A novel model concept for modelling the leaching of natural toxins: results for the case of ptaquiloside.

Phytotoxins are a large class of highly diverse emerging environmental contaminants that have been detected at high concentrations in plants, water and soils. This study presents a novel modelling approach for assessing the fate of plant toxins in the soil-plant-atmosphere continuum, developed for the specific case of ptaquiloside (PTA), a carcinogenic phytotoxin produced by Pteridium aquilinum. The mechanistic model DAISY has been adapted for reproducing phytotoxin dynamics in plants, covering processes such as toxin generation in the canopy, wash off by precipitation and toxin recovery in the canopy after depletion events. Transport of the toxin in the soil was simulated by the advection-dispersion equation assuming weak sorption and degradation for two Danish soils. The model simulates realistic toxin contents in the plant during the growing season, where the actual PTA content is dynamic and a function of the biomass. An average of 48% of the PTA produced in the canopy is washed off by precipitation, with loads in the soil often in the order of mg m-2 and up to a maximum of 13 mg m-2 in a single rain event. Degradation in the soil removes 99.9% of the total PTA input to the soil, while only 0.1% leaches into the soil. The median annual flux-averaged predicted environmental concentrations during single events are often in the order of µg L-1, reaching up to 60 µg L-1 for the worst-case scenario. The simulated results for both degradation and wash off are of the same order of magnitude as the published data. Based on the results, we conclude that DAISY, with the newly implemented processes, is a useful tool for understanding, describing and predicting the fate of PTA in the soil. Further work comparing the model results with real data is needed for the calibration and validation of the model.

A three-step test of phosphate sorption efficiency of potential agricultural drainage filter materials.

Phosphorus (P) eutrophication of lakes and streams, coming from drained farmlands, is a serious problem in areas with intensive agriculture. Installation of P sorbing filters at drain outlets may be a solution. Efficient sorbents to be used for such filters must possess high P bonding affinity to retain ortho-phosphate (Pi) at low concentrations. In addition high P sorption capacity, fast bonding and low desorption is necessary. In this study five potential filter materials (Filtralite-P(®), limestone, calcinated diatomaceous earth, shell-sand and iron-oxide based CFH) in four particle size intervals were investigated under field relevant P concentrations (0-161 µM) and retentions times of 0-24 min. Of the five materials examined, the results from P sorption and desorption studies clearly demonstrate that the iron based CFH is superior as a filter material compared to calcium based materials when tested against criteria for sorption affinity, capacity and stability. The finest CFH and Filtralite-P(®) fractions (0.05-0.5 mm) were best with P retention of ≥90% of Pi from an initial concentration of 161 µM corresponding to 14.5 mmol/kg sorbed within 24 min. They were further capable to retain ≥90% of Pi from an initially 16 µM solution within 1½ min. However, only the finest CFH fraction was also able to retain ≥90% of Pi sorbed from the 16 µM solution against 4 times desorption sequences with 6 mM KNO3. Among the materials investigated, the finest CFH fraction is therefore the only suitable filter material, when very fast and strong bonding of high Pi concentrations is needed, e.g. in drains under P rich soils during extreme weather conditions.

Adsorption of the disinfectant benzalkonium chloride on montmorillonite. Synergistic effect in mixture of molecules with different chain lengths.

The biocide benzalkonium chloride (BAC) is a mix of cationic alkylbenzyldimethylammonium surfactants having different alkyl chain lengths. A comparative study of adsorption on the phyllosilicate clay montmorillonite of two of these surfactants, with alkyl chains having respectively 12 C atoms (BAC-12) and 14 C atoms (BAC-14), and a mixture of both surfactants is presented in this work. Adsorption isotherms were performed for individual surfactants and for a 1:1 mixture BAC-12+BAC-14. The adsorption was investigated in an ample concentration range that covers almost seven orders of magnitude in concentrations (from 1 nM to 10 mM), range that includes environmentally relevant concentrations. Quantification of BAC was performed by HPLC-UV and LC-MS and the results were completed with powder X-Ray diffraction. The adsorption of both surfactants leads to adsorption isotherms with two well differentiated steps. The first step corresponds almost exclusively to a cation exchange process, and the binding constant is very similar for both surfactants. The second step of the isotherms is observed at higher concentrations and adsorption is mainly driven by lateral interactions between surfactant molecules. The binding constant of this step is larger for BAC-14 than for BAC-12. Adsorption from a BAC-12+BAC-14 mixture shows a synergistic behaviour, possibly due to a better packing arrangement in the interlayer. Calculations show that in natural systems silicate clays are major sorbents of BAC at low concentrations whereas binding to humic acid is predominant at high concentrations.

Dissipation and leaching of acephate, chlorpyrifos, and their main metabolites in field soils of Malaysia.

Preventive treatment with insecticides at high dosing rates before planting of a new crop- soil drenching- is a common practice in some tropical intensive cropping systems, which may increase the risk of leaching, soil functioning, and pesticide uptake in the next crop. The degradation rates and migration of acephate and chlorpyrifos and their primary metabolites, methamidophos and 3,5,6-trichloropyridinol (TCP), have been studied in clayey red yellow podzolic (Typic Paleudults), alluvial (Typic Udorthents), and red yellow podzolic soils (Typic Kandiudults) of Malaysia under field conditions. The initial concentrations of acephate and chlorpyrifos in topsoils were found to strongly depend on solar radiation. Both pesticides and their metabolites were detected in subsoils at the deepest sampling depth monitored (50 cm) and with maximum concentrations up to 2.3 mg kg(-1) at soil depths of 10 to 20 cm. Extraordinary high dissipation rates for weakly sorbed acephate was in part attributed to preferential flow which was activated due to the high moisture content of the soils, high precipitation and the presence of conducting macropores running from below the A horizons to at least 1 m, as seen from a dye tracer experiment. Transport of chlorpyrifos and TCP which both sorb strongly to soil organic matter was attributed to macropore transport with soil particles. The half-lives for acephate in topsoils were 0.4 to 2.6 d while substantially longer half-lives of between 12.6 and 19.8 d were observed for chlorpyrifos. The transport through preferential flow of strongly sorbed pesticides is of concern in the tropics.

Ergot alkaloids in rye flour determined by solid-phase cation-exchange and high-pressure liquid chromatography with fluorescence detection.

Ergot alkaloids are mycotoxins that are undesirable contaminants of cereal products, particularly rye. A method was developed employing clean-up by cation-exchange solid-phase extraction, separation by high-performance liquid chromatography under alkaline conditions and fluorescence detection. It is capable of separating and quantifying both C8-isomers of ergocornine, alpha-ergocryptine, ergocristine, ergonovine, and ergotamine. The average recovery was 61% +/- 10% with limits of detection from 0.2 to 1.1 microg kg(-1). Twenty-four unknown rye flour samples from Danish mills contained on average 46 microg kg(-1) with a maximum content of 234 microg kg(-1). The most common ergot alkaloids were ergotamine and alpha-ergocryptine including their C8-isomers. A total of 54% of the ergot alkaloids were detected as C(8)-S isomers.

Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil.

Mobility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from soils to surface waters. To study the sorption and mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agricultural Humic Hapludult was investigated and a kinetic model applicable in field-scale models tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrations (0-4.7 mmol L(-1)). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L(-1), the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium." The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics.

Distribution of multiple pesticide residues in apple segments after home processing.

The effects of washing, storing, boiling, peeling, coring and juicing on pesticide residue were investigated for field-sprayed Discovery and Jonagold apples. Residues of chlorpyrifos, cypermethrin, deltamethrin, diazinon, endosulfan, endosulfan sulfate, fenitrothion, fenpropathrin, iprodione, kresoxim-methyl, lambda-cyhalothrin, quinalphos, tolylfluanid and vinclozolin in the processed apples were analysed by gas chromatography. Statistical analysis showed that reductions of 18-38% were required to obtain significant effects of processing practices, depending on pesticide and apple variety. Juicing and peeling the apples significantly reduced all pesticide residues. In the case of detectable pesticide residues, 1-24% were distributed in the juice and in the peeled apple. None of the pesticide residues was significantly reduced when the apples were subject to simple washing or coring. Storing significantly reduced five of the pesticide residues: diazinon, chlorpyrifos, fenitrothion, kresoxim-methyl and tolylfluanid, by 25-69%. Residues of the metabolite endosulfan sulfate were increased by 34% during storage. Boiling significantly reduced residues of fenitrothion and tolylfluanid by 32 and 81%, respectively. Only a few of the observed effects of processing could be explained by the physical or chemical characteristics of the pesticides. No differences in effect of processing due to apple variety were identified.

Starch-encapsulated chlorpyrifos: release rate, insecticidal activity and degradation in soil.

Incorporation of chlorpyrifos into starch matrices was achieved by thermal gelatinization. The level of amylose content in the starch matrices (10 and 52%) and the addition of auxiliary agents, i.e. solvent, emulsifiers or both, were varied and eight different formulations were prepared. According to differential scanning calorimetry (DSC) and X-ray diffraction measurements, chlorpyrifos was partly present in a crystalline form in all the starch formulations. The formulations had controlled release properties, and the release rate into water could be described by a linear model. In a bioassay, the formulations killed all larvae of the cabbage root fly at a dosing of 1.4 kg a.i. per ha. The degradation of chlorpyrifos in soil from the starch formulations could be described in a non-linear logistic model and the half-life was predicted to be 88 days. Differences in the amount of amylose in the starch as well as the addition of solvent and emulsifiers in the preparation procedure had no systematic influence on the release rate, the insecticidal effect and the degradation rate. No correlation between release rate into water and degradation in soil could be established. Two commercial chlorpyrifos formulations Lorsban 15 G (granular) and Cyfos 500 gl(-1) (emulsifiable concentrate), were included in the study for comparison.

Adsorption of cadmium, copper, nickel, and zinc to a poly(tetrafluorethene) porous soil solution sampler.

Suction cups made of poly(tetrafluorethene) (PTFE) are widely used for sampling of soil solution. A brand (Prenart) of PTFE cups was tested for adsorption of Cd, Cu, Ni, and Zn at low concentrations under different conditions. In a laboratory experiment adsorption from a 10 microg L(-1) heavy metal solution with a 0.01 M NaCl background electrolyte was investigated at pH 3.6, 4.5, and 5.8 by pumping the solutions through the cups. The effect of three different ionic compositions was also investigated using 0.01 M CaCl2, 0.01 M NaCl, and no background electrolyte at pH 4.5. In 0.01 M NaCl electrolyte at pH 5.8 the cups acted as effective filters. At pH 3.6 after 300 mL of solution had passed through the cup, equivalence between the Cd and Ni concentrations in influent and effluent was found. No equivalence between effluent and influent concentrations was found for Zn and Cu at pH 4.5 and 5.8. With Ca as the electrolyte, no adsorption of Cd, Ni, or Zn was found. In Na electrolyte, equivalence between influent and effluent concentrations for Cd, Ni, and Zn was reached. The difference between effluent and influent concentrations of Zn, Ni, and Cd remained significant in the absence of electrolyte. For all pH values and electrolytes the difference between effluent and influent concentrations of Cu was significant. It is concluded that PTFE cups affect the concentrations of heavy metals sampled at low soil solution concentrations. Cadmium, Cu, Ni, and Zn adsorb to the cup at pH > 4.5 and low ionic strength.