Phosphorus speciation in manure and manure-amended soils using XANES spectroscopy

Previous studies suggested an increase in the proportion of calcium phosphates (CaP) of the total phosphorus (P) pool in soils with a long-term poultry manure application history versus those with no or limited application histories. To understand and predict long-term P accumulation and release dynamics in these highly amended soils, it is important to understand what specific P species are being formed. We assessed forms of CaP formed in poultry manure and originally acidic soil in response to different lengths of mostly poultry manure applications using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy. Phosphorus K-edge XANES spectra of poultry manure showed no evidences of crystalline P minerals but dominance of soluble CaP species and free and weakly bound phosphates (aqueous phosphate and phosphate adsorbed on soil minerals). Phosphate in an unamended neighboring forest soil (pH 4.3) was mainly associated with iron (Fe) compounds such as strengite and Fe-oxides. Soils with a short-term manure history contained both Fe-associated phosphates and soluble CaP species such as dibasic calcium phosphate (DCP) and amorphous calcium phosphate (ACP). Long-term manure application resulted in a dominance of CaP forms confirming our earlier results obtained with sequential extractions, and a transformation from soluble to more stable CaP species such as beta-tricalcium calcium phosphate (TCP). Even after long-term manure application (> 25 yr and total P in soil up to 13,307 mg kg(-1)), however, none of the manure-amended soils showed the presence of crystalline CaP. With a reduction or elimination of poultry manure application to naturally acidic soils, the pH of the soil is likely to decrease, thereby increasing the solubility of Ca-bonded inorganic P minerals. Maintaining a high pH is therefore an important strategy to minimize P leaching in these soils.     

Indicator to predict the movement of phosphorus from soil to subsurface flow

The movement of phosphorus (P) in subsurface flow can contribute to losses from agricultural land. This study aims to identify a soil P threshold above which P loss is likely to accelerate as a function of soil and management type. Lysimeters (25 cm i.d. by 30 cm deep) were taken of four soils from agricultural watersheds in Pennsylvania and New York. The soils had a range of Mehlich-3 extractable P (7-517 mg of P kg(-1)) in surface soil (0-7.5 cm for grassland and 0-23 cm for cultivated/arable) and reactive P, filtered <0.45 microm (RP(<0.45 microm) in subsurface flow (0.007-1.53 mg of P L(-1)). The loss of P from lysimeters increased greatly when Mehlich-3 extractable P was in excess of a mean concentration of 280 mg kg(-1), the degree of saturation of P sorption sites exceeded 38%, and the corrected P sorption strength (corrected for desorption) derived from the monolayer Langmuir equation was less than 0.07 L of P mg(-1). Of these variables, P sorption strength was most consistently related to RP(<0.45 microm) in subsurface flow across a range of soil managements. Use of the corrected Langmuir sorption strength parameter to estimate subsurface flow RP(<0.45 microm) derived from four U.S. soils was tested on four soils of different physiochemical characteristics (one calcareous) from the U.K. The U.K. soils showed similar concentration trends to the U.S. soils, with elevated RP(<0.45 microm) below a sorption strength of 0.07 L of P mg(-1). We propose that the P sorption strength derived from the monolayer Langmuir equation may be used to estimate the potential for P loss in subsurface flow, when simpler environmental tests such as P saturation derived from acid ammonium oxalate extraction are unclear or unsuitable.     

Biogenic phosphate minerals in manure: implications for phosphorus loss to surface waters

Phosphorus (P) is present in waterways throughout the United States at concentrations that impair water quality. Agriculture, particularly livestock production, has been identified as a major cause of this impairment Excess manure P applied to croplands has increased P losses in runoff, leading to surface water eutrophication. We conducted a long-term (36-week) incubation with poultry and dairy manures applied to a silt loam soil to elucidate mechanisms controlling manure P loss to water. Manures were applied to supply the same total P rate to soils with different antecedent plant-available P concentrations (soil test P). There was a strong synergistic effect between dairy manure and soil test P on water extractable P, while soil test P did not affect P loss from poultry manure-amended soils. Using scanning electron microscopy and energy dispersive X-ray spectroscopy, we found that poultry manure contained sparingly soluble calcium and magnesium phosphate minerals that controlled soil solution P concentrations, while dairy manure did not These minerals resemble other biogenic phosphate minerals. Our findings refute current assumptions that all manure P behaves similarly in soils and that organic forms control manure-soil P loss to water.     

Lead bioaccessibility in food web intermediates and the influence on ecological risk characterization

Models simulating gastric conditions of mammalian (eastern cottontail, Sylvilagus floridanus; short-tailed shrew, Blarina brevicauda) and avian (American robin, Turdus migratorius) receptors were used to investigate the proportion of lead (Pb) mobilized into the digestive juices (the bioaccessible fraction) from soil, earthworms, and vegetation collected at a rifle and pistol (RP) range in eastern Ontario, Canada. Pb concentrations averaged 5044 mg kg(-1) in RP range surface soils, 727 mg kg(-1) in earthworm tissue, and 2945 mg kg(-1) in unwashed vegetation. For mammalian gastric models, the bioaccessible fraction of Pb in soils was 66 +/- 22%, in earthworm tissue was 77 +/- 14%, and in unwashed vegetation was 50 +/- 37%. For the avian gastric model, the bioaccessible fraction of Pb in soil was 53 +/- 43% and in earthworm tissue was 73 +/- 13%. The incorporation of soil and food web intermediate bioaccessibility data into standard risk calculations resulted in predicted risk being reduced for all receptors. The inclusion of bioaccessibility during ecological risk assessment affords a more realistic estimate of contaminant exposure, and is a valuable tool for use in contaminated sites management.     

Regular applications of poultry litter to a sandy arable soil: effects on nitrate leaching and nitrogen balance

Intensive poultry units often have insufficient land for spreading manure at agronomically and environmentally acceptable rates. This experiment measured the effects of annual applications, at several rates, on nitrate-N leaching and the soil–crop N balance on a sandy soil. Poultry litter from a broiler unit was applied each autumn 1992–1995. Total loadings on the main experiment area (instrumented with ceramic and Teflon water samplers at 1·0 and 1·5 m, and monolith lysimeters, 1·5 m deep) were 0, 60 and 150 t ha⁻¹. Additional plots (not instrumented) received 30, 90 or 120 t ha⁻¹. There was good agreement in the nitrate-N concentrations measured by the Teflon and ceramic water samplers and the lysimeters; all three methods gave acceptable measurements of nitrate leaching on structureless sandy soils. Autumn applications of poultry manure should be avoided: leaching was much greater than when delayed into December. At rates of broiler litter which supplied more N than the crop required (generally above 10 t ha⁻¹ each year), nitrate-N leaching losses were large; at the largest application rate (akin to a disposal, rather than a planned fertiliser strategy), concentrations peaked at c 500 mg litre⁻¹ N. Despite the movement of dissolved organic carbon to 1 m depth, the N concentration profiles measured by the water samplers did not provide clear evidence of subsoil denitrification. A nitrogen balance sheet, based on available N applied (as either fertiliser or manure) with some adjustment for mineralisation of the manure's organic fraction (10% annually) and for volatilisation (15%) was strongly correlated with soil mineral N each spring. © 1998 Society of Chemical Industry.     

Bioavailable phosphorus in animal waste amended soils: using actual crop uptake and p mass balance approach

Animal manure amended soils often contain large amounts of bioavailable phosphorus (P) and constitute high risk for the deterioration of surface water quality through eutrophication. Current standards set for the safe disposal of animal manure through soil application are based on the assumption that phosphorus in all P sources would behave similarly. The primary objective of this study was to understand the influence of P from several manure and mineral fertilizer sources applied at 0, 50, and 150 mg P kg(-1) on two measures of bioavailable P to six soils of different initial soil test P levels using corn (Zea mays L.) P uptake and an iron oxide strip method for soil analysis (FeO-P). Total net bioavailable P (TNBP) was calculated by subtracting total P uptake by corn after seven consecutive harvests in control treatments that did not receive P from the P uptake from P-amended treatments. Net biovavailable P after the first harvest (NBP1) was calculated in a similar fashion but only using data from the first harvest. Significant differences in TNBP and NBP1 were found when comparing P sources. The hog (Sus scrofa) manure had the greatest P bioavailability while turkey (Meleagris gallopava) litter had the lowest among the animal P sources across all soils and levels of P application. Significant differences were also found between soils with the highest amounts of TNBP and NBP1 found in the Woodson soil and lowest detected in the Crete soil for most P sources. The FeO-P method was useful in predicting TNBP from most P sources.     

Responses of Cereals to Residual Fertiliser Nitrogen Applied to the Preceding Potato Crop

The effects of N fertiliser and poultry manure, applied to potato crops, on soil mineral N (SMN) after harvest and on the grain N offtake (N_off) and yield of subsequent unfertilised cereal crops, were measured at six sites in England during 1989–1994. At three sites of medium textured soil N_off increased by between 0 and 49 kg ha^-1 and grain yield by between 0 and 2·1 t ha^-1, with increasing potato fertiliser N (PFN). The increases were greatest at applications of fertiliser N in excess of the optimum requirement for potatoes. No responses were found on two sandy and one shallow soil. Poultry manure applied in autumn or spring before the potatoes were planted increased N_off by between 0 and 52 kg ha^-1 and yield by between 0 and 2·1 t ha^-1 at one site on medium textured soil but not on one of the two sandy soils. These results suggest that, at the rates of fertiliser N currently recommended for potatoes, the N requirement of subsequent cereal crops may be reduced by between 20 and 40 kg ha^-1 on retentive soils but not on sandy and shallow soils. These reductions are less than currently recommended. However, the results also suggest that adjusting cereal fertiliser N according only to previous crop is unsatisfactory. The range of fertiliser N applied to potato crops in commercial practice is sufficiently great to significantly affect N_off, yield and hence the fertiliser N requirement of the subsequent cereal crop. © 1997 SCI.     

A protocol to assess the enzymatic release of dissolved organic phosphorus species in waters under environmentally relevant conditions

A protocol to assess the potential release of dissolved reactive phosphorus (DRP) by enzymatic hydrolysis of dissolved organic phosphorus (DOP) in waters (sediment porewater and sewage liquors in this study) under environmental conditions is presented. This protocol enables the quantification of different classes of DOP compounds using a variety of phosphatase enzymes, i.e., alkaline phosphatase, phosphodiesterase, and phytase. All experiments were carried out within the pH range of most natural waters, i.e., at neutral (pH 7) or slightly alkaline pH (pH 9). Tri-sodium citrate and sodium dodecyl sulfate (SDS) were used in the assays to prevent interferences due to adsorption processes in the presence of multivalent metallic cations and to minimize protein binding. Applying this protocol revealed that labile phosphate monoesters always represented the largest fraction of enzymatically hydrolyzed P in sewage liquors and sediment porewater. Total enzymatically hydrolyzable P (EHP) represented only 16% of the TDP in the sediment porewater but up to 43% in sewage liquors. Because most of the enzymes used in this study are likely to exist in aquatic ecosystems, the EHP fraction might represent a source of potentially bioavailable P of similar magnitude to DRP.     

Solid-solution speciation and phytoavailability of copper and zinc in soils

The soil solution speciation and solid-phase fractionation of copper (Cu) and zinc (Zn) in 11 typical uncontaminated soils of South Australia were assessed in relation to heavy metal phytoavailability. The soils were analyzed for pH (4.9-8.4), soil organic matter content (3.5 to 23.8 g of C kg(-1)), total soil solution metal concentrations, Cu8 (49-358 microg kg(-1)) and Zn8 (121-582 microg kg(-1)), and dissolved organic matter (DOM) (69-827 mg of C L(-1)). The solid-liquid partition coefficient (Kd) ranged from between 13.9 and 152.4 L kg(-1) for Cu and 22.6 to 266.3 L kg(-1) for Zn. The phytoavailability of Cu and Zn could be predicted significantly using an empirical model with the solid-phase fractions of Cu and Zn, as obtained from selective sequential extraction scheme, as components. Phytoavailable Cu and Zn were found to significantly correlate with fulvic complex Cu (r= 0.944, P < 0.0001) and exchangeable Zn (r = 0.832, P = 0.002), respectively. The fulvic complex Cu was found to explain 89.2% of the variation in phytoavailable Cu, where as, the exchangeable Zn together with fulvic complex Zn could explain 78.9% of the variation in phytoavailable Zn. The data presented demonstrate the role of solid-phase metal fractions in understanding the heavy metal phytoavailability. The assessment of the role of solid-phase fractions in heavy metal phytoavailability is a neglected area of study and deserves close attention.     

The use of box lysimeters with freshly contaminated soils to study the phytoremediation of recalcitrant organic contaminants

The potential for phytoremediation of soil contaminated by trinitrotoluene (TNT) and 2,2',5,5'-tetrabromobiphenyl (PBB was used as a surrogate for PCBs) was examined in a 2-year study using box lysimeters under field conditions. The treatments were a warm season grass, Johnson grass, and a cool season grass, Canadian wildrye, and a rotation of Johnson grass and wildrye plus a fallow condition. The experiment was conducted using 12 large (1.50 m x 1.50 m x 0.75 m), in-ground, box lysimeters filled with a Weswood silt-loam soil freshly spiked with the TNT and PBB compounds to a concentration of 10 mg kg(-1) for each chemical. The lysimeters were sheltered to permit controlled applications of water. A total of five sampling rounds were conducted where soil, herbage, and leachate samples were collected for laboratory analysis. TNT and PBB concentrations were determined using the U.S. EPA approved immunoassay test procedures. In the soil, TNT concentrations dropped below the detection limit of 0.25 mg kg(-1) by day 92 and PBB concentrations dropped below the detection limit of 0.50 mg kg(-1) by day 184. There were no significant differences in chemical concentrations among any of the vegetated or fallow treatments at a significance level of alpha < 0.05. However, PBB soil concentrations rebounded above the 0.50 mg kg(-1) level by day 720 for all treatments. No detectable concentrations of TNT or PBB were found in any of the herbage samples or in the leachate.     

Dissipation and transport of veterinary sulfonamide antibiotics after manure application to grassland in a small catchment

The heavy use of veterinary antibiotics in modern animal production causes concern about risks of spreading antibiotic resistance after manure applications to agricultural fields. We report on a field study aiming at elucidating the fate of sulfonamide (SA) antibiotics in grassland soils and their transport to surface water. Two controlled manure applications were carried out under different weather conditions. After both applications, the SA concentrations in pore water and the total soil content declined rapidly. This stage of fast decline was followed by a second one during which the SA were rather persistent. More than 15% of the SAs applied were still present in the soil 3 months after application, always exceeding 100 microg/kg topsoil. The apparent SA sorption increased strongly with time. Accordingly, the risk for SA losses to water bodies decreased within 2 weeks to very low values. In contrast to SA concentrations in the soil, losses to the brook were strongly influenced by the weather conditions after the two manure applications. The overall losses were 15 times larger (about 0.5% of applied SA) during the wet conditions of May 2003 compared to the dry conditions following the first application (March 2003).     

Effect of a nonionic surfactant on biodegradation of slowly desorbing PAHs in contaminated soils

The influence of the nonionic surfactant Brij 35 on biodegradation of slowly desorbing polycyclic aromatic hydrocarbons (PAHs) was determined in contaminated soils. We employed a soil originated from a creosote-polluted site, and a manufactured gas plant soil that had been treated by bioremediation. The two soils differed in their total content in five indicator 3-, 4-, and 5-ring PAHs (2923 mg kg(-1) and 183 mg kg(-1) in the creosote-polluted and bioremediated soils, respectively) but had a similar content (140 mg kg(-1) vs 156 mg kg(-1)) of slowly desorbing PAHs. The PAHs present in the bioremediated soil were highly recalcitrant. The surfactant at a concentration above its critical micelle concentration enhanced the biodegradation of slowly desorbing PAHs in suspensions of both soils, but it was especially efficient with bioremediated soil, causing a 62% loss of the total PAH content. An inhibition of biodegradation was observed with the high-molecular-weight PAHs pyrene and benzo[a]pyrene in the untreated soil, possibly due to competition effects with other solubilized PAHs present at relatively high concentrations. We suggest that nonionic surfactants may improve bioremediation performance with soils that have previously undergone extensive bioremediation to enrich for a slowly desorbing profile.     

Measurement of dissolved reactive phosphorus using the diffusive gradients in thin films technique with a high-capacity binding phase

Measurement of dissolved reactive phosphorus (DRP) by the diffusive gradients in thin films (DGT) technique was investigated using a new binding phase. Half-dried amorphous zirconium oxide (with 50 ± 5% of water content) was mixed with acrylamide solution for the preparation of the new binding phase. The resulting binding gel had a high binding capacity (223 μg P cm(-2)) for phosphate. The solution of NaOH (1 M) was used for elution of phosphate from the gel, and an elution efficiency of 0.95 was obtained. A test of DGT uptake with this gel showed its dependence on temperature, and there was no influence of pH (3 to 10) and ionic strength (10 nM to 0.1 M). Its capacity for DGT response exceeded 100 μg P cm(-2), corresponding to a DRP concentration of more than 20 mg L(-1) for a 24 h deployment with a standard DGT device at 25 °C, which was at least 50 times of the Fe-oxide gel commonly used in the present DGT technique. Measurements with this high-capacity DGT technique in a laboratory microcosm of homogeneously mixed sediments gave smooth and reproducible mass-depth profiles. This technique was well demonstrated by in situ measurements in algal- and macrophyte-dominated regions of Lake Taihu. The DGT-measured concentrations of DRP were on average 20% and 40% of the DRP concentrations in pore waters, respectively, indicating a partial resupply of the sediments to the pore waters with DRP.     

Effect of feeding deoiled riche polish on the growth and subsequent productive performance of White Leghorn pullets.

An experiment was conducted to compare the feeding value of deoiled rice polish (DRP) with rice polish (RP) for White Leghorn pullets during growth and egg production. DRP was added at 20 and 40% levels replacing RP without adjusting energy and nutrients in the rations. The 40% DRP ration was offered to the pullets either at 1 week or 18 weeks of life. Results showed that the nutritive value of DRP compared well with RP for growth and productive performance though at the cost of 9 to 11% increase in feed consumption but metabolisable energy (m.e.) conversions were comparable. Furthermore, the age at which DRP feeding was initiated, had no effect on egg production. The average egg production for a period of 162 days was 73.4, 73.9 and 72.5% respectively in groups receiving 0, 20, 40% DRP. The increasing level of DRP reduced the egg size slightly but significantly probably due to low content of linoleic acid in the ration.     

Short-term changes in bacterial community fingerprints and potential activities in an alfisol supplemented with solid waste leachates

We investigated the effect on soil functioning of adding leachates from municipal solid waste incinerator (MSWI) ashes to laboratory columns (bare soil) and to field experimental plots (bare soil or grass cover). Leachate of MSWI-solidified air pollution control residues (SAPCr) contained more salts but less heavy metals than did MSWI-bottom ash (BA) leachate. Leachate-supplemented soils (BA soil, SAPCr soil) and control (water added) soil (W) were analyzed after 30 days. Potential denitrifying activity (PDA) and potential N2 fixation (acetylene reduction assay, ARA) were measured in controlled conditions. PDA was significantly lower in SAPCr soil than in W soil, both in the laboratory (-45%) and in bare soil in the field (-31%). ARA values were lower in bare SAPCr soil (-54%) and in bare BA (-25%) soil. Both activities remained unaffected by leachate supplementation in soil under permanent grass cover. Automated ribosomal intergenic spacer analysis (A-RISA) fingerprints and RFLP of nifH gene pools were used to assess changes in the structure of bacterial community. Multivariate analysis of these fingerprints revealed that SAPCr leachate had a stronger effect than BA leachate on the total and N2-fixing bacterial communities. Similar results were obtained for laboratory and bare soil field plots, but leachates did not affect nifH gene pools from soil under permanent grass cover. The stronger impact of SAPCr leachate on both structure of bacterial communities and activities supports the conclusion that observed effects would result from the abundance of salts rather than from heavy metal toxicity.     

Facilitated transport of diuron and glyphosate in high copper vineyard soils

The fate of organic herbicides applied to agricultural fields may be affected by other soil amendments, such as copper applied as a fungicide. The effect of copper on the leaching of diuron and glyphosate through a granitic and a calcareous soil was studied in the laboratory using sieved-soil columns. Each soil was enriched with copper sulfate to obtain soil copper concentrations of 125, 250, 500, and 1000 mg kg(-1). Glyphosate leaching was influenced by soil pH and copper concentration, whereas diuron leaching was not. In the calcareous soil, glyphosate leaching decreased as copper levels increased from 17 mg kg(-1) (background) to 500 mg kg(-1). In the granitic soil, glyphosate leaching increased as copper levels increased from 34 mg kg(-1) (background) to 500 mg kg(-1). The shapes of the copper elution curves in presence of glyphosate were similar to shapes of the glyphosate curves, suggesting the formation of Cu-glyphosate complexes that leach through the soil. Soil copper concentration does not influence diuron leaching. In contrast, increasing copper concentrations reduces glyphosate leaching through calcareous soils, and conversely, increases glyphosate leaching through granitic soils. Our findings suggest that the risk of groundwater contamination by glyphosate increases in granitic soils with elevated copper concentrations.     

Functional characterization of colloidal phosphorus species in the soil solution of sandy soils

The impact of mobile colloids on the transport of phosphorus in the subsurface environment is not well understood. We hypothesized that interactions between metals, organic matter, and P control the dynamics of mobile colloidal P species in excessively fertilized sandy soils. The effect of UV irradiation and additions of 32P, orthophosphate, Fe, Al, and NaF on the concentration of colloidal P was examined using gel filtration chromatography. In addition, molybdate unreactive P (MUP) was characterized using phosphomonoesterase assays. The high molecular mass reactive P (HMMRP) fraction did not react to orthophosphate additions, increased upon Al and Fe additions and decreased upon NaF addition and UV irradiation. These results support the hypothesis that HMMRP is present as organic matter-metal-orthophosphate complexes. The concentration of high molecular mass unreactive P (HMMUP) decreased upon UV irradiation. The MUP concentration slightly decreased upon incubation with phytase and acid phosphatase. These observations fitted well to the "protection" hypothesis, where hydrolyzable P bonds are protected from monoesterase attack through occlusion in colloidal material. Taken together, this study indicates the high potential for subsurface P loss by colloidal particles in soils excessively fertilized with animal manure.     

Bioaccumulation of 14C60 by the earthworm Eisenia fetida

Carbon fullerenes, including buckminsterfullerene (C(60)), are increasingly available for numerous applications, thus increasing the likelihood of environmental release. This calls for information about their bioavailability and bioaccumulation potential. In this study, (14)C-labeled C(60) and (14)C-phenanthrene (positive control) were added separately to soils of varying composition and organic carbon content (OC), and their bioaccumulation in the earthworm Eisenia fetida was compared. Biota-sediment accumulation factors (BSAF) were measured after 24 h depuration in soils with high C(60) dosages (60, 100, and 300 mg-C(60) kg(-1) dry soil), which exceed the soil sorption capacity, as well as in soils with a low C(60) dose (0.25 mg kg(-1)) conducive to a high fraction of sorbed molecular C(60). The BSAF value for the low-dose soil (0.427) was 1 order of magnitude lower than for less hydrophobic phenanthrene (7.93), inconsistent with the equilibrium partition theory that suggests that BSAF should be constant and independent of the K(OW) value of the chemical. Apparently, the large molecular size of C(60) hinders uptake and bioaccumulation. Lower BSAF values (0.065-0.13) were measured for high-dose soils, indicating that C(60) bioaccumulates more readily when a higher fraction of molecular C(60) (rather than larger precipitates) is available. For the high-dose tests (heterogeneous C(60) system), soil OC content did not significantly affect the extent of C(60) bioaccumulation after 28 d of incubation, although higher OC content resulted in faster initial bioaccumulation. For low-dose soils, C(60) BSAF decreased with increasing soil OC, as commonly reported for hydrophobic chemicals due to partitioning into soil OC. There was no detectable transformation of (14)C(60) in either soil or worm tissue. Overall, the relatively low extent but rapid bioaccumulation of C(60) in E. fetida suggests the need for further studies on the potential for trophic transfer and biomagnification.     

Combined gel probes for the in situ determination of dissolved reactive phosphorus in porewaters and characterization of sediment reactivity

Diffusive equilibrium in thin films (DET) and diffusive gradients in thin films (DGT) were applied in situ to obtain high spatial resolution dissolved reactive phosphorus (DRP) sediment porewater profiles in two lagoons of the Gippsland Lakes (SE Australia) during summer. Although the DRP depth profiles were different in each lake, highlighting the sensitivity of DRP to the redox state of the sediment spatial DRP variations obtained from DET and DGT showed striking similarities with depth in each lake. Comparison of DRP concentrations obtained from DGT and DET allows an assessment of the reactivity of the sediment. A dynamic numerical model of DGT-induced flux in sediments (DIFS) quantified reactivity kinetics. Sediment response time (Tc) related to sedimentary phosphorus resupply resulting from DGT-induced lowering of the porewater DRP concentration was calculated. Values of Tc ranged from 4128 to 183 400 s and from 55 to 149 400 s for Lakes Victoria and Wellington, respectively. These results indicate the limited capacity of the sediment to quickly resupply DRP to the porewater, especially in surface sediment which was always characterized by the highest Tc. Adsorption and desorption rate constants were also calculated from DIFS with values ranging from 2 x 10(-3) to 2 x 10(-2) day(-1) and from 0.3 to 21 day(-1) for Lake Victoria and from 2 x 10(-4) to 0.8 day(-1) and from 0.6 to 1558 day(-1) for Lake Wellington, respectively. Diffusive fluxes estimated from the in situ DRP gradient at the sediment-water interface by DET were 558 and 1.2 micromol m(-2) day(-1) in lakes Victoria and Wellington, respectively. Despite only a single measurement, these fluxes highlight a substantial contribution of P from the sediment to the water column in summer for Lake Victoria which is likely to contribute to the recurring blooms of blue-green algae. These calculated fluxes obtained with minimal sediment disturbance and high spatial resolution were substantially different (by a factor of 6-180) from other reported values using more conventional quantitative assessments such as diffusive fluxes (from core slicing) and benthic chambers.     

Zinc-sulfur and cadmium-sulfur association in metalliferous peats: evidence from spectroscopy,distribution coefficients,and phytoavailability

Peat deposits can concentrate chalcophilic metals such as Zn and Cd by biogeochemical processes; as a result, there is a possibility that the solubility, mobility, and bioavailability of these metals could increase when such deposits are drained and cropped, initiating oxidation of organic matter and sulfides under aerobic conditions. We use spectroscopic, chemical, and bioassay approaches to characterize high Zn (88-15,800 mg kg(-1)), Cd (0.55-83.0 mg kg(-1)), and S (3.52-9.54 g kg(-1)) peat soils collected from locations in New York State and Ontario that overlie Silurian-age metal-enriched dolomite bedrock. Total and KNO3-extractable trace metals were determined by ICP emission spectrometry, and labile Cd and Zn were measured in the KNO3 extracts by anodic stripping voltammetry. A greenhouse bioassay with maize and canola was conducted to determine the bioavailability and toxicity of the soil Zn and Cd. The electronic oxidation states of sulfur in the peat soils were determined by X-ray absorption near edge spectroscopy (XANES) and Zn and S distribution in soil particles by energy-dispersive X-ray absorption (EDX) spectroscopy. Sulfur-XANES analyses show that a high percentage (35-45%) of the total soil S exists in the most reduced electronic oxidation states (such as sulfides and thiols), while <5% exists in the most oxidized forms (such as sulfate). EDX analyses indicate a microscopic elemental association between Zn and S in these soils. Despite the EDX evidence of close association between Zn and S in soil particles, conventional X-ray diffraction analyses of the bulk soils did not detect a mineral phase of sphalerite (ZnS) in any of the soils. The distribution coefficients (Kd) for Zn and Cd increased with soil pH and indicated stronger Cd retention than Zn in the peats. The results of the bioassaytests showed that most of the high-Zn soils were very phytotoxic, with plant shoot Zn levels exceeding 400 mg kg(-1). Conversely, Cd concentrations in the plant shoots were generally below 2 mg kg(-1), showing a tendency toward low Cd phytoavailability relative to Zn. The information gained from the spectroscopic analyses (S-XANES and EDX) was used to explain the macroscopic observations (Cd and Zn Kd values and phytoavailability data) in these peat soils; we conclude that sulfur biogeochemical cycling may play an important role in Zn and Cd retention in these organic soils.