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Widespread occurrence of neuro-active pharmaceuticals and metabolites in 24 Minnesota rivers and wastewaters

Concentrations of 17 neuro-active pharmaceuticals and their major metabolites (bupropion, hydroxy-bupropion, erythro-hydrobupropion, threo-hydrobupropion, carbamazepine, 10,11,-dihydro-10,11,-dihydroxycarbamazepine, 10-hydroxy-carbamazepine, citalopram, N -desmethyl-citalopram, fluoxetine, norfluoxetine, gabapentin, lamotrigine, 2-N-glucuronide-lamotrigine, oxcarbazepine, venlafaxine and O-desmethyl-venlafaxine), were measured in treated wastewater and receiving surface waters from 24 locations across Minnesota, USA. The analysis of upstream and downstream sampling sites indicated that the wastewater treatment plants were the major source of the neuro-active pharmaceuticals and associated metabolites in surface waters of Minnesota. Concentrations of parent compound and the associated metabolite varied substantially between treatment plants (concentrations ± standard deviation of the parent compound relative to its major metabolite) as illustrated by the following examples; bupropion and hydrobupropion 700 ± 1000 ng L − 1 , 2100 ± 1700 ng L − 1 , carbamazepine and 10-hydroxy-carbamazepine 480 ± 380 ng L − 1 , 360 ± 400 ng L − 1 , venlafaxine and O -desmethyl-venlafaxine 1400 ± 1300 ng L − 1 , 1800 ± 2300 ng L − 1 . Metabolites of the neuro-active compounds were commonly found at higher or comparable concentrations to the parent compounds in wastewater effluent and the receiving surface water. Neuro-active pharmaceuticals and associated metabolites were detected only sporadically in samples upstream from the effluent outfall. Metabolite to parent ratios were used to evaluate transformation, and we determined that ratios in wastewater were much lower than those reported in urine, indicating that the metabolites are relatively more labile than the parent compounds in the treatment plants and in receiving waters. The widespread occurrence of neuro-active pharmaceuticals and metabolites in Minnesota effluents and surface waters indicate that this is likely a global environmental issue, and further understanding of the environmental fate and impacts of these compounds is warranted.

Minnesota↗

Mercury cycling in agricultural and managed wetlands of California: seasonal influences of vegetation on mercury methylation, storage, and transport

Plants are a dominant biologic and physical component of many wetland capable of influencing the internal pools and fluxes of methylmercury (MeHg). To investigate their role with respect to the latter, we examined the changing seasonal roles of vegetation biomass and Hg, C and N composition from May 2007-February 2008 in 3 types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields), and in adjacent managed natural wetlands dominated by cattail and bulrush (tule). We also determined the impact of vegetation on seasonal microbial Hg methylation rates, and Hg and MeHg export via seasonal storage in vegetation, and biotic consumption of rice seed. Despite a compressed growing season of ~ 3 months, annual net primary productivity (NPP) was greatest in white rice fields and carbon more labile (leaf median C:N ratio = 27). Decay of senescent litter (residue) was correlated with microbial MeHg production in winter among all wetlands. As agricultural biomass accumulated from July to August, THg concentrations declined in leaves but MeHg concentrations remained consistent, such that MeHg pools generally increased with growth. Vegetation provided a small, temporary, but significant storage term for MeHg in agricultural fields when compared with hydrologic export. White rice and wild rice seeds reached mean MeHg concentrations of 4.1 and 6.2 ng g dw - 1 , respectively. In white rice and wild rice fields, seed MeHg concentrations were correlated with root MeHg concentrations (r = 0.90, p < 0.001), suggesting transport of MeHg to seeds from belowground tissues. Given the proportionally elevated concentrations of MeHg in rice seeds, white and wild rice crops may act as a conduit of MeHg into biota, especially waterfowl which forage heavily on rice seeds within the Central Valley of California, USA. Thus, while plant tissues and rhizosphere soils provide temporary storage for MeHg during the growing season, export of MeHg is enhanced post-harvest through increased hydrologic and biotic export.

California↗

Mercury cycling in agricultural and managed wetlands of California: experimental evidence of vegetation-driven changes in sediment biogeochemistry and methylmercury production

The role of live vegetation in sediment methylmercury (MeHg) production and associated biogeochemistry was examined in three types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields) and adjacent managed natural wetlands (cattail- and bulrush or tule-dominated) in the Yolo Bypass region of California's Central Valley, USA. During the active growing season for each wetland, a vegetated:de-vegetated paired plot experiment demonstrated that the presence of live plants enhanced microbial rates of mercury methylation by 20 to 669% (median = 280%) compared to de-vegetated plots. Labile carbon exudation by roots appeared to be the primary mechanism by which microbial methylation was enhanced in the presence of vegetation. Pore-water acetate (pw[Ac]) decreased significantly with de-vegetation (63 to 99%) among all wetland types, and within cropped fields, pw[Ac] was correlated with both root density (r = 0.92) and microbial Hg(II) methylation (k meth . r = 0.65). Sediment biogeochemical responses to de-vegetation were inconsistent between treatments for “reactive Hg” (Hg(II)R), as were reduced sulfur and sulfate reduction rates. Sediment MeHg concentrations in vegetated plots were double those of de-vegetated plots (median = 205%), due in part to enhanced microbial MeHg production in the rhizosphere, and in part to rhizoconcentration via transpiration-driven pore-water transport. Pore-water concentrations of chloride, a conservative tracer, were elevated (median = 22%) in vegetated plots, suggesting that the higher concentrations of other constituents around roots may also be a function of rhizoconcentration rather than microbial activity alone. Elevated pools of amorphous iron (Fe) in vegetated plots indicate that downward redistribution of oxic surface waters through transpiration acts as a stimulant to Fe(III)-reduction through oxidation of Fe(II)pools. These data suggest that vegetation significantly affected rhizosphere biogeochemistry through organic exudation and transpiration-driven concentration of pore-water constituents and oxidation of reduced compounds. While the relative role of vegetation varied among wetland types, macrophyte activity enhanced MeHg production.

California↗

River flow changes related to land and water management practices across the conterminous United States

The effects of land and water management practices (LWMP)—such as the construction of dams and roads—on river flows typically have been studied at the scale of single river watersheds or for a single type of LWMP. For the most part, assessments of the relative effects of multiple LWMP within many river watersheds across regional and national scales have been lacking. This study assesses flow alteration—quantified as deviation of several flow metrics from natural conditions—at 4196 gauged rivers affected by a variety of LWMP across the conterminous United States. The most widespread causes of flow changes among the LWMP considered were road density and dams. Agricultural development and wastewater discharges also were associated with flow changes in some regions. Dams generally reduced most attributes of flow, whereas road density, agriculture and wastewater discharges tended to be associated with increased flows compared to their natural condition.

Science of the Total Environment↗

Predicting the toxicity of metal mixtures

The toxicity of single and multiple metal (Cd, Cu, Pb, and Zn) solutions to trout is predicted using an approach that combines calculations of: (1) solution speciation; (2) competition and accumulation of cations (H, Ca, Mg, Na, Cd, Cu, Pb, and Zn) on low abundance, high affinity and high abundance, low affinity biotic ligand sites; (3) a toxicity function that accounts for accumulation and potency of individual toxicants; and (4) biological response. The approach is evaluated by examining water composition from single metal toxicity tests of trout at 50% mortality, results of theoretical calculations of metal accumulation on fish gills and associated mortality for single, binary, ternary, and quaternary metal solutions, and predictions for a field site impacted by acid rock drainage. These evaluations indicate that toxicity of metal mixtures depends on the relative affinity and potency of toxicants for a given aquatic organism, suites of metals in the mixture, dissolved metal concentrations and ratios, and background solution composition (temperature, pH, and concentrations of major ions and dissolved organic carbon). A composite function that incorporates solution composition, affinity and competition of cations for two types of biotic ligand sites, and potencies of hydrogen and individual metals is proposed as a tool to evaluate potential toxicity of environmental solutions to trout.

Science of the Total Environment↗

Health status of Largescale Sucker ( Catostomus macrocheilus ) collected along an organic contaminant gradient in the lower Columbia River, Oregon and Washington, USA

The health of Largescale Sucker ( Catostomus macrocheilus ) in the lower Columbia River (USA) was evaluated using morphometric and histopathological approaches, and its association with organic contaminants accumulated in liver was evaluated in males. Fish were sampled from three sites along a contaminant gradient In 2009, body length and mass, condition factor, gonadosomatic index, and hematocrit were measured in males and females; liver and gonad tissue were collected from males for histological analyses; and organ composites were analyzed for contaminant content in males. In 2010, additional data were collected for males and females, including external fish condition assessment, histopathologies of spleen, kidney and gill and, for males, liver contaminant content. Multivariate analysis of variance indicated that biological traits in males, but not females, differed among sites in 2009 and 2010. Discriminant function analysis indicated that site-related differences among male populations were relatively small in 2009, but in 2010, when more variables were analyzed, males differed among sites in regards to kidney, spleen, and liver histopathologies and gill parasites. Kidney tubular hyperplasia, liver and spleen macrophage aggregations, and gill parasites were generally more severe in the downstream sites compared to the reference location. The contaminant content of male livers was also generally higher downstream, and the legacy pesticide hexachlorobenzene and flame retardants BDE-47 and BDE-154 were the primary drivers for site discrimination. However, bivariate correlations between biological variables and liver contaminants retained in the discriminant models failed to reveal associations between the two variable sets. In conclusion, whereas certain non-reproductive biological traits and liver contaminant contents of male Largescale Sucker differed according to an upstream-downstream gradient in the lower Columbia River, results from this study did not reveal the specific environmental factors responsible for the differences in health status among fish populations.

Science of the Total Environment↗

Spatial and temporal trends in occurrence of emerging and legacy contaminants in the Lower Columbia River 2008-2010

The Lower Columbia River in Oregon and Washington, USA, is an important resource for aquatic and terrestrial organisms, agriculture, and commerce. An 86-mile stretch of the river was sampled over a 3 year period in order to determine the spatial and temporal trends in the occurrence and concentration of water-borne organic contaminants. Sampling occurred at 10 sites along this stretch and at 1 site on the Willamette River using the semipermeable membrane device (SPMD) and the polar organic chemical integrative sampler (POCIS) passive samplers. Contaminant profiles followed the predicted trends of lower numbers of detections and associated concentrations in the rural areas to higher numbers and concentrations at the more urbanized sites. Industrial chemicals, plasticizers, and PAHs were present at the highest concentrations. Differences in concentrations between sampling periods were related to the amount of rainfall during the sampling period. In general, water concentrations of wastewater-related contaminants decreased and concentrations of legacy contaminants slightly increased with increasing rainfall amounts.

Oregon;Washington↗

Discharges of produced waters from oil and gas extraction via wastewater treatment plants are sources of disinfection by-products to receiving streams

Fluids co-produced with oil and gas production (produced waters) are often brines that contain elevated concentrations of bromide. Bromide is an important precursor of several toxic disinfection by-products (DBPs) and the treatment of produced water may lead to more brominated DBPs. To determine if wastewater treatment plants that accept produced waters discharge greater amounts of brominated DBPs, water samples were collected in Pennsylvania from four sites along a large river including an upstream site, a site below a publicly owned wastewater treatment plant (POTW) outfall (does not accept produced water), a site below an oil and gas commercial wastewater treatment plant (CWT) outfall, and downstream of the POTW and CWT. Of 29 DBPs analyzed, the site at the POTW outfall had the highest number detected (six) ranging in concentration from 0.01 to 0.09 μg L − 1 with a similar mixture of DBPs that have been detected at POTW outfalls elsewhere in the United States. The DBP profile at the CWT outfall was much different, although only two DBPs, dibromochloronitromethane (DBCNM) and chloroform, were detected, DBCNM was found at relatively high concentrations (up to 8.5 μg L − 1 ). The water at the CWT outfall also had a mixture of inorganic and organic precursors including elevated concentrations of bromide (75 mg L − 1 ) and other organic DBP precursors (phenol at 15 μg L − 1 ). To corroborate these DBP results, samples were collected in Pennsylvania from additional POTW and CWT outfalls that accept produced waters. The additional CWT also had high concentrations of DBCNM (3.1 μg L − 1 ) while the POTWs that accept produced waters had elevated numbers (up to 15) and concentrations of DBPs, especially brominated and iodinated THMs (up to 12 μg L − 1 total THM concentration). Therefore, produced water brines that have been disinfected are potential sources of DBPs along with DBP precursors to streams wherever these wastewaters are discharged.

Science of the Total Environment↗

Correlation of gene expression and contaminat concentrations in wild largescale suckers: a field-based study

Toxic compounds such as organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ether flame retardants (PBDEs) have been detected in fish, birds, and aquatic mammals that live in the Columbia River or use food resources from within the river. We developed a custom microarray for largescale suckers (Catostomus macrocheilus) and used it to investigate the molecular effects of contaminant exposure on wild fish in the Columbia River. Using Significance Analysis of Microarrays (SAM) we identified 72 probes representing 69 unique genes with expression patterns that correlated with hepatic tissue levels of OCs, PCBs, or PBDEs. These genes were involved in many biological processes previously shown to respond to contaminant exposure, including drug and lipid metabolism, apoptosis, cellular transport, oxidative stress, and cellular chaperone function. The relation between gene expression and contaminant concentration suggests that these genes may respond to environmental contaminant exposure and are promising candidates for further field and laboratory studies to develop biomarkers for monitoring exposure of wild fish to contaminant mixtures found in the Columbia River Basin. The array developed in this study could also be a useful tool for studies involving endangered sucker species and other sucker species used in contaminant research.

Oregon;Washington↗

Mercury in gray wolves (Canis lupus) in Alaska: Increased exposure through consumption of marine prey

Mercury (Hg) bioaccumulates in the tissues of organismsand biomagnifies within food-webs. Graywolves (Canis lupus) in Alaska primarily acquire Hg through diet; therefore, comparing the extent of Hg exposure inwolves, in conjunction with stable isotopes, from interior and coastal regions of Alaska offers important insight into their feeding ecology. Liver, kidney, and skeletal muscle samples from 162 graywolves were analyzed for total mercury (THg) concentrations and stable isotopic signatures (δ 13 C, δ 15 N, and δ 34 S).Median hepatic THg concentrations were significantly higher in wolves with coastal access compared to wolves from interior Alaska. Stable isotope ratios, in conjunction with THg concentrations, provide strong evidence that coastal wolves are utilizing marine prey representing several trophic levels. The utilization of cross-ecosystem food resources by coastal wolves is clearly contributing to increased THg exposure, and may ultimately have negative health implications for these animals.

Alaska↗

A GIS-based vulnerability assessment of brine contamination to aquatic resources from oil and gas development in eastern Sheridan County, Montana

Water (brine) co-produced with oil in the Williston Basin is some of the most saline in the nation. The Prairie Pothole Region (PPR), characterized by glacial sediments and numerous wetlands, covers the northern and eastern portion of the Williston Basin. Sheridan County, Montana, lies within the PPR and has a documented history of brine contamination. Surface water and shallow groundwater in the PPR are saline and sulfate dominated while the deeper brines are much more saline and chloride dominated. A Contamination Index (CI), defined as the ratio of chloride concentration to specific conductance in a water sample, was developed by the Montana Bureau of Mines and Geology to delineate the magnitude of brine contamination in Sheridan County. Values > 0.035 indicate contamination. Recently, the U.S. Geological Survey completed a county level geographic information system (GIS)-based vulnerability assessment of brine contamination to aquatic resources in the PPR of the Williston Basin based on the age and density of oil wells, number of wetlands, and stream length per county. To validate and better define this assessment, a similar approach was applied in eastern Sheridan County at a greater level of detail (the 2.59 km 2 Public Land Survey System section grid) and included surficial geology. Vulnerability assessment scores were calculated for the 780 modeled sections and these scores were divided into ten equal interval bins representing similar probabilities of contamination. Two surface water and two groundwater samples were collected from the section with the greatest acreage of Federal land in each bin. Nineteen of the forty water samples, and at least one water sample from seven of the ten selected sections, had CI values indicating contamination. Additionally, CI values generally increased with increasing vulnerability assessment score, with a stronger correlation for groundwater samples (R 2 = 0.78) than surface water samples (R 2 = 0.53).

Montana↗

Mycotoxins: diffuse and point source contributions of natural contaminants of emerging concern to streams

To determine the prevalence of mycotoxins in streams, 116 water samples from 32 streams and three wastewater treatment plant effluents were collected in 2010 providing the broadest investigation on the spatial and temporal occurrence of mycotoxins in streams conducted in the United States to date. Out of the 33 target mycotoxins measured, nine were detected at least once during this study. The detections of mycotoxins were nearly ubiquitous during this study even though the basin size spanned four orders of magnitude. At least one mycotoxin was detected in 94% of the 116 samples collected. Deoxynivalenol was the most frequently detected mycotoxin (77%), followed by nivalenol (59%), beauvericin (43%), zearalenone (26%), β-zearalenol (20%), 3-acetyl-deoxynivalenol (16%), α-zearalenol (10%), diacetoxyscirpenol (5%), and verrucarin A (1%). In addition, one or more of the three known estrogenic compounds (i.e. zearalenone, α-zearalenol, and β-zearalenol) were detected in 43% of the samples, with maximum concentrations substantially higher than observed in previous research. While concentrations were generally low (i.e. < 50 ng/L) during this study, concentrations exceeding 1000 ng/L were measured during spring snowmelt conditions in agricultural settings and in wastewater treatment plant effluent. Results of this study suggest that both diffuse (e.g. release from infected plants and manure applications from exposed livestock) and point (e.g. wastewater treatment plants and food processing plants) sources are important environmental pathways for mycotoxin transport to streams. The ecotoxicological impacts from the long-term, low-level exposures to mycotoxins alone or in combination with complex chemical mixtures are unknown

Science of the Total Environment↗

Evaluation of wastewater contaminant transport in surface waters using verified Lagrangian sampling

Contaminants released from wastewater treatment plants can persist in surface waters for substantial distances. Much research has gone into evaluating the fate and transport of these contaminants, but this work has often assumed constant flow from wastewater treatment plants. However, effluent discharge commonly varies widely over a 24-hour period, and this variation controls contaminant loading and can profoundly influence interpretations of environmental data. We show that methodologies relying on the normalization of downstream data to conservative elements can give spurious results, and should not be used unless it can be verified that the same parcel of water was sampled. Lagrangian sampling, which in theory samples the same water parcel as it moves downstream (the Lagrangian parcel), links hydrologic and chemical transformation processes so that the in-stream fate of wastewater contaminants can be quantitatively evaluated. However, precise Lagrangian sampling is difficult, and small deviations – such as missing the Lagrangian parcel by less than 1 h – can cause large differences in measured concentrations of all dissolved compounds at downstream sites, leading to erroneous conclusions regarding in-stream processes controlling the fate and transport of wastewater contaminants. Therefore, we have developed a method termed “verified Lagrangian” sampling, which can be used to determine if the Lagrangian parcel was actually sampled, and if it was not, a means for correcting the data to reflect the concentrations which would have been obtained had the Lagrangian parcel been sampled. To apply the method, it is necessary to have concentration data for a number of conservative constituents from the upstream, effluent, and downstream sites, along with upstream and effluent concentrations that are constant over the short-term (typically 2–4 h). These corrections can subsequently be applied to all data, including non-conservative constituents. Finally, we show how data from other studies can be corrected.

Science of the Total Environment↗

Methylmercury production in sediment from agricultural and non-agricultural wetlands in the Yolo Bypass, California, USA

As part of a larger study of mercury (Hg) biogeochemistry and bioaccumulation in agricultural (rice growing) and non-agricultural wetlands in California's Central Valley, USA, seasonal and spatial controls on methylmercury (MeHg) production were examined in surface sediment. Three types of shallowly-flooded agricultural wetlands (white rice, wild rice, and fallow fields) and two types of managed (non-agricultural) wetlands (permanently and seasonally flooded) were sampled monthly-to-seasonally. Dynamic seasonal changes in readily reducible ‘reactive’ mercury (Hg(II) R ), Hg(II)-methylation rate constants (k meth ), and concentrations of electron acceptors (sulfate and ferric iron) and donors (acetate), were all observed in response to field management hydrology, whereas seasonal changes in these parameters were more muted in non-agricultural managed wetlands. Agricultural wetlands exhibited higher sediment MeHg concentrations than did non-agricultural wetlands, particularly during the fall through late-winter (post-harvest) period. Both sulfate- and iron-reducing bacteria have been implicated in MeHg production, and both were demonstrably active in all wetlands studied. Stoichiometric calculations suggest that iron-reducing bacteria dominated carbon flow in agricultural wetlands during the growing season. Sulfate-reducing bacteria were not stimulated by the addition of sulfate-based fertilizer to agricultural wetlands during the growing season, suggesting that labile organic matter, rather than sulfate, limited their activity in these wetlands. Along the continuum of sediment geochemical conditions observed, values of k meth increased approximately 10,000-fold, whereas Hg(II) R decreased 100-fold. This suggests that, with respect to the often opposing trends of Hg(II)-methylating microbial activity and Hg(II) availability for methylation, microbial activity dominated the Hg(II)-methylation process, and that along this biogeochemical continuum, conditions that favored microbial sulfate reduction resulted in the highest calculated MeHg production potential rates. Rice straw management options aimed at limiting labile carbon supplies to surface sediment during the post-harvest fall–winter period may be effective in limiting MeHg production within agricultural wetlands.

California↗

Mercury accumulation in sea lamprey ( Petromyzon marinus ) from Lake Huron

We determined whole-fish total mercury (Hg) concentrations of 40 male and 40 female adult sea lampreys ( Petromyzon marinus ) captured in the Cheboygan River, a tributary to Lake Huron, during May 2011. In addition, bioenergetics modeling was used to explore the effects of sex-related differences in activity and resting (standard) metabolic rate (SMR) on mercury accumulation. The grand mean for Hg concentrations was 519 ng/g (standard error of the mean = 46 ng/g). On average, males were 16% higher in Hg concentration than females. Bioenergetics modeling results indicated that 14% higher activity and SMR in males would account for this observed sex difference in Hg concentrations. We concluded that the higher Hg concentration in males was most likely due to higher rate of energy expenditure in males, stemming from greater activity and SMR. Our findings have implications for estimating the effects of sea lamprey populations on mercury cycling within ecosystems, as well as for the proposed opening of sea lamprey fisheries. Eventually, our results may prove useful in improving control of sea lamprey, a pest responsible for substantial damage to fisheries in lakes where it is not native.

Michigan↗

Mercury cycling in agricultural and managed wetlands, Yolo Bypass, California: Spatial and seasonal variations in water quality

The seasonal and spatial variability of water quality, including mercury species, was evaluated in agricultural and managed, non-agricultural wetlands in the Yolo Bypass Wildlife Area, an area managed for multiple beneficial uses including bird habitat and rice farming. The study was conducted during an 11-month period (June 2007 to April 2008) that included a summer growing season and flooded conditions during winter. Methylmercury (MeHg) concentrations in surface water varied over a wide range (0.1 to 37 ng L&minus;1 unfiltered; 0.04 to 7.3 ng L&minus;1 filtered). Maximum MeHg values are among the highest ever recorded in wetlands. Highest MeHg concentrations in unfiltered surface water were observed in drainage from wild rice fields during harvest (September 2007), and in white rice fields with decomposing rice straw during regional flooding (February 2008). The ratio of MeHg to total mercury (MeHg/THg) increased about 20-fold in both unfiltered and filtered water during the growing season (June to August 2007) in the white and wild rice fields, and about 5-fold in fallow fields (July to August 2007), while there was little to no change in MeHg/THg in the permanent wetland. Sulfate-bearing fertilizer had no effect on Hg(II) methylation, as sulfate-reducing bacteria were not sulfate limited in these agricultural wetlands. Concentrations of MeHg in filtered and unfiltered water correlated with filtered Fe, filtered Mn, DOC, and two indicators of sulfate reduction: the SO4 2 &minus;/Cl&minus; ratio, and &delta;34S in aqueous sulfate. These relationships suggest that microbial reduction of SO4 2&minus;, Fe(III), and possibly Mn(IV) may contribute to net Hg(II)-methylation in this setting.

California↗

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 flowrates and tracer concentrations atwetland inflows and outflows. We used two ideal reactormodel solutions, a continuous flowstirred 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 nonideal agricultural wetlands in which check ponds are in series. Using a fluxmodel, 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&ndash;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 Fick's First Law calculations when determining diffusion fluxes using pore water concentration data; and misinterpreting biogeochemicalmechanisms 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.

Science of the Total Environment↗