Selenium volatilization in vegetated agricultural drainage sediment from the San Luis Drain, Central California

The presence of large amounts of Se-laden agricultural drainage sediment in the San Luis Drain, Central California, poses a serious toxic threat to wildlife in the surrounding environment. Effective management of the drainage sediment becomes a practical challenge because the sediment is polluted with high levels of Se, B, and salts. This two-year field study was conducted to identify the best plant species that are salt and B tolerant and that have a superior ability of volatilizing Se from drainage sediment. The drainage sediment was mixed with clean soil, and vegetated with salado alfalfa (Medicago sativa 'salado'), salado grass (Sporobulus airoides 'salado'), saltgrass-turf (Distichlis spp. 'NYPA Turf'), saltgrass-forage (Distichlis spicata (L.) Greene), cordgrass (Spartina patens 'Flageo'), Leucaenia (Leucaena leucocephola), elephant grass (Pennistum purpureum), or wild type-Brassica (Brassica spp.). Results show that elephant grass produced the greatest amount of biomass and accumulated highest concentrations of B. Highest concentrations of Se, S, and Cl were observed in wild-type Brassica. Biogenic volatilization of Se by plants and soil microbes was greater in summer. Among the treatments, the mean daily rates of Se volatilization (microg Se m(-2)d(-1)) were wild-type Brassica (39) > saltgrass-turf (31) > cordgrass (27) > saltgrass forage (24) > elephant grass (22) > salado grass (21) > leucaenia (19) > salado alfalfa (14) > irrigated bare soil (11) > non-irrigated bare soil (6). Overall, rates of Se volatilization in drainage sediment were relatively low due to high levels of sulfate. To manage Se in drainage sediment by phytoremediation, the biological volatilization process needs to be enhanced substantially under field conditions.     

Tillage management to mitigate herbicide loss in runoff under simulated rainfall conditions

Conservation tillage mitigates soil loss in cropland because plant residues help protect the soil, but effects on pesticide movement in surface runoff are not as straightforward. Effects of soil disturbance on surface runoff loss of chlorimuron and alachlor were evaluated utilizing runoff trays. Soil in the trays was either disturbed (tilled) and kept bare or was not tilled, and existing decomposed plant residue was left on the surface. Rainfall (25mm, 20min) was simulated 1d after alachlor (2.8kg ha(-1)) or chlorimuron (54g ha(-1)) application, and runoff was collected. Runoff fractions were analyzed for herbicide and sediment. Total alachlor loss from bare plots was greater than that in no-tillage plots (4.5% vs. 2.3%, respectively). More than one-third of total alachlor lost from bare plots occurred in the first l of runoff, while no-tillage plots had less runoff volume with a more even distribution of alachlor concentration in the runoff during the rainfall simulation and subsequent runoff period. In contrast, more chlorimuron was lost from no-tillage plots than bare plots (12% vs. 1.5%) even though total runoff volume was lower in the no-tillage plots (10.6mm vs. 13.6mm). This was attributed to dense coverage with partially decomposed plant residue in no-tillage plots (1652kg ha(-1)) that intercepted chlorimuron. It was likely that chlorimuron, a polar compound, was more easily washed off surface plant residues and transported in runoff.     

Dissipation of the herbicide clopyralid in an allophanic soil: laboratory and field studies

Soil dissipation of the herbicide clopyralid (3,6-dichloropicolinic acid) was measured in laboratory incubations and in field plots under different management regimes. In laboratory studies, soil was spiked with commercial grade liquid formulation of clopyralid (Versatill, 300 g a.i. L(-1) soluble concentrate) @ 0.8 microg a.i. g(-1) dry soil and the soil water content was maintained at 60% of water holding capacity of the soil. Treatments included incubation at 10 degrees C, 20 degrees C, 30 degrees C, day/night cycles (25/15 degrees C) and sterilized soil (20 degrees C). Furthermore, a field study was conducted at the Waikato Research Orchard near Hamilton, New Zealand starting in November 2000 to measure dissipation rates of clopyralid under differing agricultural situations. The management regimes were: permanent pasture, permanent pasture shielded from direct sunlight, bare ground, and bare ground shielded from direct sunlight. Clopyralid was sprayed in dilute solution @ 600 g a.i. ha(-1) on to field plots. Herbicide residue concentrations in soil samples taken at regular intervals after application were determined by gas chromatograph with electron capture detector. The laboratory experiments showed that dissipation rate of clopyralid was markedly faster in non-sterilized soil (20 degrees C), with a half-life (t1/2) of 7.3 d, than in sterilized soil (20 degrees C) with t1/2 of 57.8 d, demonstrating the importance of micro-organisms in the breakdown process. Higher temperatures led to more rapid dissipation of clopyralid (t1/2, 4.1 d at 30 degrees C vs 46.2 d at 10 degrees C). Dissipation was also faster in the day/night (25/15 degrees C) treatment (t1/2, 5.4 d), which could be partly due to activation of soil microbes by temperature fluctuations. In the field experiment, decomposition of clopyralid was much slower in the shaded plots under pasture (t1/2, 71.5 d) and bare ground (t1/2, 23.9 d) than in the unshaded pasture (t1/2, 5.0 d) and bare ground plots (t1/2, 12.9 d). These studies suggest that environmental factors such as temperature, soil water content, shading, and different management practices would have considerable influence on rate of clopyralid dissipation.     

Distribution and bioaccumulation of selenium in aquatic microcosms

Closed-system microcosms were used to study factors affecting the fate of selenium (Se) in aquatic systems. Distribution and bioaccumulation of Se varied among sediment types and Se species. A mixture of dissolved (75)Se species (selenate, selenite and selenomethionine) was sorbed more rapidly to fine-textured, highly organic pond sediments than to sandy riverine sediments. Sulfate did not affect the distribution and bioaccumulation of (75)Se over the range 80-180 mg SO(4) liter(-1). When each Se species was labeled separately, selenomethionine was lost from the water column more rapidly than selenate or selenite. Selenium lost from the water column accumulated primarily in sediments, but volatilization was also an important pathway for loss of Se added as selenomethionine. Loss rates of dissolved Se residues were more rapid than rates reported from mesocosm and field studies, suggesting that sediment: water interactions are more important in microcosms than in larger test systems. Daphnids accumulated highest concentrations of Se, followed by periphyton and macrophytes. Selenium added as selenomethionine was bioaccumulated preferentially compared to that added as selenite or selenate. Organoselenium compounds such as selenomethione may thus contribute disproportionately to Se bioaccumulation and toxicity in aquatic organisms.     

Characterizing kinetics of transport and transformation of selenium in water-sediment microcosm free from selenium contamination using a simple mathematical model

This study developed a seven-compartment model for predicting the fate of selenium (Se) in an aquatic environment containing a water-sediment boundary. Speciation of Se in water-sediment microcosms under microaerobic conditions was measured to evaluate first-order kinetics of Se transportation and transformation. The microcosm consisted of a 10-ml solution containing 1mM soluble Se as selenate (Se6+) or selenite (Se4+) and 8 g wet sediment that was free from Se contamination, sampled from the Senri, Yamato, or Yodo Rivers in Osaka, Japan. Stepwise reaction coefficients describing transportation and transformation were determined using an inverse method on this model which includes: selenate (Se(W)6+) and selenite (Se(W)4+) in ponded water; selenate (Se(S)6+) and selenite (Se(S)4+), elemental Se (Se0), organic Se (Se2-) in sediment; and gaseous Se (DMSe). During this 1-month experiment, soluble Se was transported from ponded water to the sediment and Se was transformed sequentially to other Se species through biochemical reactions. Experimental and kinetic analyses indicated quantitatively that the Yamato River microcosm, with its high organic matter content, had a high adsorption rate of soluble Se. The Yodo River microcosm had a low adsorption rate for Se6+ and a low Se reduction rate. The Senri River microcosm had an apparent high volatilization rate of DMSe. The model developed in this study is extremely useful for predicting fate of Se in aquatic environment in the field.     

Methane consumption by soils of dryland rice agriculture: influence of varieties and N-fertilization

Growth of three rice varieties (Heera, Dhala Heera and Narendra-118) and their relationship with methane consumption was investigated under rainfed (dryland) condition. Overall methane flux rates ranged between -0.58 to 1.25 mg m(-2) h(-1) across varieties, treatments, and dates of measurements. Except for two days when soil was saturated, the soil consumed 0.05-0.58 mg CH4 m(-2) h(-1); these rates were inversely related with soil moisture. N-fertilization reduced consumption rates. Although all plant growth parameters, except for number of tillers, exhibited relationship with methane consumption in control plots, only root porosity did so in fertilized plots. Combinations of plant growth characteristics explained 74-92% variability in seasonal CH4 consumption in unfertilized plots. It was concluded that methane consumption by dryland soils was influenced by rice variety, soil moisture and nitrogen fertilization.     

Measurement of trifluralin volatilization in the field: Relation to soil residue and effect of soil incorporation

Volatilization may represent a major dissipation pathway for pesticides applied to soils or crops. A field experiment (September, 2002), consisted in volatilization fluxes measurements during 6 days, covering the periods before and after soil incorporation carried out 24 h after trifluralin spraying on bare soil. Evolution of concentration in soil was measured during 101 days, together with soil physical and meteorological variables. Volatilization fluxes were very high immediately after application (1900 ng m(-2) s(-1)), decreased down to 100 ng m(-2) s(-1) in the following 24 h. Soil incorporation strongly abated trifluralin concentration in the air. 99% of the total volatilization losses recorded over the 6 days following application occurred before incorporation. Volatilization fluxes evidenced a diurnal cycle driven by environmental conditions. Soil trifluralin residues could still be quantified 101 days after application. Our results highlight the caution required when using soil degradation half-life values in the field for volatile compounds.     

Napropamide residues in runoff and infiltration water from pepper production

A field study was conducted on a Lowell silty loam soil of 2.7% organic matter at the Kentucky State University Research Farm, Franklin County, Kentucky. Eighteen universal soil loss equation (USLE) standard plots (22 x 3.7 m each) were established on a 10% slope. Three soil management practices were used: (i) class-A biosolids (sewage sludge), (ii) yard waste compost, each mixed with native soil at a rate of 50 ton acre(-1) on a dry-weight basis, and (iii) a no-mulch (NM) treatment (rototilled bare soil), used for comparison purposes. Devrinol 50-DF "napropamide" [N,N-diethyl-2-(1-naphthyloxy) propionamide] was applied as a preemergent herbicide, incorporated into the soil surface, and the plots were planted with 60-day-old sweet bell pepper seedlings. Napropamide residues one hour following spraying averaged 0.8, 0.4, and 0.3 microg g(-1) dry soil in sewage sludge, yard waste compost, and no-mulch treatments, respectively. Surface runoff water, runoff sediment, and napropamide residues in runoff were significantly reduced by the compost and biosolid treatments. Yard waste compost treatments increased water infiltration and napropamide residues in the vadose zone compared to sewage sludge and NM treatments. Total pepper yields from yard waste compost amended soils (9187 lbs acre(-1)) was significantly higher (P < 0.05) than yield from either the soil amended with class-A biosolids (6984 lbs acre(-1)) or the no-mulch soil (7162 lbs acre(-1)).     

Dissipation of some organochlorine insecticides in cropped and uncropped soil

Dissipation of four organochlorine insecticides, viz. aldrin, HCH, chlordane and heptachlor was studied in a sandy loam soil with and without crops during a period of 10 cropping seasons. Dissipation of all chemicals followed first-order kinetics (r(2)=0.537 - 0.976) with almost similar persistence in cropped and uncropped soils for all the insecticides. The average half-lives, (t(1/2) values) for total residues of aldrin, HCH, chlordane, and heptachlor in cropped treatments were 80.7, 58.8, 93.2, and 110 days. Their respective values in fallow plots were 78.4, 83.8, 154, and 116 days. None of the parent compounds or their isomers could be detected below the 20 cm depth at the termination of the experiment. Highest residue concentrations were observed in the surface 10 cm layer in fallow plots, but in the deeper (10-20 cm) layer in cropped plots. Analysis of plants and grains showed significant residues of all the chemicals. Degradation of these compounds in cropped and uncropped plots is discussed with regard to their volatilization, microbial degradation, leaching, and plant uptake.     

Coupled production and transport of selenium vapor in unsaturated soil: evaluation by experiments and numerical simulation

Volatilization of selenium (Se) from soil to the atmosphere involves several sequential chemical reactions that form volatile Se species, followed by transport of the gaseous Se through the soil. This paper describes a numerical model that simulates the chemical and physical processes governing the production and transport of Se vapor in unsaturated soil. The model couples the four Se species involved in the production of Se vapor through chemical reactions, and allows each to migrate through the soil by advection, liquid or vapor diffusion depending on its affinity for the dissolved or vapor phase. The coupled transformations and transport of the four Se species, i.e., selenate, selenite, elemental and organic Se, and Se vapor, were calculated based on the Crank-Nicolson finite difference method. The model was used to analyze fluxes of Se vapor measured from a soil amended with inorganic Se in the form of selenate and covered with unamended clean soil of various thicknesses. Evolution of Se vapor from the soil was very fast, with measurable amounts of Se detected within 24 h. The peak of Se volatilization, detected at the 6th day, reached 3.31 Se microgram/day for the uncovered soil, but was reduced to near the detection limit (0.05 microgram/day) in the presence of a 8- or 16-cm clean soil cover. With two reaction rate coefficients fitted to the data, the model described Se volatilization very well. The estimated rate coefficient of Se methylation was unexpectedly high, with a value of 0.167/day. The net volatilization of Se, however, was severely inhibited by the fast demethylation, i.e., the reverse reaction which converted volatile Se species back into nonvolatile forms. As a result, Se vapor only penetrated a few centimeters in the soil. The demethylation rate coefficient, assessed by independent transport experiments using dimethyl selenide, was estimated as 186.8/day, corresponding to a half-life of only 5.3 min for Se vapor. Results of this study indicated that rapid demethylation of Se vapor during its diffusive transport through a soil is probably an important limiting factor in the volatilization of Se under natural conditions.     

Absorption of selenium by Lactuca sativa as affected by carboxymethylcellulose

Several organic compounds of high molecular weight present in soil interact with selenium and may act as active binding agents affecting its availability in soil, and, consequently, selenium uptake by plants. This study is aimed at investigating the effects of polysaccharides on selenium speciation in soil and on selenium absorption by Lactuca sativa L. plants. Three-week-old seedlings were transplanted into pots filled with soil, and sodium selenite at rates of 1.5 and 5mgSekg(-1) of soil, or sodium selenate at a rate of 1.5mgSekg(-1) of soil were applied. Carboxymethylcellulose (CMC) was added to the soil at rates of 0, 3 and 30mgkg(-1) of soil. After 48 and 110d from transplanting plants were harvested, separated into root and shoot, and fresh and dry matter weights were recorded. Total selenium was determined in both soil and plant samples. A sequential extraction was used to investigate the different Se oxidation states and assess the availability of Se in soil after the final harvesting. Both selenite and selenate were absorbed by roots, but plants amended with Se(VI+) showed higher selenium concentration than plants amended with Se(IV+). Selenite appears to be less mobile than selenate both in soil and plants. The addition of carboxymethylcellulose to soil decreased the amount of selenium absorbed by plants. CMC interacted with Se, making it less mobile as evidenced by the increase in the insoluble fractions. The insoluble Se forms in soil may represent environmental Se sinks potentially available for plants if the substrate is re-used for subsequent growth cycles and selenium species are mobilized as a result of biological and chemical processes.     

New methodology to investigate potential contaminant mass fluxes at the stream-aquifer interface by combining integral pumping tests and streambed temperatures

The spatial pattern and magnitude of mass fluxes at the stream-aquifer interface have important implications for the fate and transport of contaminants in river basins. Integral pumping tests were performed to quantify average concentrations of chlorinated benzenes in an unconfined aquifer partially penetrated by a stream. Four pumping wells were operated simultaneously for a time period of 5 days and sampled for contaminant concentrations. Streambed temperatures were mapped at multiple depths along a 60m long stream reach to identify the spatial patterns of groundwater discharge and to quantify water fluxes at the stream-aquifer interface. The combined interpretation of the results showed average potential contaminant mass fluxes from the aquifer to the stream of 272microgm(-2)d(-1) MCB and 71microgm(-2)d(-1) DCB, respectively. This methodology combines a large-scale assessment of aquifer contamination with a high-resolution survey of groundwater discharge zones to estimate contaminant mass fluxes between aquifer and stream.     

Anaerobic biodegradation of biphenyl in various paddy soils and river sediment

The anaerobic degradation of biphenyl was investigated in four uncontaminated Japanese paddy soils and one river sediment sample contaminated with benzene and chlorinated aliphatics. Two of the paddy soils and the sediment were capable of degrading biphenyl anaerobically without any additional medium or electron acceptors. The half-lives of biphenyl biodegradation in the three samples were 212 d in the Kuridashi soil, 327 d in the Kamajima soil, and 429 d in the river sediment. The Kuridashi soil metabolized 1+/-0.3% of [U-14C]-biphenyl into CO2 and 5+/-2% into water-soluble metabolites after 45 d of incubation. Submerged conditions, which result in lower nitrate and iron oxide contents, and neutral pH, appeared to be the common properties among the samples that influenced their degradation capacities. The addition of 10mM sulfate and 20mM Fe(III) as electron acceptors did not enhance the biphenyl degradation rate, whereas 10mM nitrate completely inhibited biphenyl degradation. The addition of different electron donors (lactate, acetate, or pyruvate) slightly slowed the degradation. Molybdate (an inhibitor of sulfate-reducing bacteria) had an inhibitory effect on biphenyl biodegradation, but bromoethanesulfonic acid (an inhibitor of methanogens) did not. Most biphenyl degradation was observed when only water was added, with no other electron acceptors or donors. These results suggest that sulfate-reducing bacteria and fermentative microbial populations play important roles in anaerobic biphenyl biodegradation in paddy soil.     

Leaching of glyphosate and AMPA under two soil management practices in Burgundy vineyards (Vosne-Romanée, 21-France)

Some drinking water reservoirs under the vineyards of Burgundy are contaminated with herbicides. Thus the effectiveness of alternative soil management practices, such as grass cover, for reducing the leaching of glyphosate and its metabolite, AMPA, through soils was studied. The leaching of both molecules was studied in structured soil columns under outdoor conditions for 1 year. The soil was managed under two vineyard soil practices: a chemically treated bare calcosol, and a vegetated calcosol. After 680 mm of rainfall, the vegetated calcosol leachates contained lower amounts of glyphosate and AMPA (0.02% and 0.03%, respectively) than the bare calcosol leachates (0.06% and 0.15%, respectively). No glyphosate and only low amounts of AMPA (<0.01%) were extracted from the soil. Glyphosate, and to a greater extent, AMPA, leach through the soils; thus, both molecules may be potential contaminants of groundwater. However, the alternative soil management practice of grass cover could reduce groundwater contamination by the pesticide.     

A PAH fate model for San Francisco Bay

A mass balance model was applied to simulate the long-term fate of PAHs in San Francisco Bay. The model treats the Bay as a single box with interacting water and sediment compartments, and includes loading, volatilization, outflow to the ocean, degradation, and burial in deep sediment. The estimated time required for loss of one-half of the mass in the Bay in the absence of loading ranged from 20 d for naphthalene to 5 yr for benzo(b)fluoranthene. Uncertainty analysis using Monte Carlo simulation indicated a high degree of influence and uncertainty for degradation rates, suggesting that improved estimates of degradation would significantly improve the predictive ability of the model. A comparison of model calculations to literature values suggested that external PAH loading to San Francisco Bay was at or above previous estimates of 3600 kgyr(-1), and that degradation in the Bay was within the range of commonly published estimates for high molecular weight PAHs (4.0 x 10(-5) to 4.0 x 10(-4)d(-1)).     

Denitrification in cypress swamp within the Atchafalaya River Basin, Louisiana

Nitrogen has been implicated as a major cause of hypoxia in shallow water along the Louisiana/Texas, USA coasts. Excess nitrogen (mainly nitrate) from Mississippi and Atchafalaya River drainage basins may drive the onset and duration of hypoxia in the northern Gulf of Mexico. Restoring and enhancing denitrification have been proposed to reduce and control coastal hypoxia and improve water quality in the Mississippi River Basin. Sediments were collected from six baldcypress restoration sites within the Atchafalaya River Basin, Louisiana, USA. The acetylene blockage technique was used to measure background and potential sediment denitrification rates. Denitrification fluxes were measured before nitrate addition (background rates) and after nitrate addition of 100mgNl(-1) (potential denitrification) at three seasonal temperatures. Background denitrification was low across all cypress swamp sites ranging from 0.9 to 8.8, 0.6 to 28.5 and 8.8 to 47.5g N evolved ha(-1)d(-1) at water/sediment column temperatures of 8, 22 and 30 degrees C, respectively. After nitrate addition, temperature had a significant effect on sediment denitrification potential. Maximum rates measured at 8, 22 and 30 degrees C were approximately 250-260, 550 and 970gNha(-1)d(-1), respectively. Most of the added nitrate in water columns, incubated at 8 degrees C, was removed after 65d compared to 32d and 17d at 22 and 30 degrees C, respectively. These results indicate cypress swamps have the potential to assimilate and process elevated levels of floodwater nitrate with denitrification being a major removal mechanism.     

Napropamide Residues in Runoff and Infiltration Water from Pepper Production

Abstract

A field study was conducted on a Lowell silty loam soil of 2.7% organic matter at the Kentucky State University Research Farm, Franklin County, Kentucky. Eighteen universal soil loss equation (USLE) standard plots (22 × 3.7 m each) were established on a 10% slope. Three soil management practices were used: (i) class-A biosolids (sewage sludge), (ii) yard waste compost, each mixed with native soil at a rate of 50 ton acre^?1 on a dry-weight basis, and (iii) a no-mulch (NM) treatment (rototilled bare soil), used for comparison purposes. Devrinol 50-DF “napropamide” [N,N-diethyl-2-(1-naphthyloxy) propionamide]was applied as a preemergent herbicide, incorporated into the soil surface, and the plots were planted with 60-day-old sweet bell pepper seedlings. Napropamide residues one hour following spraying averaged 0.8, 0.4, and 0.3 μ g g^{? 1} dry soil in sewage sludge, yard waste compost, and no-mulch treatments, respectively. Surface runoff water, runoff sediment, and napropamide residues in runoff were significantly reduced by the compost and biosolid treatments. Yard waste compost treatments increased water infiltration and napropamide residues in the vadose zone compared to sewage sludge and NM treatments. Total pepper yields from yard waste compost amended soils (9187 lbs acre^?1) was significantly higher (P < 0.05) than yield from either the soil amended with class-A biosolids (6984 lbs acre^?1) or the no-mulch soil (7162 lbs acre ^?1).     

Behavior of pesticides in sediment/water systems in outdoor mesocosms

The distribution of eight pesticides between sediment and water held in 1-m square outdoor stainless-steel mesocosms was studied, simulating both spring and autumn applications. Pesticide behavior was largely independent of rate of application, chosen in the first three experiments to be 4% or 40% of the normal field rate so as to simulate spray drift or partial overspray. Following application by spray to the water surface, all compounds were uniformly distributed in the 30 cm of overlying water within 24 h. The lipophilic pesticides (chlorpyrifos, pendimethalin, and permethrin) moved into the sediment within 30 d but with little penetration below 2.5 cm depth, and only chlorpyrifos persisted beyond 30 d. The mass balance of these lipophilic pesticides at 1 d was only 26.3% to 61%, with these initial losses attributed to processes such as volatilization. Isoproturon and chlorotoluron persisted for around 120 d, remaining largely in the overlying water with a maximum of 15% in the sediment. Permethrin and difenoconazole were much less persistent in these mesocosms, with very little ever found in the sediment in contrast to previous findings in laboratory-scale stirred systems as used in registration tests. The polar mecoprop remained almost entirely in the water phase and was rapidly degraded. Two further experiments examined also the influence of the submerged plant Lagarosiphon major in the mesocosms, the first experiment simulating a full-rate overspray with chlorpyrifos and linuron and the second a repeat in spring of the earlier main autumn experiment. Both chlorpyrifos and linuron applied in the autumn were quite persistent over the winter period, with about 20% still remaining after 152 d. Uptake into L. major was correlated with pesticide lipophilicity, but was only a small factor compared to uptake by sediment and degradation in these lightly vegetated systems.     

Effects of long-term de-vegetation on the quantity and quality of water extractable organic matter (WEOM): biogeochemical implications

The effects of five decades of de-vegetation on the quantity and quality of water extractable organic matter (WEOM) in soils were investigated. The WEOM was sampled from the A(p)-horizon of an agricultural plot and a neighboring bare plot 5 times during the spring. The quantity of WEOM was determined by measuring its organic carbon content, and its quality was characterized by its UV absorptivity, by a humification index based on the fluorescence emission spectrum, and by its fluorescence efficiency (fluorescence divided by UV absorption). The potential substrate value of WEOC was also determined by its microbial metabolic loss over 7d. As expected, long-term de-vegetation decreased WEOC significantly (by 70%). Not expected were two results: (1) Qualitative de-vegetation effects were relatively small. In some cases they were statistically significant, but in all cases differences compared to the vegetated plots were less than 13%; and (2) Despite a major increase in vegetation (from essentially 0% to 100% plant coverage) on the agricultural plot during the spring, there was no seasonal trend to be seen in any of the measured parameters. These unexpected field based results indicate that vegetal input into the ecologically relevant dissolved organic matter pool occurs only to a minor degree directly. Most of the fresh material must be initially sequestered into the soil matrix from which it is then subsequently released. This also indicates that there is a strong "buffering" in soils of freshly introduced organic matter. These results should be considered in our attempt to understand biogeochemical cycles in soil.     

Modelling pesticide volatilization after soil application using the mechanistic model Volt'Air

Volatilization of pesticides participates in atmospheric contamination and affects environmental ecosystems including human welfare. Modelling at relevant time and spatial scales is needed to better understand the complex processes involved in pesticide volatilization. Volt'Air-Pesticides has been developed following a two-step procedure to study pesticide volatilization at the field scale and at a quarter time step. Firstly, Volt'Air-NH₃ was adapted by extending the initial transfer of solutes to pesticides and by adding specific calculations for physico-chemical equilibriums as well as for the degradation of pesticides in soil. Secondly, the model was evaluated in terms of 3 pesticides applied on bare soil (atrazine, alachlor, and trifluralin) which display a wide range of volatilization rates. A sensitivity analysis confirmed the relevance of tuning to K_h. Then, using Volt'Air-Pesticides, environmental conditions and emission fluxes of the pesticides were compared to fluxes measured under 2 environmental conditions. The model fairly well described water temporal dynamics, soil surface temperature, and energy budget. Overall, Volt'Air-Pesticides estimates of the order of magnitude of the volatilization flux of all three compounds were in good agreement with the field measurements. The model also satisfactorily simulated the decrease in the volatilization rate of the three pesticides during night-time as well as the decrease in the soil surface residue of trifluralin before and after incorporation. However, the timing of the maximum flux rate during the day was not correctly described, thought to be linked to an increased adsorption under dry soil conditions. Thanks to Volt'Air's capacity to deal with pedo-climatic conditions, several existing parameterizations describing adsorption as a function of soil water content could be tested. However, this point requires further investigation. Practically speaking, Volt'Air-Pesticides can be a useful tool to make decision about agricultural practices such as incorporation or for the estimation of overall pesticide volatilization rates, and it holds promise for time specific dynamics.