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.

Effects of ferric sulfate and polyaluminum chloride coagulation enhanced treatment wetlands on Typha growth, soil and water chemistry.

Land surface subsidence is a concern in many deltas worldwide as it contributes to water quality degradation, loss of fertile land and increased potential for levee failure. As a possible solution to these concerns, on-site coagulation enhanced treatment wetlands (CETWs), coagulation water treatment followed by wetland passage serving as a settling basin, were implemented in a field-scale study located on a subsided island of the Sacramento-San Joaquin Delta in northern California under three treatments; coagulation with polyaluminum chloride (PAC), coagulation with ferric sulfate and an untreated control. Because CETWs offer a relatively novel solution for water quality improvement and subsidence reversal due to its low-infrastructure requirements and in-situ nature, effects from these systems remain uncharted and they may have adverse effects on plant biomass production that also contribute to sediment accretion. This study focuses on the effect CETWs had on the growth of Typha spp.; the dominant vegetation in the wetlands. Plant growth parameters and nutrient content were measured in conjunction with soil, pore water and surface water chemistry. Soil analysis indicated there was no intermixing of newly formed flocs and original soil material. Where there was significant deposition of floc, PAC treatment reduced phosphate concentrations and ferric sulfate treatment increased total Fe concentrations in surrounding water compared to the control. Results indicated coagulation treatments had no negative effects on Typha leaf nutrient content, Typha growth or allometric parameters. Additionally, no signs of plant toxicity such as necrosis, wilting or chlorosis were observed in any of the treatments. Overall, this study suggests that CETWs are viable treatment option for water quality improvement and sediment accretion while having no negative impact on the growth of Typha plants.

Mercury sequestration and transformation in chemically enhanced treatment wetlands.

Mercury (Hg) pollution is a concern to human and wildlife health worldwide, and management strategies that reduce Hg inputs to aquatic systems are of broad interest. Using a replicated field-scale study in California's Sacramento-San Joaquin Delta, we tested the effectiveness of chemically enhanced treatment wetlands (CETWs) under two coagulation treatments, polyaluminum chloride (Al treatment) and ferric sulfate (Fe treatment), in their initial removal and longer-term sequestration of Hg compared to untreated control wetlands. The primary mechanism for Hg removal by CETWs was the transfer of Hg from filtered forms to insoluble particulate forms and enhanced settling of particles. CETWs resulted in total Hg annual load removals of 63 ng m-2 yr-1 (71%) and 54 ng m-2 yr-1 (54%) for the Al and Fe treatments, respectively. Control wetlands removed significantly less at 13 ng m-2 yr-1 (14%). Load removals indicate that Fe treatment wetlands more effectively reduced filtered and total methylmercury (MeHg) exports, while Al treatment wetlands more effectively reduced particulate MeHg and total Hg exports. These differences in Hg species load reductions possibly indicate different mechanisms of Hg sequestration; current data suggest more effective floc formation and particle settling was likely responsible for the Al treatment behavior, while either preferential MeHg sequestration or methylation suppression was potentially responsible for Fe treatment behavior. Differences in Hg sequestration behavior post-coagulation between the flocs formed by different coagulants indicate the importance of in-situ studies and the need for careful selection of coagulant treatment depending on the Hg species requiring remediation.

Wetlands receiving water treated with coagulants improve water quality by removing dissolved organic carbon and disinfection byproduct precursors.

Constructed wetlands are used worldwide to improve water quality while also providing critical wetland habitat. However, wetlands have the potential to negatively impact drinking water quality by exporting dissolved organic carbon (DOC) that upon disinfection can form disinfection byproducts (DBPs) like trihalomethanes (THMs) and haloacetic acids (HAAs). We used a replicated field-scale study located on organic rich soils in California's Sacramento-San Joaquin Delta to test whether constructed flow-through wetlands which receive water high in DOC that is treated with either iron- or aluminum-based coagulants can improve water quality with respect to DBP formation. Coagulation alone removed DOC (66-77%) and THM (67-70%) precursors, and was even more effective at removing HAA precursors (77-90%). Passage of water through the wetlands increased DOC concentrations (1.5-7.5mgL-1), particularly during the warmer summer months, thereby reversing some of the benefits from coagulant addition. Despite this addition, water exiting the wetlands treated with coagulants had lower DOC and DBP precursor concentrations relative to untreated source water. Benefits of the coagulation-wetland systems were greatest during the winter months (approx. 50-70% reduction in DOC and DBP precursor concentrations) when inflow water DOC concentrations were higher and wetland DOC production was lower. Optical properties suggest DOC in this system is predominantly comprised of high molecular weight, aromatic compounds, likely derived from degraded peat soils.

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.

Investigating the Temporal Effects of Metal-Based Coagulants to Remove Mercury from Solution in the Presence of Dissolved Organic Matter.

The presence of mercury (Hg), particularly methylmercury (MeHg), is a concern for both human and ecological health as MeHg is a neurotoxin and can bioaccumulate to lethal levels in upper trophic level organisms. Recent research has demonstrated that coagulation with metal-based salts can effectively remove both inorganic mercury (IHg) and MeHg from solution through association with dissolved organic matter (DOM) and subsequent flocculation and precipitation. In this study, we sought to further examine interactions between Hg and DOM and the resulting organo-metallic precipitate (floc) to assess if (1) newly added IHg could be removed to the same extent as ambient IHg or whether the association between IHg and DOM requires time, and (2) once formed, if the floc has the capacity to remove additional Hg from solution. Agricultural drainage water samples containing ambient concentrations of both DOM and IHg were spiked with a traceable amount of isotopically enriched IHg and dosed with ferric sulfate after 0, 1, 5, and 30 days. Both ambient and newly added IHg were removed within hours, with 69-79 % removed. To a separate sample set, isotopically enriched IHg was added to solution after floc had formed. Under those conditions, 81-95 % of newly added Hg was removed even at Hg concentrations 1000-fold higher than ambient levels. Results of this study indicate coagulation with ferric sulfate effectively removes both ambient and newly added IHg entering a system and suggests rapid association between IHg and DOM. This work also provides new information regarding the ability of floc to remove additional Hg from solution even after it has formed.

Experimental dosing of wetlands with coagulants removes mercury from surface water and decreases mercury bioaccumulation in fish.

Mercury pollution is widespread globally, and strategies for managing mercury contamination in aquatic environments are necessary. We tested whether coagulation with metal-based salts could remove mercury from wetland surface waters and decrease mercury bioaccumulation in fish. In a complete randomized block design, we constructed nine experimental wetlands in California's Sacramento-San Joaquin Delta, stocked them with mosquitofish (Gambusia affinis), and then continuously applied agricultural drainage water that was either untreated (control), or treated with polyaluminum chloride or ferric sulfate coagulants. Total mercury and methylmercury concentrations in surface waters were decreased by 62% and 63% in polyaluminum chloride treated wetlands and 50% and 76% in ferric sulfate treated wetlands compared to control wetlands. Specifically, following coagulation, mercury was transferred from the filtered fraction of water into the particulate fraction of water which then settled within the wetland. Mosquitofish mercury concentrations were decreased by 35% in ferric sulfate treated wetlands compared to control wetlands. There was no reduction in mosquitofish mercury concentrations within the polyaluminum chloride treated wetlands, which may have been caused by production of bioavailable methylmercury within those wetlands. Coagulation may be an effective management strategy for reducing mercury contamination within wetlands, but further studies should explore potential effects on wetland ecosystems.

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10(-3)m(2)mol(-1) (s.d. 3.5×10(-3)) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg-DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

Removal of inorganic mercury and methylmercury from surface waters following coagulation of dissolved organic matter with metal-based salts.

The presence of inorganic mercury (IHg) and methylmercury (MeHg) in surface waters is a health concern worldwide. This study assessed the removal potential use of metal-based coagulants as a means to remove both dissolved IHg and MeHg from natural waters and provides information regarding the importance of Hg associations with the dissolved organic matter (DOM) fraction and metal hydroxides. Previous research indicated coagulants were not effective at removing Hg from solution; however these studies used high concentrations of Hg and did not reflect naturally occurring concentrations of Hg. In this study, water collected from an agricultural drain in the Sacramento-San Joaquin Delta was filtered to isolate the dissolved organic matter (DOM) fraction. The DOM was then treated with a range of coagulant doses to determine the efficacy of removing all forms of Hg from solution. Three industrial-grade coagulants were tested: ferric chloride, ferric sulfate, and polyaluminum chloride. Coagulation removed up to 85% of DOM from solution. In the absence of DOM, all three coagulants released IHg into solution, however in the presence of DOM the coagulants removed up to 97% of IHg and 80% of MeHg. Results suggest that the removal of Hg is mediated by DOM-coagulant interactions. There was a preferential association of IHg with the more aromatic, higher molecular weight fraction of DOM but no such relationship was found for MeHg. This study offers new fundamental insights regarding large-scale removal of Hg at environmentally relevant regarding large-scale removal of Hg at environmentally relevant concentrations.

Determining sources of dissolved organic carbon and disinfection byproduct precursors to the McKenzie River, Oregon.

This study was conducted to determine the main sources of dissolved organic carbon (DOC) and disinfection byproduct (DBP) precursors to the McKenzie River, Oregon (USA). Water samples collected from the mainstem, tributaries, and reservoir outflows were analyzed for DOC concentration and DBP formation potentials (trihalomethanes [THMFPs] and haloacetic acids [HAAFPs]). In addition, optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) were measured to provide insight into DOM composition and assess whether optical properties are useful proxies for DOC and DBP precursor concentrations. Optical properties indicative of composition suggest that DOM in the McKenzie River mainstem was primarily allochthonous--derived from soils and plant material in the upstream watershed. Downstream tributaries had higher DOC concentrations than mainstem sites (1.6 +/- 0.4 vs. 0.7 +/- 0.3 mg L(-1)) but comprised < 5% ofmainstem flows and had minimal effect on overall DBP precursor loads. Water exiting two large upstream reservoirs also had higher DOC concentrations than the mainstem site upstream of the reservoirs, but optical data did not support in situ algal production as a source of the added DOC during the study. Results suggest that the first major rain event in the fall contributes DOM with high DBP precursor content. Although there was interference in the absorbance spectra in downstream tributary samples, fluorescence data were strongly correlated to DOC concentration (R2 = 0.98), THMFP (R2 = 0.98), and HAAFP (R2 = 0.96). These results highlight the value of using optical measurements for identifying the concentration and sources of DBP precursors in watersheds, which will help drinking water utilities improve source water monitoring and management programs.