Persistence of fermentative process to phenolic toxicity in groundwater

The fermentation process is an important component in the biodegradation of organic compounds in natural and contaminated systems. Comparing with terminal electron-accepting processes (TEAPs), however, research on fermentation processes has to some extent been ignored in the past decades, particularly on the persistence of fermentation process in the presence of toxic organic pollutants. Both field and laboratory studies, presented here, showed that microbial processes in a groundwater-based system exhibited a differential inhibitory response to toxicity of phenolic compounds from coal tar distillation, thus resulting in the accumulation of volatile fatty acids (VFAs) and hydrogen. This indicated that fermentation processes could be more resistant to phenol toxicity than the subsequent TEAPs such as methanogenesis and sulfate reduction, thus providing us with more options for enhancing bioremediation processes.     

Estimating plant-available nitrogen release from manures, composts, and specialty products

Recent adoption of national rules for organic crop production have stimulated greater interest in meeting crop N needs using manures, composts, and other organic materials. This study was designed to provide data to support Extension recommendations for organic amendments. Specifically, our objectives were to (i) measure decomposition and N released from fresh and composted amendments and (ii) evaluate the performance of the model DECOMPOSITION, a relatively simple N mineralization/immobilization model, as a predictor of N availability. Amendment samples were aerobically incubated in moist soil in the laboratory at 22 degrees C for 70 d to determine decomposition and plant-available nitrogen (PAN) (n = 44), and they were applied preplant to a sweet corn crop to determine PAN via fertilizer N equivalency (n = 37). Well-composted materials (n = 14) had a single decomposition rate, averaging 0.003 d(-1). For uncomposted materials, decomposition was rapid (>0.01 d(-1)) for the first 10 to 30 d. The laboratory incubation and the full-season PAN determination in the field gave similar estimates of PAN across amendments. The linear regression equation for lab PAN vs. field PAN had a slope not different from one and a y-intercept not different than zero. Much of the PAN released from amendments was recovered in the first 30 d. Field and laboratory measurements of PAN were strongly related to PAN estimated by DECOMPOSITION (r(2) > 0.7). Modeled PAN values were typically higher than observed PAN, particularly for amendments exhibiting high initial NH(4)-N concentrations or rapid decomposition. Based on our findings, we recommend that guidance publications for manure and compost utilization include short-term (28-d) decomposition and PAN estimates that can be useful to both modelers and growers.     

Nitrogen- vs. phosphorus-based dairy manure applications to field crops: nitrate and phosphorus leaching and soil phosphorus accumulation

Management of animal manures to provide nutrients for crop growth has generally been based on crop N needs. However, because manures have a lower N/P ratio than most harvested crops, N-based manure management often oversupplies the crop-soil system with P, which can be lost into the environment and contribute to eutrophication of water bodies. We examined the effects of N- vs. P-based manure applications on N and P uptake by alfalfa (Medicago sativa L.), corn (Zea mays L.) for silage, and orchardgrass (Dactylis glomerata L.), leaching below the root zone, and accumulation of P in soil. Treatments included N- and P-based manure rates, with no nutrient input controls and inorganically fertilized plots for comparison. Nitrate concentrations in leachate from inorganic fertilizer or manure treatments averaged 14 mg NO(3)-N L(-1), and did not differ by nutrient treatment. Average annual total P losses in leachate did not exceed 1 kg ha(-1). In the top 5 cm of soil in plots receiving the N-based manure treatment, soil test P increased by 47%, from 85 to 125 mg kg(-1). Nitrogen- and P-based manure applications did not differ in ability to supply nutrients for crop growth, or in losses of nitrate and total P in leachate. However, the N-based manure led to significantly greater accumulation of soil test P in the surface 5 cm of soil. Surface soil P accumulation has implications for increased risk of off-field P movement.     

Mapping ground water vulnerability to pesticide leaching with a process-based metamodel of EuroPEARL

To support EU policy, indicators of pesticide leaching at the European level are required. For this reason, a metamodel of the spatially distributed European pesticide leaching model EuroPEARL was developed. EuroPEARL considers transient flow and solute transport and assumes Freundlich adsorption, first-order degradation and passive plant uptake of pesticides. Physical parameters are depth dependent while (bio)-chemical parameters are depth, temperature, and moisture dependent. The metamodel is based on an analytical expression that describes the mass fraction of pesticide leached. The metamodel ignores vertical parameter variations and assumes steady flow. The calibration dataset was generated with EuroPEARL and consisted of approximately 60,000 simulations done for 56 pesticides with different half-lives and partitioning coefficients. The target variable was the 80th percentile of the annual average leaching concentration at 1-m depth from a time series of 20 yr. The metamodel explains over 90% of the variation of the original model with only four independent spatial attributes. These parameters are available in European soil and climate databases, so that the calibrated metamodel could be applied to generate maps of the predicted leaching concentration in the European Union. Maps generated with the metamodel showed a good similarity with the maps obtained with EuroPEARL, which was confirmed by means of quantitative performance indicators.     

Evaluation of the ADAPT model for simulating nitrogen dynamics in a tile-drained agricultural watershed in central Illinois

Assessing the accuracy of agronomic and water quality simulation models in different soils, land-use systems, and environments provides a basis for using and improving these models. We evaluated the performance of the ADAPT model for simulating riverine nitrate-nitrogen (NO3-N) export from a 1500-km2 watershed in central Illinois, where approximately 85% of the land is used for maize-soybean production and tile drainage is common. Soil chemical properties, crop nitrogen (N) uptake coefficient, dry matter ratio, and a denitrification reduction coefficient were used as calibration parameters to optimize the fit between measured and simulated NO3-N load from the watershed for the 1989 to 1993 period. The applicability of the calibrated parameter values was tested by using these values for simulating the 1994 to 1997 period on the same watershed. Willmott's index of agreement ranged from 0.91 to 0.97 for daily, weekly, monthly, and annual comparisons of riverine nitrate N loads. Simulation accuracy generally decreased as the time interval decreased. Willmott's index for simulated crop yields ranged from 0.91 to 0.99; however, observed crop yields were used as input to the model. The partial N budget results suggested that 52 to 72 kg N ha(-1) yr(-1) accumulated in the soil, but simulated biological N fixation associated with soybeans was considerably greater than literature values for the region. Improvement of the N fixation algorithms and incorporation of mechanisms that describe soybean yield in response to environmental conditions appear to be needed to improve the performance of the model.     

Recycling of an industrial sludge and marine clay as light-weight aggregates

The geographical limitations of Singapore, its restricted natural resources and voluminous municipal and industrial waste streams, make environmental management a major challenge for the island state. In an attempt to find ways to reduce importation of raw materials and the waste sent to landfill, light weight aggregates were produced from marine clay and a CaF(2)-rich semiconductor industry sludge. Aggregates were produced in a bench-scale rotary kiln with three clay/sludge loadings (90/10, 70/30 and 50/50%). All three mixtures showed good bloating behavior during firing and the ceramic pellets (1-1.5cm diameter) had densities well below that required for light-weight aggregates. In the initial tests, the pore sizes of the aggregates were in general too large resulting in high water absorption. Comparisons between the composition of the two waste products and the aggregates showed a significant loss of fluorine (40-60%) during processing; a problem which may require flue gas treatment. Leach testing showed that the formed aggregates would not pose a human or environmental hazard in terms of fluorine mobilization.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

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.     

Trace elements and microbiological parameters in farmed Nile tilapia with emphasis on muscle,water, sediment and feed

Fish may bioaccumulate contaminants from the aquatic environment and extend them to the food chain provoking risks to human health. This study evaluated the microbiological parameters of the pond´s water and trace elements concentrations in samples of water, sediment, feed and muscle of farmed Nile tilapia used for human consumption in southern Brazil. A total of 240 fish were collected from 12 tilapia farms. Sediment, tank water and dry ration used in the animals' diet were collected for analysis. Analysis were performed by Energy Dispersion X-ray Fluorescence (EDXRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Induced Coupled Plasma Optical Emission Spectrometer (ICP-OES), and Atomic Absorption Spectrometer (AAS-VGA). In addition, the microbiological analysis of the water was carried out. The concentrations of Se, I, Fe, Cu and Zn in fish muscle were higher than the recommended by the Brazilian legislation, considering the advised daily intake for adults. The arsenic element had concentrations above the limit stipulated by the present Brazilian legislation, observed in all samples of muscle, sediment and tank water highlighting a possible environmental and fish contamination by the toxic element. Moreover, the arsenic concentration in the water presented a positive correlation (ρ?=?0.33) with arsenic in the muscle, suggesting that tilapia is a good environmental bioindicator, once they properly reflect the levels of arsenic in the water. It is suggested to perform an arsenic speciation for quantification of the inorganic form and accurate assessment of the degree of toxicity in the muscle samples and risks it can bring to human health. Regarding the other potentially toxic elements (Hg, Pb and Cd), and microbiological analysis of water it was verified that the consumption of the fish in question does not raise risks, since the values are within a quality benchmark established by law. The concentration of total and fecal coliforms in pond´s water in the facilities was in agreement with the microbiological indexes required by the legislation of CONAMA class II. Western region presented the lowest concentrations of fecal coliforms when compared to the other regions. There was no significant difference in the microbiological counts of total heterotrophic bacteria, Vibrio spp. and Pseudomonas spp. among the regions.