Philip A.M. Bachand

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.

Mercury cycling in agricultural and managed wetlands: A synthesis of methylmercury production, hydrologic export, and bioaccumulation from an integrated field study

With seasonal wetting and drying, and high biological productivity, agricultural wetlands (rice paddies) may enhance the conversion of inorganic mercury (Hg(II)) to methylmercury (MeHg), the more toxic, organic form that biomagnifies through food webs. Yet, the net balance of MeHg sources and sinks in seasonal wetland environments is poorly understood because it requires an annual, integrated assessment across biota, sediment, and water components. We examined a suite of wetlands managed for rice crops or wildlife during 2007-2008 in Californias Central Valley, in an area affected by Hg contamination from historic mining practices. Hydrologic management of agricultural wetlands for rice, wild rice, or fallowed - drying for field preparation and harvest, and flooding for crop growth and post-harvest rice straw decay - led to pronounced seasonality in sediment and aqueous MeHg concentrations that were up to 95-fold higher than those measured concurrently in adjacent, non-agricultural permanently-flooded and seasonally-flooded wetlands. Flooding promoted microbial MeHg production in surface sediment of all wetlands, but extended water residence time appeared to preferentially enhance MeHg degradation and storage. When incoming MeHg loads were elevated, individual fields often served as a MeHg sink, rather than a source. Slow, horizontal flow of shallow water in the agricultural wetlands led to increased importance of vertical hydrologic fluxes, including evapoconcentration of surface water MeHg and transpiration-driven advection into the root zone, promoting temporary soil storage of MeHg. Although this hydrology limited MeHg export from wetlands, it also increased MeHg exposure to resident fish via greater in situ aqueous MeHg concentrations. Our results suggest that the combined traits of agricultural wetlands - slow-moving shallow water, manipulated flooding and drying, abundant labile plant matter, and management for wildlife - may enhance microbial methylation of Hg(II) and MeHg exposure to local biota, as well as export to downstream habitats during uncontrolled winter-flow events.

Differentiating transpiration from evaporation in seasonal agricultural wetlands and the link to advective fluxes in the root zone

The current state of science and engineering related to analyzing wetlands overlooks the importance of transpiration and risks data misinterpretation. In response, we developed hydrologic and mass budgets for agricultural wetlands using electrical conductivity (EC) as a natural conservative tracer. We developed simple differential equations that quantify evaporation and transpiration rates using flow rates and tracer concentrations at wetland inflows and outflows. We used two ideal reactor model solutions, a continuous flow stirred tank reactor (CFSTR) and a plug flow reactor (PFR), to bracket real non-ideal systems. From those models, estimated transpiration ranged from 55% (CFSTR) to 74% (PFR) of total evapotranspiration (ET) rates, consistent with published values using standard methods and direct measurements. The PFR model more appropriately represents these non-ideal agricultural wetlands in which check ponds are in series. Using a flux model, we also developed an equation delineating the root zone depth at which diffusive dominated fluxes transition to advective dominated fluxes. This relationship is similar to the Peclet number that identifies the dominance of advective or diffusive fluxes in surface and groundwater transport. Using diffusion coefficients for inorganic mercury (Hg) and methylmercury (MeHg) we calculated that during high ET periods typical of summer, advective fluxes dominate root zone transport except in the top millimeters below the sediment-water interface. The transition depth has diel and seasonal trends, tracking those of ET. Neglecting this pathway has profound implications: misallocating loads along different hydrologic pathways; misinterpreting seasonal and diel water quality trends; confounding Ficks First Law calculations when determining diffusion fluxes using pore water concentration data; and misinterpreting biogeochemical mechanisms affecting dissolved constituent cycling in the root zone. In addition, our understanding of internal root zone cycling of Hg and other dissolved constituents, benthic fluxes, and biological irrigation may be greatly affected.

Methylmercury production in and export from agricultural wetlands in California, USA: The need to account for physical transport processes into and out of the root zone

Concentration and mass balance analyses were used to quantify methylmercury (MeHg) loads from conventional (white) rice, wild rice, and fallowed fields in northern Californias Yolo Bypass. These analyses were standardized against chloride to distinguish transport pathways and net ecosystem production (NEP). During summer, chloride loads were both exported with surface water and moved into the root zone at a 2:1 ratio. MeHg and dissolved organic carbon (DOC) behaved similarly with surface water and root zone exports at ~3:1 ratio. These trends reversed in winter with DOC, MeHg, and chloride moving from the root zone to surface waters at rates opposite and exceeding summertime root zone fluxes. These trends suggest that summer transpiration advectively moves constituents from surface water into the root zone, and winter diffusion, driven by concentration gradients, subsequently releases those constituents into surface waters. The results challenge a number of paradigms regarding MeHg. Specifically, biogeochemical conditions favoring microbial MeHg production do not necessarily translate to synchronous surface water exports; MeHg may be preserved in the soils allowing for release at a later time; and plants play a role in both biogeochemistry and transport. Our calculations show that NEP of MeHg occurred during both summer irrigation and winter flooding. Wild rice wet harvesting and winter flooding of white rice fields were specific practices that increased MeHg export, both presumably related to increased labile organic carbon and disturbance. Outflow management during these times could reduce MeHg exports. Standardizing MeHg outflow:inflow concentration ratios against natural tracers (e.g. chloride, EC) provides a simple tool to identify NEP periods. Summer MeHg exports averaged 0.2 to 1 μg m(-2) for the different agricultural wetland fields, depending upon flood duration. Average winter MeHg exports were estimated at 0.3 μg m(-2). These exports are within the range reported for other shallow aquatic systems.

Implications of using On-Farm Flood Flow Capture to recharge groundwater and mitigate flood risks along the Kings River, CA

The agriculturally productive San Joaquin Valley faces two severe hydrologic issues: persistent groundwater overdraft and flooding risks. Capturing flood flows for groundwater recharge could help address both of these issues, yet flood flow frequency, duration, and magnitude vary greatly as upstream reservoir releases are affected by snowpack, precipitation type, reservoir volume, and flood risks. This variability makes dedicated, engineered recharge approaches expensive. Our work evaluates leveraging private farmlands in the Kings River Basin to capture flood flows for direct and in lieu recharge, calculates on-farm infiltration rates, assesses logistics, and considers potential water quality issues. The Natural Resources Conservation Service (NRCS) soil series suggested that a cementing layer would hinder recharge. The standard practice of deep ripping fractured the layer, resulting in infiltration rates averaging 2.5 in d(-1) (6 cm d(-1)) throughout the farm. Based on these rates 10 acres are needed to infiltrate 1 cfs (100 m(3) h(-1)) of flood flows. Our conceptual model predicts that salinity and nitrate pulses flush initially to the groundwater but that groundwater quality improves in the long term due to pristine flood flows low in salts or nitrate. Flood flow capture, when integrated with irrigation, is more cost-effective than groundwater pumping.

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 Californias 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.

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 Californias 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.

Dissolved Organic Matter Compositional Change and Biolability During Two Storm Runoff Events in a Small Agricultural Watershed

Agricultural watersheds are globally pervasive, supporting fundamentally different organic matter source, composition, and concentration profiles in comparison to natural systems. Similar to natural systems, agricultural storm runoff exports large amounts of organic carbon from agricultural land into waterways. But intense management of upper soil layers, waterway channelization, wetland and riparian habitat removal, and post-harvest vegetation removal promise to uniquely drive organic matter release to waterways. During a winter first flush and a subsequent storm event, this study investigated the influence of a small agricultural watershed on dissolved organic matter (DOM) source, composition, and biolability. Stormwater discharge released strongly terrestrial yet biolabile (23 to 32%) dissolved organic carbon (DOC). Following a 21 day bioassay, a parallel factor (PARAFAC) analysis identified an 80% reduction in a protein-like (phenylpropyl) component (C2) that was previously correlated to lignin phenol concentration, and a 10% reduction in a humic-like, terrestrially sourced component (C4). Storm-driven releases tripled DOC concentration (from 2.8 to 8.7 mg L-1) during the first flush event in comparison to base flow, and were terrestrially sourced, with an 8-fold increase in vascular plant derived lignin phenols (23.0 to 185 μg L-1). As inferred from system hydrology, lignin composition, and nitrate as a groundwater tracer, an initial pulse of dilute water from the upstream watershed caused a counterclockwise DOC hysteresis loop. DOC concentrations peaked after 3.5 days, with the delay between peak discharge and peak DOC attributed to stormwater hydrology and a period of initial water repellency of agricultural soils, which delayed DOM leaching.

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.

Rice Drain Management to Reduce Seepage Exports in the Sacramento–San Joaquin Delta, California

Many deltas worldwide face subsidence issues due to increased anthropogenic activity. The Sacramento-San Joaquin delta similarly faces ongoing subsidence, more than 8 m in some areas, that increases levee failure risks and threatens the security of this water source for 25 million California residents and 1.2 million ha of agriculture. Rice ( L.) fields are an integral part of a proposed new strategy for managing subsidence because they have been shown to stop subsidence and provide an alternative crop for growers. Two important considerations for implementing rice fields are additional water requirement and the effect on water quality from mobilized dissolved organic carbon (DOC) and disinfection byproduct precursors. To understand constituent transport and potential management opportunities for rice farming, a plug flow reactor mass balance model was used to quantify surface and subsurface hydrologic pathways. Management of adjacent drainage ditch water levels under low and high scenarios were tested as a strategy to reduce seepage and water quality loads. Under high drains, groundwater met 10% of evapotranspiration (ET). Low drains resulted in a 100% increase in ET demand, which was met by surface water applied for irrigation. High drains reduced subsurface seepage by 95%. Subsurface DOC, trihalomethane, and total dissolved nitrogen loads were reduced 10-fold in high drains compared with low drains. Flow rate accounted for 74 to 90% of load variance and was the primary determinant of constituent loads. Thoughtful implementation of rice cultivation, with high water levels in adjacent drains, can be leveraged to reduce irrigation water demand and constituent load outputs.