Selenium stable isotope investigation into selenium biogeochemical cycling in a lacustrine environment: Sweitzer Lake, Colorado

We present a comprehensive set of Se concentration and isotope ratio data collected over a 3-yr period from dissolved, sediment-hosted, and organically bound Se in a Se-contaminated lake and littoral wetland. Median isotope ratios of these various pools of Se spanned a narrow isotopic range (delta80/76Se(SRM-3149)) = 1.14-2.40 per thousand). Selenium (VI) reduction in the sediments is an important process in this system, but its isotopic impact is muted by the lack of direct contact between surface waters and reduction sites within sediments. This indicates that using Se isotope data as an indicator of microbial or abiotic Se oxyanion reduction is not effective in this or other similar systems. Isotopic data suggest that most Se(IV) in the lake originates from oxidation of organically bound Se rather than directly through Se(VI) reduction. Mobilization of Se(VI) from bedrock involves only a slight isotopic shift. Temporally constant isotopic differences observed in Se(VI) from two catchment areas suggest the potential for tracing Se(VI) from different source areas. Phytoplankton isotope ratios are close to those of the water, with a small depletion in heavy isotopes (0.56 per thousand). Fish tissues nearly match the phytoplankton, being only slightly depleted in the heavier isotopes. This suggests the potential for Se isotopes as migration indicators. Volatile, presumably methylated Se was isotopically very close to median values for phytoplankton and macrophytes, indicating a lack of isotopic fractionation during methylation.     

Selenium distribution and fluxes in intertidal wetlands, San Francisco Bay, California

Selenium (Se) concentrations exceeding ecological guidelines for sediments and suspended particulate matter (SPM) have been observed in the northern reach of the San Francisco Bay estuary. Longterm availability of elevated Se in wetland sediments depends in part on the fluxes controlling Se distribution. The relative contribution of sedimentary vs. post-depositional Se fluxes in two San Francisco Bay intertidal wetlands was estimated. Selenium concentrations on surface wetland sediments were compared with levels on SPM, and with previously established background levels in San Francisco Bay sediments. Sediment Se fluxes to the wetlands were measured directly using sediment traps. Although dissolved Se concentrations are higher than particulate Se concentrations in San Francisco Bay water, sediment input into the system provides the major flux of Se. Strong correlation between Se and C on SPM (r2 = 0.81) indicates the importance of organic particulate deposition. Dependence on sediment texture was qualitatively established by measuring Se on particle-size separates. Normalization to Al showed that 65% of Se spatial variability is related to sediment texture. Selenium is further enriched in the marsh via post-depositional inputs, probably due to in situ adsorption from overlying water and chemical reduction. According to sediment flux measurements, enrichment in the marsh is equivalent to 20 to 25% of the particulate Se flux, thereby defining the marsh as a Se sink. These findings highlight the need for more intensive monitoring of SPM as the major source of Se to intertidal wetlands.     

Evaluation of the macroalga,muskgrass, for the phytoremediation of selenium-contaminated agricultural drainage water by microcosms

Previous field studies suggested that the macroalga, muskgrass (Chara canescens Desv. & Lois), plays an important role in the removal of selenium (Se) from agricultural drainage water. This study evaluated the efficiency of Se removal from drainage water by muskgrass-vegetated wetland microcosms, and determined the extent to which muskgrass removed Se through phytoextraction and biovolatilization. Six flow-through wetland microcosms were continuously supplied with drainage water containing an average Se concentration of 22 microg L(-1) over a 24-d experimental period. The Se mass input and outflow and the rate of Se volatilization were monitored daily for each microcosm. Three microcosms containing muskgrass reduced the daily mass Se input in the inflow drainage water by 72.1%; this compared with a reduction of 50.6% of the mass Se input for three unvegetated control microcosms. Selenium accumulated in muskgrass tissues accounted for 1.9% of the total mass Se input in the microcosm, followed by 0.5% via biological volatilization. The low rates of Se volatilization from selenate-supplied muskgrass, which were 10-fold less than from selenite, were probably due to a major rate limitation in the reduction of selenate to organic forms of Se in muskgrass. This conclusion was derived from X-ray absorption spectroscopy speciation analysis, which showed that muskgrass treated with selenite contained 91% of the total Se in organic forms (selenoethers and diselenides), compared with 47% in muskgrass treated with selenate.     

Sources of salinity near a coal mine spoil pile, north-central Colorado

A small (1 km2) salt-affected stream drainage on the High Plains north of Denver, Colorado was sampled to determine the near-surface dispersion of soluble salts and metals from low-sulfur coal mining waste (spoil). Surface waters collected along the 0.8-km stream reach, and aqueous leachates of spoil and naturally saline local soil, were analyzed for chemical constituents and sulfur isotopes. In this semiarid setting with abundant carbonate-bearing surficial sediments, the limited, mildly acidic drainage from the spoil pile is quickly neutralized, restricting the mobility of many elements. However, some spoil-derived constituents were clearly traceable within the upper 0.4 km of the stream reach. Spoil leachates and surface water near the spoil pile have distinctive compositions of major anions and cations, and elevated levels of dissolved nitrate compared with downstream waters. Spoil-derived sulfate was traceable because it has generally positive values of delta34S that contrasted with generally negative values of delta34S in soil leachates and evaporite salts from the surrounding area. Spatial-chemical sampling of surface water showed an abrupt increase in dissolved U, Se, B, Li, and Mn in the lower 0.4 km of the stream reach where shallow ground water from surrounding irrigated fields contributed to surface flow. The downstream evolution of surface water chemistry and sulfur isotopic composition is consistent with mixing between spoil-affected upstream water and irrigation-return water. The methods described should be applicable at other sites in similar settings where the environmental effect of low-sulfur coal mining waste must be assessed and where access to samples of shallow ground water is limited.     

Characterization of selenate removal from drainage water using rice straw

Removal of selenium (Se) from agricultural drainage water is very important for protecting wildlife in wetland systems. We conducted a series of experiments on selenite [Se(IV)] adsorption and selenate [Se(VI)] reduction to determine Se removal from drainage water amended with 1000 microg/L of Se(VI) or Se(IV) and 5 g of rice (Oryza sativa L.) straw. Under sterile conditions, the added Se(IV) was not adsorbed to the rice straw within 2 d of the experiment and the added Se(VI) was not reduced within 14 d. In contrast, added Se(VI) in a nonsterile rice-straw solution was reduced rapidly, from 930 microg/L at Day 3 to 20 microg/L at Day 5, with an increase in unprecipitated elemental Se [Se(0)] and total Se(0). In the last several days of the experiments, unprecipitated Se(0) was the major Se form in the rice-straw solution, with a small amount of organic Se(-II). This study showed that Se removal from drainage water in the presence of rice straw involves a two-step process. The first is the microbial reduction of Se(VI) to Se(IV) and then to colloidal Se(0). The second is flocculation and precipitation of colloidal Se(0) to the bottom of the experimental flasks and the surface of rice straw.     

Removal of selenate in simulated agricultural drainage water by a rice straw bioreactor channel system

Removal of selenium (Se) from agricultural drainage water is important in protecting wetland wildlife. Three flow-through bioreactor channel systems (BCSs), each with three channels filled with rice (Oryza sativa L.) straw, were set in the laboratory to determine removal of selenate [Se(VI)] (1020 microg L(-1)) from drainage water with a salinity of 10.4 dS m(-1), a pH of 8.1, and a nitrate (NO3-) range of 0 to 100 mg L(-1). Results showed that the rice straw effectively reduced Se(VI) during 122 to 165 d of the experiments. Calculation of Se mass in the three BCSs showed that 89.5 to 91.9% of the input Se(VI) was reduced to red elemental Se [Se(0)], where 96.6 to 98.2% was trapped in the BCSs. Losses of each gram of rice straw were almost equal to the removal of 1.66 mg of Se from the drainage water as a form of red Se(0), indicating that rice straw is a very effective organic source for removing Se(VI) from drainage water.     

Inundation influences on bioavailability of phosphorus in managed wetland sediments in agricultural landscapes

Agricultural runoff carries high nutrient loads to receiving waters, contributing to eutrophication. Managed wetlands can be used in integrated management efforts to intercept nutrients before they enter downstream aquatic systems, but detailed information regarding sorption and desorption of P by wetland sediments during typical inundation cycles is lacking. This study seeks to quantify and elucidate how inundation of wetland sediments affects bioavailability of P and contributions of P to downstream systems. A managed wetland cell in Tunica County, Mississippi was subjected to a simulated agricultural runoff event and was monitored for bioavailable phosphorus (water-extractable P [P], Fe-P, and Al-P) of wetland sediments and water level during the runoff event and for 130 d afterward. Inundation varied longitudinally within the wetland, with data supporting significant temporal relationships between inundation and P desorption. Concentrations of P were significantly higher at the site that exhibited variable hydroperiods (100 m) as compared with sites under consistent inundation. This suggests that sites that are inundated for longer periods of time desorb less P immediately to the environment than sites that have periodic or ephemeral inundation. Concentrations of iron oxalate and NaOH-P were significantly higher at the least inundated site as compared with all other sites (F = 5.43; = 0.001) irrespective of time. These results support the hypothesis that increased hydraulic residence time decreases the bioavailability of P in wetland sediments receiving agricultural runoff. This finding suggests that the restoration of wetlands in the mid-southern United States may be hydrologically managed to improve P retention.     

Strontium isotope study of coal utilization by-products interacting with environmental waters

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.     

ISOTOPIC EVALUATION OF Pb OCCURRENCES IN THE RIVERINE ECOSYSTEMS OF THE KANKAKEE WATERSHED,ILLINOIS‐INDIANA1

ABSTRACT: Environmental background levels of Pb were measured in ponds, river waters, sediments, suspended sediments, rocks, and air particulates within the Kankakee watershed during the period of 1995 to 1999. Stable isotopic Pb distinguished airborne Pb and its incorporation into riverine wetland sediments from geogenic Pb measured in river sediments. The provenance of the naturally‐occurring Pb is from carbonate bedrock and contributes comparable concentrations in riverbank sediments (25.9–30.4 mg kg^?1) as Pb found in wetland sediments (18.6–24.8 mg kg^?1). Estimates of anthropogenic Pb contributions from airfall into the Kankakee wetlands were found to be near 0.43–0.71 Bq cm^?2 yr^?1 during 1995 to 1999. While leachable Pb data suggests the uppermost layers of pond sediments were disturbed, ²¹⁰Pb analyses from undisturbed sedimentation suggests Pb‐bearing sediments accumulate approximately 0.46–0.51 cm yr^?1 in the ponds within the riparian zones. Transboundary Pb pollution from aerosols of industrial Pb across the Great Lakes occurs, but Pb isotopy indicates that the Pb concentrations are comparable to natural concentrations of Pb in both waters and sediments within the Kankakee watershed.     

Selenium removal and mass balance in a constructed flow-through wetland system

A field study on the removal of Se from agricultural subsurface drainage was conducted from May 1997 to February 2001 in the Tulare Lake Drainage District (TLDD) of San Joaquin Valley, California. A flow-through wetland system was constructed consisting of ten 15- x 76-m unlined cells that were continuously flooded and planted with either a monotype or combination of plants, including sturdy bulrush [Schoenoplectus robustus (Pursh) M.T. Strong], baltic rush (Juncus balticus Willd.), smooth cordgrass (Spartina alterniflora Loisel.), rabbitsfoot grass [Polypogon monspeliensis (L.) Desf.], salt-grass lDistichlis spicata (L.) Greene], cattail (Typha latifolia L.), tule [Schoenoplectus acutus (Muhl. ex Bigelow) A. L?ve & D. L?ve], and widgeon grass (Ruppia maritima L.). One cell had no vegetation planted. The objectives of this research were to evaluate Se removal efficiency of each wetland cell and to carry out a mass balance on Se. The inflow drainage water to the cells had average annual Se concentrations of 19 to 22 microg L(-1) dominated by selenate [Se(VI), 95%]. Average weekly water residence time varied from about 3 to 15 d for Cells 1 through 7 (target 7 d), 19 to 33 d for Cells 8 and 9 (target 21 d), and 13 to 18 d for Cell 10 (target 14 d). Average weekly Se concentration ratios of outflow to inflow ranged from 0.45 to 0.79 and mass ratio (concentration x water volume) from 0.24 to 0.52 for year 2000, that is, 21 to 55% reduction in Se concentration and 48 to 76% Se removal in mass by the wetland, respectively. The nonvegetated cell showed the least Se removal both in concentration and in mass. The global mass balance showed that on the average about 59% of the total inflow Se was retained within the cells and Se outputs were outflow (35%), seepage (4%), and volatilization (2%). Independent measurements of the Se retained in the cells totaled 53% of the total Se inflow: 33% in the surface (0-20 cm) sediment, 18% in the organic detrital layer above the sediment, 2% in the fallen litter, < 1% in the standing plants, and < 1% in the surface water. Thus, about 6% of the total Se inflow was unaccounted for in the internal compartments.     

ALTERNATIVES TO THE USE OF AGRICULTURAL DRAINAGE WELLS1

ABSTRACT: A large number of agricultural drainage wells (ADWs) are located in north-central Iowa. These wells permit sediments, pesticides, nitrate, and bacteria in surface and subsurface drainage water to enter regional aquifers that are currently being used for drinking-water supplies, mostly by rural families and communities. This paper reports some possible alternatives to control the entry of surface and subsurface drainage waters into groundwater systems, and describes a methodology to make comprehensive economic feasibility studies of alternative drainage outlets. The estimated cost of providing main subsurface drains varied from $220 to $960 per hectare. If the use of ADWs was completely eliminated without providing alternative drainage, it is estimated that the average annual loss to the farmers of the area would be at least $270 per hectare in reduced crop yields. Of course, losses would be weather dependent and highly variable. Management practices to reduce the pollutant load in water draining to ADWs are also discussed.     

Irrigation of broccoli and canola with boron- and selenium-laden effluent

Selenium (Se), boron (B), and salinity contamination of agricultural drainage water is potentially hazardous for water reuse strategies in central California. To demonstrate the feasibility of using plants to extract Se from drainage water, Se accumulation was determined in canola (Brassica napus L.) and broccoli (Brassica oleracea L.) irrigated with drainage effluent in the San Joaquin Valley, California. In the 2-yr field study, both crops were irrigated with a typical drainage water containing Se (150 microg L(-1)), B (5 mg L(-1)), and a sulfate dominated salinity (EC of 7 dS m(-1)). Total dry matter yields were at least 11 Mg ha(-1) for both canola and broccoli, and plant tissue Se concentrations did not exceed 7 mg kg(-1) DM for either crop. Based on the amount of soluble Se applied to crops with drainage water and the estimated amount of soluble Se remaining in soil to a depth of 90 cm at harvest, both canola and broccoli accumulated at least 40% of the estimated soluble Se lost from the soil for both years. Applied Se not accounted for in plant tissue or as soluble Se in the soil was presumably lost by biological volatilization. This study suggests that irrigating two high value crops such as canola and broccoli with Se-laden effluent helps manage Se-laden effluent requiring treatment, and also produces economically viable Se-enriched crops. Future research should focus on managing residual salt and B in the soil for sustaining long time water reuse strategies.     

Mine-drainage treatment wetland as habitat for herptofaunal wildlife

Land reclamation techniques that incorporate habitat features for herptofaunal wildlife have received little attention. We assessed the suitability of a wetland, constructed for the treatment of mine-water drainage, for supporting herptofaunal wildlife from 1988 through 1990 using diurnal and nocturnal surveys. Natural wetlands within the surrounding watershed were also monitored for comparison. The treatment wetland supported the greatest abundance and species richness of herptofauna among the sites surveyed. Abundance was a function of the frog density, particularly green frogs (Rana clamitans) and pickerel frogs (R. palustris), while species richness was due to the number of snake species found. The rich mix of snake species present at the treatment wetland was believed due to a combination of an abundant frog prey base and an amply supply of den sites in rock debris left behind from earlier surface-mining activities. Nocturnal surveys of breeding male frogs demonstrated highest breeding activity at the treatment wetland, particularly for spring peepers (Hyla crucifer). Whole-body assays of green frog and bullfrog (R. catesbeiana) tissues showed no differences among sites in uptake of iron, aluminum, and zinc; managanese levels in samples from the treatment wetland were significantly lower than those from natural wetlands. These results suggest that wetlands established for water quality improvement can provide habitat for reptiles and amphibians, with the species composition dependent on the construction design, the proximity to source populations, and the degree of acidity and heavy-metal concentrations in drainage waters.     

“The Kesterson effect”

Hypothesized to be derived from Cretaceous marine sedimentary rocks, selenium contamination of the Kesterson National Wildlife Refuge is traced through irrigation drainage to the source bedrock of the California Coast Ranges. This biogeochemical pathway of selenium is defined here as the “Kesterson effect.” At the refuge ponds, this effect culminated in 1983 in a 64% rate of deformity and death of embryos and hatchlings of wild aquatic birds. From the previous companion paper on irrigation drainage, the Kesterson effect has been implicated in nine of 11 reconnaissance areas studied in the western United States. Deformities have resulted in at least five of these sites. Climatic, geologic, hydrologic, and soil conditions in these reconnaissance areas are similar to those in the area surrounding Kesterson National Wildlife Refuge in the west-central San Joaquin Valley of California. In California, selenium, as selenate, was ultimately found weathered with sulfur from marine sources in soluble sodium and magnesium sulfate salts, which are concentrated by evaporation on farmland soils. The Se, mobilized by irrigation drainage, is bioaccumulated to toxic levels in refuge wetland ponds that are located mainly in hydrologically closed basins and thus act as concentrating disposal points. The depositional environment of the ponds may be similar to that of the nutrient-rich continental shelf edge and slope in which Cretaceous, Eocene, and Miocene sediments found to be seleniferous in the California Coast Ranges were deposited. Bioaccumulation may be therefore a primary mechanism of selenium enrichment in ancient sediments in addition to that of the formerly suggested Cretaceous volcanic pathway.     

STABLE HYDROGEN AND OXYGEN ISOTOPE COMPOSITION OF PRECIPITATION IN NORTHEASTERN COLORADO1

ABSTRACT: Where data are available, hydrologic studies may use precipitation's stable oxygen and hydrogen isotope composition to investigate streamflow, ground water/surface water interaction, and ground water recharge. Paleoclimate studies utilize the δ¹⁸O_{precipitation}‐T_air relationship, in conjunction with lake sediments, fossils, or old ground waters, for example, to estimate pale‐otemperatures. Ecological studies utilize precipitation and soil water isotope composition to track moisture uptake in plants, and to trace species migration patterns. Such studies require that the isotopic composition of precipitation be known. Oxygen‐18 (δ¹⁸O) and deuterium (δ²H) data for precipitation are lacking in the semi‐arid portion of the north‐central U.S. Great Plains, and thus there is a need to establish additional meteoric water lines as isotope input functions across the region, as well as to develop better understanding of the isotopic climate linkages that control oxygen and hydrogen isotope ratios in precipitation. This study determined the δ¹⁸O and δ²H composition of precipitation in the Pawnee Grasslands of northeastern Colorado from 1994 through 1998 using archived National Atmospheric Deposition Program samples. The resulting local water line follows the relationship δ²H = 7.86 δ¹⁸O‐7.66, and the data show a δ¹⁸O_weekly ‐ T_weekly relationship of δ¹⁸O = 0.560‐T (°C)‐18.8.     

Use of Microbial Community to Evaluate Performance of a Wetland System in Treating Pb/Zn Mine Drainage

The performance of a wetland system in treating lead (Pb)/zinc (Zn) mine drainage was evaluated by using the polyurethane foam unit (PFU) microbial community (method), which has been adopted by China as a standardized procedure for monitoring water quality. The wetland system consisted of four cells with three dominant plants: Typha latifolia, Phragmites australis and Paspalum distichum. Physicochemical characteristics [pH, EC, content of total suspended solid (TSS) and metals (Pb, Zn, Cd, and Cu)] and PFU microbial community in water samples had been investigated from seven sampling sites. The results indicated that the concentrations of Pb, Zn, Cd, Cu, and TSS in the mine drainage were gradually reduced from the inlet to the outlet of the wetland system and 99%, 98%, 75%, 83%, and 68% of these metals and TSS respectively, had been reduced in concentration after the drainage passed through the wetland system. A total of 105 protozoan species were identified, the number of protozoa species and the diversity index (DI) gradually increased, while the heterotrophic index (HI) gradually decreased from the inlet to the outlet of the wetland system. The results indicated that DI, HI, and total number species of protozoa could be used as biological indicators indicating the improvement of water quality.     

Soil and plant selenium at a reclaimed uranium mine

Selenium (Se) associated with reclaimed uranium (U) mine lands may result in increased food chain transfer and water contamination. To assess post-reclamation bioavailability of Se at a U mine site in southeastern Wyoming, we studied soil Se distribution, dissolution, speciation, and sorption characteristics and plant Se accumulation. Phosphate-extractable soil Se exceeded the critical limit of 0.5 mg/kg in all the samples, whereas total soil Se ranged from a low (0.6 mg/kg) to an extremely high (26 mg/kg) value. Selenite was the dominant species in phosphate and ammonium bicarbonate-diethylenetriamine pentaacetic acid (AB-DTPA) extracts, whereas selenate was the major Se species in hot water extracts. Extractable soil Se concentrations were in the order of KH2PO4 > AB-DTPA > hot water > saturated paste. The soils were undersaturated with respect to various Se solid phases, albeit with high levels of extractable Se surpassing the critical limit. Calcium and Mg minerals were the potential primary solids controlling Se dissolution, with dissolved organic carbon in the equilibrium solutions resulting in enhanced Se availability. Adsorption was a significant (r2 = 0.76-0.99 at P < 0.05) mechanism governing Se availability and was best described by the initial mass isotherm model, which predicted a maximum reserve Se pool corresponding to 87% of the phosphate-extractable Se concentrations. Grasses, forbs, and shrubs accumulated 11 to 1800 mg Se/kg dry weight. While elevated levels of bioavailable Se may be potentially toxic, the plants accumulating high Se may be used for phytoremediation, or the palatable forage species may be used as animal feed supplements in Se-deficient areas.     

Nitrate loading and isotopic signatures in subsurface agricultural drainage systems

Artificially draining soils using subsurface tiles is a common practice on many agricultural fields. High levels of nitrate-nitrogen (NO-N) are often released from these systems; therefore, knowledge on the sources and processes controlling NO-N in drainage systems is needed. A dual isotope study (δN and δO) was used to investigate three subsurface drainage systems (shallow, conventional, and controlled) in Onslow, Nova Scotia, Canada. The objectives of this study were (i) to identify which drainage system more effectively reduced the NO-N loading, (ii) to examine differences in isotopic signatures under identical nutrient and cropping regimes for a fixed soil type, and (iii) to identify the utility of different drainage systems in controlling nutrient flows. Nitrate concentrations measured ranged from 0.92 to 11.8, from 2.3 to 17.3, and from 2.1 to 19.8 mg L for the shallow, conventional, and controlled drains, respectively. Total NO-N loading from shallow and controlled drains were 20 and 5.6 kg ha, respectively, lower than conventional (39.1 kg ha). The isotopic composition of NO-N for all drainage types appeared to be a mixture of two organic sources (manure and soil organic matter) via the process of nitrification. There was no evidence that denitrification played a significant role in removing NO-N during transport. Overall, shallow drainage reduced NO-N loading but offered no water conservation benefits. Combining the benefits of decreased NO-N loading from shallow systems with water control capability may offer the best solution to reducing nutrient loadings into water systems, achieving optimal crop yield, and decreasing drainage installation costs.     

Particulate phosphorus and sediment in surface runoff and drainflow from clayey soils

Recent work has shown that a significant portion of the total loss of phosphorus (P) from agricultural soils may occur via subsurface drainflow. The aim of this study was to compare the concentrations of different P forms in surface and subsurface runoff, and to assess the potential algal availability of particulate phosphorus (PP) in runoff waters. The material consisted of 91 water-sample pairs (surface runoff vs. subsurface drainage waters) from two artificially drained clayey soils (a Typic Cryaquept and an Aeric Cryaquept) and was analyzed for total suspended solids (TSS), total phosphorus (TP), dissolved molybdate-reactive phosphorus (DRP), and anion exchange resin-extractable phosphorus (AER-P). On the basis of these determinations, we calculated the concentrations of PP, desorbable particulate phosphorus (PPi), and particulate unavailable (nondesorbable) phosphorus (PUP). Some water samples and the soils were also analyzed for 137Cs activity and particle-size distribution. The major P fraction in the waters studied was PP and, on average, only 7% of it was desorbable by AER. However, a mean of 47% of potentially bioavailable P (AER-P) consisted of PPi. The suspended soil material carried by drainflow contained as much PPi (47-79 mg kg-1) as did the surface runoff sediment (45-82 mg kg-1). The runoff sediments were enriched in clay-sized particles and 137Cs by a factor of about two relative to the surface soils. Our results show that desorbable PP derived from topsoil may be as important a contributor to potentially algal-available P as DRP in both surface and subsurface runoff from clayey soils.     

Wetland Flowpaths Mediate Nitrogen and Phosphorus Concentrations across the Upper Mississippi River Basin

Eutrophication, harmful algal blooms, and human health impacts are critical environmental challenges resulting from excess nitrogen and phosphorus in surface waters. Yet we have limited information regarding how wetland characteristics mediate water quality across watershed scales. We developed a large, novel set of spatial variables characterizing hydrological flowpaths from wetlands to streams, that is, “wetland hydrological transport variables,” to explore how wetlands statistically explain the variability in total nitrogen (TN) and total phosphorus (TP) concentrations across the Upper Mississippi River Basin (UMRB) in the United States. We found that wetland flowpath variables improved landscape-to-aquatic nutrient multilinear regression models (from R² = 0.89 to 0.91 for TN; R² = 0.53 to 0.84 for TP) and provided insights into potential processes governing how wetlands influence watershed-scale TN and TP concentrations. Specifically, flowpath variables describing flow-attenuating environments, for example, subsurface transport compared to overland flowpaths, were related to lower TN and TP concentrations. Frequent hydrological connections from wetlands to streams were also linked to low TP concentrations, which likely suggests a nutrient source limitation in some areas of the UMRB. Consideration of wetland flowpaths could inform management and conservation activities designed to reduce nutrient export to downstream waters.