Simple Model of Dissolved Oxygen Consumption in a Bay within High Organic Loading: An Applied Remediation Tool

San Vicente Bay is a coastal shallow embayment in Central Chile with multiple uses, one of which is receiving wastewater from industrial fisheries, steel mill effluents, and domestic sewage. A simulation model was developed and applied to dissolved oxygen consumption by organic residues released into this embayment. Three compartments were established as function of: depth, circulation and outfall location. The model compartments had different volumes, and their oxygen saturation value was used as baseline. The parameters: (a) BOD₅ of the industrial and urban effluents, (b) oxygen demand by organic sediments, (c) respiration, (d) photosynthesis and (e) re-aeration were included in the model. Iteration results of the model showed severe alterations in Compartment 1, with a decrease of 65% in the oxygen below saturation. Compartment 2 showed a small decline (10%) and compartment 3 did not show apparent changes in oxygen values. Measures recommended for remediation were to decrease the BOD₅ loading by 30% in the affected sector. Iteration of the model for 200 h following recommendations derived from the preceding results produced an increase in saturation of 60% (5 ml O₂ L⁻¹), which suggested an improvement of the environmental conditions.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

Reclamation and revegetation of fly ash disposal sites - Challenges and research needs

Coal-fired power generation is a principal energy source throughout the world. Approximately, 70-75% of coal combustion residues are fly ash and its utilization worldwide is only slightly above 30%. The remainder is disposed of in landfills and fly ash basins. It is desirable to revegetate these sites for aesthetic purposes, to stabilize the surface ash against wind and water erosion and to reduce the quantity of water leaching through the deposit. Limitations to plant establishment and growth in fly ash can include a high pH (and consequent deficiencies of Fe, Mn, Cu, Zn and P), high soluble salts, toxic levels of elements such as B, pozzalanic properties of ash resulting in cemented/compacted layers and lack of microbial activity. An integrated organic/biotechnological approach to revegetation seems appropriate and should be investigated further. This would include incorporation of organic matter into the surface layer of ash, mycorrhizal inoculation of establishing vegetation and use of inoculated legumes to add N. Leaching losses from ash disposal sites are likely to be site-specific but a sparse number of studies have revealed enriched concentrations of elements such as Ca, Fe, Cd, Pb, and Sb in surrounding groundwater. This aspect deserves further study particularly in the longer-term. In addition, during weathering of the ash and deposition of organic matter during plant growth, a soil will form with properties vastly different to that of the parent ash. In turn, this will influence the effect that the disposal site has on the surrounding environment. Nevertheless, the effects of ash weathering and organic matter accumulation over time on the chemical, physical and biological properties of the developing ash-derived soil are not well understood and require further study.     

Occurrence and distribution of trifluralin,ethalfluralin, and pendimethalin in soils used for long-term intensive cotton cultivation in central Greece

In the present study, a soil monitoring program was undertaken in Greek cotton cultivated areas in 2012. Twenty-seven soil samples were collected from the entire Thessaly plain in early summer of 2012, corresponding to approximately three months (current use of pendimethalin), up to one year (for the banned ethalfluralin), and three years (for the also banned trifluralin), after the last dinitroaniline application. Low but not negligible levels of dinitroanilines were detected, ranging from 0.01 to 0.21 μg g^?1 d.w. for trifluralin and 0.01–0.048 μg g^?1 d.w. for pendimethalin, respectively. Trifluralin was the herbicide most frequently detected (44.4%). The high historic application of trifluralin and its high persistence and accumulation potential is in line with the abundance of the detected residues. The present data indicate that soil samples contain extractable residues of banned trifluralin, but based on the comparison of the theoretical PECplateau for trifluralin (0.277 µg g^?1) and the maximum Measured Environmental Concentration, it was concluded that the detected residues should be attributed to previous years’ application. The latter suggested the need for continual monitoring of the dinitroaniline family of pesticides, including the banned substances, aiming thus to an improved environmental profile for agricultural areas.     

Pesticide residue removal in classic domestic processing of tomato and its effects on product quality

This study was undertaken to evaluate the effectiveness of several household practices (washing with water or acidic, alkaline, and oxidizing solutions, and peeling) in minimizing pesticide residue contamination of tomatoes, as well as the impact on the quality of the treated fruit. Tests were performed using two systemic fungicides (azoxystrobin and difenoconazole) and one contact fungicide (chlorothalonil). Solid-liquid extraction with low temperature partition (SLE/LTP) and liquid-liquid extraction with low temperature partition (LLE/LTP) were used to prepare the samples for pesticides determination by gas chromatography. Washing the tomatoes with water removed approximately 44% of chlorothalonil, 26% of difenoconazole, and 17% of azoxystrobin. Sodium bicarbonate (5%) and acetic acid (5%) solutions were more efficient, removing between 32 and 83% of the residues, while peeling removed from 68 to 88% of the pesticides. The washing solutions altered some fruit quality parameters, including acidity and chroma, and also caused weight loss. Acetic acid (0.15 and 5%) and hypochlorite (1%) solutions had the greatest effect on these parameters.     

Persistence,degradation and leaching of coumaphos in soil

Abstract

Dissipation, degradation and leaching of fresh ¹⁴C coumaphos, alkylated ¹⁴C coumaphos and aged residues of ¹⁴C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4 ‐ methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of ¹⁴C-labeled sulfadiazine (¹⁴C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A_p horizon of loamy sand, orthic luvisol; A_p horizon of silt loam, cambisol) amended with fresh and aged (6 months) ¹⁴C-manure [40 g kg^?1 of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with ¹⁴C-SDZ. Mineralization of ¹⁴C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable ¹⁴C (ethanol-water, 9:1, v/v) decreased with time to 4–13% after 218 days of incubation with fresh and aged ¹⁴C-manure and both soils. Non-extractable residues were the main route of the fate of the ¹⁴C-SDZ residues (above 90% of total recovered ¹⁴C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the ¹⁴C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl₂ solution) also decreased with increasing incubation period (5–7% after 218 days). Due to thin-layer chromatography (TLC), 500 μg of ¹⁴C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh ¹⁴C-manure, and about 50 μg kg^?1 after 218 days. Bioavailable ¹⁴C-SDZ portions present in the CaCl₂ extracts were about 350 μg kg^?1 with amendment. Higher concentrations were initially detected with aged ¹⁴C-manure (ethanol-water extracts: 1,920 μg kg^?1; CaCl₂ extracts: 1,020 μg kg^?1), probably due to release of ¹⁴C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the ¹⁴C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble ¹⁴C-SDZ residues contained in ¹⁴C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Estimation of sampling uncertainty for determination of pesticide residues in plant commodities

In order to provide residue data for refining the estimated sampling uncertainty, a coordinated research program was initiated for performing field studies on residues in individual items of leafy vegetables, small and large crops. The trials were carried out in 13 countries with 3 small fruits, 5 large crops, 2 medium/large crops and 3 leafy vegetables. The 25 pesticide active ingredients applied represented the dicarboximide (3), organophosphorus (8), synthetic pyrethroids (5), phthalimides (2), organochlorine (1) and other types of pesticides (6). In addition, 11 supervised field trials were performed in grapes and lettuce by the pesticide manufacturers, and their results were provided for evaluation. The studies represented actual agriculture practice around the world, and provide reliable data for estimation of sampling uncertainty. Based on the 12346 residue data, the best estimate for the relative sampling uncertainty for composite samples, assuming sample size of 10 for small crops and leafy vegetables and 5 for large crops, with 95% confidence limits in brackets are: small commodities: 0.25 (0.20–0.29); Brassica leafy vegetables: 0.20 (0.16–0.24); large commodities: 0.33 (0.29–0.38).     

Efficacy of new mass-trapping devices against Bactrocera oleae (Diptera tephritidae) for minimizing pesticide input in agroecosystems

Decreasing pesticide use in olive groves is central to controlling pathogens and pests such as Bactrocera oleae. This has led to the development of mass trapping devices which not only minimize pesticide use but, with improved efficacy of attractants, also decrease costs associated with pest control and ensures that the quality of olive oil is safe for human consumption. This study was undertaken to test a new device which utilizes reduced quantities of both insecticide (lambda-cyalothrin) as well as the female olive fly pheromone (1,7-dioxaspiro-(5.5)-undecane). The new device was tested against an older device manufactured by the same company. The use of plastic polymers as substrate for encapsulating the pheromone allowed for a slower pheromone release, prolonging the efficacy and duration and thus reducing costs. The density of adult populations was monitored using yellow chromotropic traps that were checked every ten days and the degree of olive infestation, as determined by preimago stages, was assessed by analyzing 100 drupes per plot. Infestation analyses were performed every ten days. The control plot had the lowest density of adults and the highest drupe infestation rate. The new devices were more effective than the older devices in both attracting adults and controlling infestation of drupes. Moreover, the new devices containing reduced amounts of pheromone and insecticide were cheaper and exhibited longer functional efficacy. In addition to the slower release of attractants, the plastic polymers used in these newer devices were also more resistant to mechanical and weather degradations. Results demonstrate that mass trapping can indeed be an effective means of controlling B. oleae via eco-sustainable olive farming.