs of unprocessed atmospheric nitrate, which has rarely been reported for nonsnowmelt events. A maximum input of 33% unprocessed atmospheric nitrate to the stream occurred during one event. Large inputs of unprocessed atmospheric nitrate show direct and rapid effects on forest streams that may be widespread, although undocumented, throughout nitrogen-polluted temperate forests. In contrast to a week-long nitrate decline during peak autumn litterfall, base flow DON concentrations increased after leaf fall and remained high for 2 months. Dissolved organic nitrogen was hydrologically flushed to the stream from riparian soils during stormflow. In contrast to distinct seasonal changes in base flow nitrate and DON concentrations, ammonium concentrations were typically at or below the detection limit, similar to the rest of the year. Our findings reveal couplings among catchment flow paths, nutrient sources, and transformations that control seasonal extremes of stream nitrogen in forested landscapes.

Vermont

Transport of nitrate in the Mississippi river in July-August 1999

Lagrangian sampling was conducted on the Mississippi River in late July through early August 1999 to test the hypothesis that nitrate (NO 3 - ) is transported conservatively in the Mississippi River. Three different approaches were pursued to test the hypothesis: (1) a mass balance for NO 3 - was evaluated for evidence of net gains and losses, (2) stable isotopes of NO 3 - were measured (δ 15 N and δ 18 O) to determine if fractionation occurred, and (3) the concentrations of dissolved gases (N 2 O, N 2 and Ar) in river water were measured and compared to theoretical equilibrium concentrations. Integrated water samples and flow measurements were obtained at 10 sites on the Mississippi River and 7 sites near the mouths of major tributaries from northern Iowa to southern Louisiana, a distance of about 2,250 river kilometers. Mass balance calculations indicate that more than 80 percent of the NO 3 - mass discharged from the Mississippi River (1,930 metric tons/day) during the study period originated in the first 500 river kilometers of the study reach. The mass balance calculations also indicate that NO 3 - was not lost from the water column upstream of Vicksburg, MS, but that there might have been some loss of NO 3 - in the lower 700 kilometers of the study reach. The stable isotope ratios of N and O (δ 15 N and δ 18 O) of NO 3 - were consistent with mixing and transport in the absence of fractionating gains or losses. The concentrations of nitrogen (N 2 ) and argon (Ar) dissolved in river water decreased in the downstream direction, approximately in equilibrium with air at increasing temperatures, giving no evidence of gains or losses of N 2 by nitrogen fixation or denitrification. Nitrous oxide (N 2 O) concentrations in the Mississippi River were approximately 26 to 200 percent of air saturation, indicating relatively low net production by combination of nitrification and denitrification. Results from this study indicate that most (>90%) of the NO 3 - that entered the Mississippi River during July-August 1999 was transported to the Gulf of Mexico.

Mississippi River

The contribution of evaporation from the Great Lakes to the continental atmosphere: estimate based on stable isotope data

The isotopic composition of precipitation and river runoff in the vicinity of the North American Great Lakes is characterized by a higher deuterium-excess value than observed in the advecting air masses. It is suggested that this indicates that evaporated moisture from the surface waters is mixed with the atmosphere waters. A preliminary estimate of the atmospheric water balance during summer and autumn indicates that between 4.6%–15.7% of the atmospheric water content downwind from the Great Lakes is derived from lake evaporation during summer.

Geophysical Research Letters

Tracking nonpoint source nitrogen pollution in human-impacted watersheds

Nonpoint source nitrogen (N) pollution is a leading contributor to U.S. water quality impairments. We combined watershed N mass balances and stable isotopes to investigate fate and transport of nonpoint N in forest, agricultural, and urbanized watersheds at the Baltimore Long-Term Ecological Research site. Annual N retention was 55%, 68%, and 82% for agricultural, suburban, and forest watersheds, respectively. Analysis of &delta; 15 N-NO 3 &ndash; , and &delta; 18 O-NO 3 &ndash; indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between &delta; 15 N-NO 3 &ndash; and &delta; 18 O-NO 3 &ndash; in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed &sim;50% at peak storm N loads). Positive correlations between &delta; 15 N-NO 3 &ndash; and &delta; 18 O-NO 3 &ndash; in watersheds suggested denitrification was removing septic system and agriculturally derived N, but N from belowground leaking sewers was less susceptible to denitrification. N transformations were also observed in a storm drain (no natural drainage network) potentially due to organic carbon inputs. Overall, nonpoint sources such as atmospheric deposition, wastewater, and fertilizer showed different susceptibility to watershed N export. There were large changes in nitrate sources as a function of runoff, and anticipating source changes in response to climate and storms will be critical for managing nonpoint N pollution.

Environmental Science & Technology

How reservoirs alter drinking water quality: Organic matter sources, sinks, and transformations

Within reservoirs, production, transformation, and loss of dissolved organic matter (DOM) occur simultaneously. While the balance between production and loss determines whether a reservoir is a net sink or source of DOM, changes in chemical composition are also important because they affect DOM reactivity with respect to disinfection by-product (DBP) formation. The composition of the DOM pool also provides insight into DOM sources and processing, which can inform reservoir management. We examined the concentration and composition of DOM in San Luis Reservoir, a large off-stream impoundment of the California State Water Project. We used a wide array of DOM chemical tracers including dissolved organic carbon (DOC) concentration, trihalomethane and haloacetic acid formation potentials (THMFP and HAAFP, respectively), absorbance properties, isotopic composition, lignin phenol content, and structural groupings determined by 13 C nuclear magnetic resonance (NMR). There were periods when the reservoir was a net source of DOC due to the predominance of algal production (summer), a net sink due to the predominance of degradation (fall&ndash;winter), and balanced between production and consumption (spring). Despite only moderate variation in bulk DOC concentration (3.0&ndash;3.6 mg C/L), changes in DOM composition indicated that terrestrial-derived material entering the reservoir was being degraded and replaced by aquatic-derived DOM produced within the reservoir. Substantial changes in the propensity of the DOM pool to form THMs and HAAs illustrate that the DBP precursor pool was not directly coupled to bulk DOC concentration and indicate that algal production is an important source of DBP precursors. Results suggest reservoirs have the potential to attenuate DOM amount and reactivity with respect to DBP precursors via degradative processes; however, these benefits can be decreased or even negated by the production of algal-derived DOM.

California

Phosphorus dynamics in soils irrigated with reclaimed waste water or fresh water - A study using oxygen isotopic composition of phosphate

Transformations of phosphate (Pi) in different soil fractions were tracked using the stable isotopic composition of oxygen in phosphate ( δ 18 O p ) and Pi concentrations. Clay soil from Israel was treated with either reclaimed waste water (secondary, low grade) or with fresh water amended with a chemical fertilizer of a known isotopic signature. Changes of δ 18 O p and Pi within different soil fractions, during a month of incubation, elucidate biogeochemical processes in the soil, revealing the biological and the chemical transformation impacting the various P pools. P in the soil solution is affected primarily by enzymatic activity that yields isotopic equilibrium with the water molecules in the soil solution. The dissolved P interacts rapidly with the loosely bound P (extracted by bicarbonate). The oxides and mineral P fractions (extracted by NaOH and HCl, respectively), which are considered as relatively stable pools of P, also exhibited isotopic alterations in the first two weeks after P application, likely related to the activity of microbial populations associated with soil surfaces. Specifically, isotopic depletion which could result from organic P mineralization was followed by isotopic enrichment which could result from preferential biological uptake of depleted P from the mineralized pool. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with reclaimed waste water compared to the fertilizer treated soil.

Geoderma

Sources of aerosol nitrate to the Gulf of Aqaba: Evidence from δ15N and δ18O of nitrate and trace metal chemistry

The nitrogen (N) and oxygen (O) isotopic composition (δ 15 N and δ 18 O) of water soluble aerosol nitrate was measured in aerosol samples collected in Eilat, Israel, from August 2003 to November 2004. During this period δ 15 N values ranged from − 6.9‰ to + 1.9‰ and δ 18 O from + 65.1‰ to + 84.9‰ and exhibited strong seasonal variability with higher average δ 15 N values observed in the summer and higher δ 18 O values in the winter. Nitrate isotopic composition was compared with bulk chemical composition and extractable ion and trace metals on co-collected samples linking nitrate isotopic composition to various sources of aerosols to this region. Atmospheric processes impacting the isotopic signatures of nitrate were also considered. Based on back trajectory analyses, the majority of NO 3 − came from air masses originating over the Mediterranean Sea (34%), Western Europe (20%) and the local Negev desert (19%), which contain a larger anthropogenic imprint compared to southern and eastern air masses which are dominated by mineral dust. The potential role of reactive mineral dust aerosols as a regulator of NO 3 − isotopic composition is considered; however, based on factor analysis, neither δ 15 N nor δ 18 O were associated with mineral dust components (such as Fe or Al), but rather with anthropogenic indicators such as Cu, Cd, P and Pb. Seasonality in primary NO x cycling reactions driven by seasonal changes in solar radiation, relative humidity and temperature also influence the observed isotopic signatures. The isotope data, together with trace element analysis, suggests that seasonal variations in both δ 15 N NO3 and δ 18 O NO3 are related to both NO x source and transport processes as well as NO x chemical reactions in the atmosphere. The flux-weighted δ 15 N of aerosol NO 3 − in this area averaged − 2.6‰ making aerosol deposition a substantial contributor of low δ 15 N nitrogen to the oligotrophic waters of the Gulf of Aqaba. Thus, while the flux of atmospheric N to oligotrophic marine systems is smaller than the upward flux of NO 3 − from deep water, it nonetheless represents an important source of new N having a low δ 15 N. Further, if this low δ 15 N signature is not considered, it could interfere with N-fixation estimates based on isotopic composition of dissolved nitrate or particulate organic nitrogen. Thus, atmospheric deposition should be constrained for accurate estimates of marine N-fixation when based on δ 15 N in the ocean. Indeed, in the Gulf of Aqaba, low upper water δ 15 N NO3 values could be related to inputs of atmospheric NO 3 − as well as N-fixation.

Gulf of Aqaba, Eliat

Rainfall-runoff paradox from a natural experimental catchment

As a part of the Chuzhou hydrological experimental system,the No.1 experimental catchment,Nandadish,with drainage area of 7 897 m2 sits on the andesite bedrock with Quaternary deposit of 2.46 m in average.Various runoff components,surface runoff and subsurface runoff including interflow from unsaturated zone,groundwater flow from saturated zone are physically measured using special designed troughs.Several combined types of runoff components are identified as the SR type with surface runoff dominated,SSR type with subsurface runoff dominated and other intermediate types.Examples show that surface runoff accounts for 65% of total runoff for SR type,while the subsurface runoff accounts for 90% in SSR type.In July,the main rainy season,in total,the subsurface runoff contributes an amount of 54.5% of total runoff while groundwater flow accounts for 33.0%.Most 18O data of surface runoff is quite different from that of precipitation.Within the rainfall-runoff process with duration of about 1 400 minutes,averaged 18O of precipitation is -1.210%,while that of surface runoff is -1.132% for Hydrohill catchment (512 m2),-1.065% for Nandadish catchment and -0.801% for Morningflower(4573 m2)which is a catchment with thin layer of rock debris on bedrock.It challenges the assumptions involved in current isotopic hydrograph separation,i.e.,the 18O of surface runoff will not always equal to that of event precipitation and,the evaporation fractionation during the pathway of runoff components could not always be ignored.Event rainfall produces runoff but such runoff contains an amount of water not from the event rainfall,such a paradox exists in all of our experimental catchments.The total old water involved in event runoff accounts for 16% for the SR type while 64% for SSR type.

Chuzhou

Dual nitrate isotopes in dry deposition: Utility for partitioning NOx source contributions to landscape nitrogen deposition

Dry deposition is a major component of total atmospheric nitrogen deposition and thus an important source of bioavailable nitrogen to ecosystems. However, relative to wet deposition, less is known regarding the sources and spatial variability of dry deposition. This is in part due to difficulty in measuring dry deposition and associated deposition velocities. Passive sampling techniques offer potential for improving our understanding of the spatial distribution and sources of gaseous and aerosol N species, referred to here as dry deposition. We report dual nitrate isotopic composition ( δ 15 N and δ 18 O) in actively collected dry and wet deposition across the high‐deposition region of Ohio, New York, and Pennsylvania. We also present results from initial tests to examine the efficacy of using passive nitric acid collectors as a collection medium for isotopic analysis at a site in New York. Isotopic values in actively collected dry deposition, including particulate nitrate and gaseous nitric acid, are compared with those in wet nitrate deposition and surrounding NO x emission sources. δ 15 N values in dry and wet fractions are highest at the westernmost sites and lowest at the easternmost sites, and stationary source NO x emissions (e.g., power plants and incinerators) appear to be the primary control on δ 15 N spatial variability. In contrast, δ 18 O values show a less consistent spatial pattern in dry deposition. Both δ 15 N and δ 18 O show strong seasonality, with higher values in winter than summer. Seasonal variations in stationary source NO x emissions appear to be the most likely explanation for seasonal variations in δ 15 N, whereas seasonal variations in air temperature and solar radiation indicate variable chemical oxidation pathways control δ 18 O patterns. Additionally, we demonstrate the utility of passive samplers for collecting the nitric acid (HNO 3 ) component of dry deposition suitable for isotopic analysis. We observe slight differences in δ 15 N‐HNO 3 values between simultaneous samples collected actively and passively (0.6‰). However, we observe a larger offset in δ 18 O values between actively and passively collected samples; the causes for this offset warrant further investigation. Nonetheless, passive sample collection represents a significant cost savings over active sampling techniques and could allow a more extensive understanding of patterns of dry deposition and associated insights to nitrogen sources across landscapes.

Journal of Geophysical Research: Biogeosciences

Applications of stable isotopes for regional to national-scale water quality and environmental monitoring programs

Isotopes are a potentially powerful component of monitoring and assessment programs aimed at quantifying and mitigating alterations to environments from human activities. In particular, isotopic techniques have proved useful for tracing sources and sinks of various pollutants in large river basins, wetlands, and airsheds. Many of these studies have been conducted at the regional to national scale by building on existing large-scale water, air, and ecological monitoring programs managed by federal and state agencies, and demonstrate the usefulness of isotopes as a complement to standard chemical and hydrological mass balance methods. This chapter presents an overview of how nitrate, particulate organic matter, and water isotopes can be used to interpret spatial patterns and temporal changes in pollution sources, biogeochemical processes, and ecosystem function in watersheds, at the regional to national scale. Examples from several recent and ongoing studies are presented. From the insights developed using varied sampling strategies and isoscapes, we suggest guidelines for future studies in biologically active and human-impacted rivers.

Book chapter