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 NH4+ from treated wastewater effluent and that NH4+ was lost rapidly while NO3- 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 NH4+ from the Sacramento River and higher conductivity water elevated in NO3- from landward tributaries. Deviations from expected conservative mixing of these sources were spatially variable but broadly indicative of local inputs of treated wastewater effluent NO3-, conversion of Sacramento River NH4+ to NO3- via nitrification, uptake of NH4+ and NO3- 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.

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 ±â€¯4 µg L-1) and were comprised primarily of small phytoplankton cells (<5 µm, 74 ±â€¯8%), lower ammonium concentrations (1 ±â€¯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 ±â€¯5 µM) and lower chlorophyll-a concentration (5 ±â€¯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 ±â€¯17% of the chlorophyll-a - nearly double the concentration seen in shorter residence time zones (22 ±â€¯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.

Unprocessed Atmospheric Nitrate in Waters of the Northern Forest Region in the U.S. 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 (δ18O and δ15N) 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.

Internal loading of phosphate in Lake Erie Central Basin.

After significant reductions in external phosphorus (P) loads, and subsequent water quality improvements in the early 1980s, the water quality of Lake Erie has declined considerably over the past decade. The frequency and magnitude of harmful algal blooms (primarily in the western basin) and the extent of hypoxic bottom waters in the central basin have increased. The decline in ecosystem health, despite meeting goals for external P loads, has sparked a renewed effort to understand P cycling in the lake. We use pore-water P concentration profiles and sediment cores incubation experiments to quantify the P flux from Lake Erie central basin sediments. In addition, the oxygen isotopes of phosphate were investigated to assess the isotopic signature of sedimentary phosphate inputs relative to the isotopic signature of phosphate in lake water. Extrapolating the total P sediment flux based on the pore-water profiles to the whole area of the central basin ranged from 300 to 1250metric tons per year and using the flux based on core incubation experiments an annual flux of roughly 2400metric tons of P is calculated. These estimates amount to 8-20% of the total external input of P to Lake Erie. The isotopic signature of phosphate in the extractable fraction of the sediments (~18‰) can explain the non-equilibrium isotope values of dissolved phosphate in the deep water of the central basin of Lake Erie, and this is consistent with sediments as an important internal source of P in the Lake.

Using Continuous Underway Isotope Measurements To Map Water Residence Time in Hydrodynamically Complex Tidal Environments.

Stable isotopes present in water (δ2H, δ18O) have been used extensively to evaluate hydrological processes on the basis of parameters such as evaporation, precipitation, mixing, and residence time. In estuarine aquatic habitats, residence time (τ) is a major driver of biogeochemical processes, affecting trophic subsidies and conditions in fish-spawning habitats. But τ is highly variable in estuaries, owing to constant changes in river inflows, tides, wind, and water height, all of which combine to affect τ in unpredictable ways. It recently became feasible to measure δ2H and δ18O continuously, at a high sampling frequency (1 Hz), using diffusion sample introduction into a cavity ring-down spectrometer. To better understand the relationship of τ to biogeochemical processes in a dynamic estuarine system, we continuously measured δ2H and δ18O, nitrate and water quality parameters, on board a small, high-speed boat (5 to >10 m s-1) fitted with a hull-mounted underwater intake. We then calculated τ as is classically done using the isotopic signals of evaporation. The result was high-resolution (∼10 m) maps of residence time, nitrate, and other parameters that showed strong spatial gradients corresponding to geomorphic attributes of the different channels in the area. The mean measured value of τ was 30.5 d, with a range of 0-50 d. We used the measured spatial gradients in both τ and nitrate to calculate whole-ecosystem uptake rates, and the values ranged from 0.006 to 0.039 d-1. The capability to measure residence time over single tidal cycles in estuaries will be useful for evaluating and further understanding drivers of phytoplankton abundance, resolving differences attributable to mixing and water sources, explicitly calculating biogeochemical rates, and exploring the complex linkages among time-dependent biogeochemical processes in hydrodynamically complex environments such as estuaries.

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 (δ(34)S VCDT) of -0.8‰. Bulk deposition on the island of Maui had a δ(34)S VCDT that varied temporally, spanned a range from +8.2 to +19.7‰, and reflected isotopic mixing from three sources: sea-salt (+21.1‰), marine biogenic emissions (+15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to +2.7‰) to relatively high (+17.8 to +19.3‰) soil δ(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‰ and generally decreased with increasing elevation (0-2000 m), distance from the coast (0-12 km), and annual rainfall (180-5000 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.

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 δ(15)N-NO(3)(-), and δ(18)O-NO(3)(-) indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between δ(15)N-NO(3)(-) and δ(18)O-NO(3)(-) in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed ∼50% at peak storm N loads). Positive correlations between δ(15)N-NO(3)(-) and δ(18)O-NO(3)(-) 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.

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems.

The oxygen isotopic composition of dissolved inorganic phosphate (delta18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source delta18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for delta18Op to be a useful tool for source tracking, the delta18Op of phosphate sources must be distinguishable from one another; however, the delta18Op of potential sources has not been well characterized. We measured the delta18Op of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of delta18Op, values (from +8.4 to +24.9 per thousand) for the various sources, and statistically significant differences were found between several of the source types. delta18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in delta18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and delta18Op can be used for identifying phosphate sources to aquatic systems.

Using oxygen isotopes of phosphate to trace phosphorus sources and cycling in Lake Erie.

Water samples collected during three sampling trips to Lake Erie displayed oxygen isotopic values of dissolved phosphate (delta18Op) that were largely out of equilibrium with ambient conditions, indicating that source signatures may be discerned. delta18Op, values in the Lake ranged from +10% per hundred to +17% per hundred, whereas the equilibrium value was expected to be around +14% per hundred. The riverine weighted average delta18Op, value was +11% per hundred and may represent one source of phosphate to the Lake. The lake delta18Op, values indicated that there must be one or more as yet uncharacterized source(s) of phosphate with a high delta18Op value. Potential sources other than rivers are not yet well-characterized with respectto delta18Op of phosphate, but we speculate that a likely source may be the release of phosphate from sediments under reducing conditions created during anoxic events in the hypolimnion of the central basin of Lake Erie. Identifying potential phosphorus sources to the Lake is vital for designing effective management plans for reducing nutrient inputs and associated eutrophication.

Sources and transformations of nitrate from streams draining varying land uses: evidence from dual isotope analysis.

Knowledge of key sources and biogeochemical processes that affect the transport of nitrate (NO(3)(-)) in streams can inform watershed management strategies for controlling downstream eutrophication. We applied dual isotope analysis of NO(3)(-) to determine the dominant sources and processes that affect NO(3)(-) concentrations in six stream/river watersheds of different land uses. Samples were collected monthly at a range of flow conditions for 15 mo during 2004-05 and analyzed for NO(3)(-) concentrations, delta(15)N(NO3), and delta(18)O(NO3). Samples from two forested watersheds indicated that NO(3)(-) derived from nitrification was dominant at baseflow. A watershed dominated by suburban land use had three delta(18)O(NO3) values greater than +25 per thousand, indicating a large direct contribution of atmospheric NO(3)(-) transported to the stream during some high flows. Two watersheds with large proportions of agricultural land use had many delta(15)N(NO3) values greater than +9 per thousand, suggesting an animal waste source consistent with regional dairy farming practices. These data showed a linear seasonal pattern with a delta(18)O(NO3):delta (15)N(NO3) of 1:2, consistent with seasonally varying denitrification that peaked in late summer to early fall with the warmest temperatures and lowest annual streamflow. The large range of delta (15)N(NO3) values (10 per thousand) indicates that NO(3)(-) supply was likely not limiting the rate of denitrification, consistent with ground water and/or in-stream denitrification. Mixing of two or more distinct sources may have affected the seasonal isotope patterns observed in these two agricultural streams. In a mixed land use watershed of large drainage area, none of the source and process patterns observed in the small streams were evident. These results emphasize that observations at watersheds of a few to a few hundred km(2) may be necessary to adequately quantify the relative roles of various NO(3)(-) transport and process patterns that contribute to streamflow in large basins.

Investigation of river eutrophication as part of a low dissolved oxygen total maximum daily load implementation.

In the United States, environmentally impaired rivers are subject to regulation under total maximum daily load (TMDL) regulations that specify watershed wide water quality standards. In California, the setting of TMDL standards is accompanied by the development of scientific and management plans directed at achieving specific water quality objectives. The San Joaquin River (SJR) in the Central Valley of California now has a TMDL for dissolved oxygen (DO). Low DO conditions in the SJR are caused in part by excessive phytoplankton growth (eutrophication) in the shallow, upstream portion of the river that create oxygen demand in the deeper estuary. This paper reports on scientific studies that were conducted to develop a mass balance on nutrients and phytoplankton in the SJR. A mass balance model was developed using WARMF, a model specifically designed for use in TMDL management applications. It was demonstrated that phytoplankton biomass accumulates rapidly in a 88 km reach where plankton from small, slow moving tributaries are diluted and combined with fresh nutrient inputs in faster moving water. The SJR-WARMF model was demonstrated to accurately predict phytoplankton growth in the SJR. Model results suggest that modest reductions in nutrients alone will not limit algal biomass accumulation, but that combined strategies of nutrient reduction and algal control in tributaries may have benefit. The SJR-WARMF model provides stakeholders a practical, scientific tool for setting remediation priorities on a watershed scale.

Evaluating regional patterns in nitrate sources to watersheds in National Parks of the Rocky Mountains using nitrate isotopes.

In the Rocky Mountains, there is uncertainty about the source areas and emission types that contribute to nitrate (NO3) deposition, which can adversely affect sensitive aquatic habitats of high-elevation watersheds. Regional patterns in NO3 deposition sources were evaluated using NO3 isotopes in five National Parks, including 37 lakes and 7 precipitation sites. Results indicate that lake NO3 ranged from detection limit to 38 microeq/L, delta18O (NO3) ranged from -5.7 to +21.3% per thousand, and delta15N (NO3) ranged from -6.6 to +4.6 per thousand. delta18O (NO3) in precipitation ranged from +71 to +78% per thousand. delta15N (NO3) in precipitation and lakes overlap; however, delta15N (NO3) in precipitation is more depleted than delta15N (NO3) in lakes, ranging from -5.5 to -2.0 per thousand. delta15N (NO3) values are significantly related (p < 0.05) to wet deposition of inorganic N, sulfate, and acidity, suggesting that spatial variability of delta15N (NO3) over the Rocky Mountains may be related to source areas of these solutes. Regional patterns show that NO3 and delta15N (NO3) are more enriched in lakes and precipitation from the southern Rockies and at higher elevations compared to the northern Rockies. The correspondence of high NO3 and enriched delta15N (NO3) in precipitation with high NO3 and enriched delta15N (NO3) in lakes, suggests that deposition of inorganic N in wetfall may affect the amount of NO3 in lakes through a combination of direct and indirect processes such as enhanced nitrification.

Identifying sources of nitrogen to Hanalei Bay, Kauai, utilizing the nitrogen isotope signature of macroalgae.

Sewage effluent, storm runoff, discharge from polluted rivers, and inputs of groundwater have all been suggested as potential sources of land derived nutrients into Hanalei Bay, Kauai. We determined the nitrogen isotopic signatures (delta(15)N) of different nitrate sources to Hanalei Bay along with the isotopic signature recorded by 11 species of macroalgal collected in the Bay. The macroalgae integrate the isotopic signatures of the nitrate sources over time, thus these data along with the nitrate to dissolved inorganic phosphate molar ratios (N:P) of the macroalgae were used to determine the major nitrate source to the bay ecosystem and which of the macro-nutrients is limiting algae growth, respectively. Relatively low delta(15)N values (average -0.5% per hundred) were observed in all algae collected throughout the Bay; implicating fertilizer, rather than domestic sewage, as an important external source of nitrogen to the coastal water around Hanalei. The N:P ratio in the algae compared to the ratio in the Bay waters imply that the Hanalei Bay coastal ecosystem is nitrogen limited and thus, increased nitrogen input may potentially impact this coastal ecosystem and specifically the coral reefs in the Bay. Identifying the major source of nutrient loading to the Bay is important for risk assessment and potential remediation plans.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails.

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail delta13C values (mean +/- standard deviation) were -15.4 +/- 1.0 and -18.8 +/- 0.8 per thousand and delta15N values were 10.4 +/- 0.7 and 9.4 +/- 0.6 per thousand for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region.

Stable isotope food web analysis of a large subtropical lake: alternative explanations for 15N enrichment of pelagic vs. littoral fisheries.

The food webs of littoral, pelagic, and littoral-pelagic ecotone (interface) regions of a large subtropical lake were investigated using stable isotope ratio methods, expanding the focus of a previous fish-only study to include other food web components such as primary producers and invertebrates. In these food webs, delta13C increased approximately 4 per thousand and delta15N increased approximately 10 per thousand from primary producers to fish. The delta15N of fish was approximately 9 per thousand in the littoral zone, approximately 10 per thousand in the ecotone, and approximately 12 per thousand in the pelagic zone. The cross-habitat enrichment in fish 15N corresponded with both an increase in the size of fish and an increase in the d15N of primary consumers (mollusks). Despite larger body size in the pelagic zone, fish in all three habitats appear to occur at the same average trophic level (TL = 4), assuming an enrichment factor of 3.4 per thousand per trophic level, and normalizing to the delta15N of primary consumers.

Oxygen isotope corrections for online delta(34)S analysis.

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the delta(34)S isotopic composition of plants, animals and soils. We found that the online technology for automated delta(34)S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO(2) produced, and as a result calculated delta(34)S values were often 1-3 per thousand 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 SO(2)-SiO(2) buffering method that minimizes detrimental oxygen isotope variations in SO(2).