溶胶凝胶法制备铜催化剂及其稳定性的研究

介绍了利用溶胶凝胶方法制备铜系催化剂，并考察了制备过程中各个工艺参数对铜系催化剂稳定性的影响。通过优化催化剂的设计和制备方法，可有效地改善Cu^2＋的溶出问题，使该类催化剂具有广阔的应用前景。     

Sublethal impact of paraquat on the life span and parasitic behavior of Diaeretiella rapae M’Intosh

This study focuses on assessing the impact of sublethal doses of paraquat on the survival, the emergence, the life span and the parasitic behavior of Diaeretiella rapae M’Intosh (Hymenoptera: Braconidae). The impact of sublethal doses was measured at room temperature using different densities of the cabbage aphid Brevicoryne brassicae. The results reveal that the field dose of paraquat caused 100% mortality in D. rapae. The percentage emergence of D. rapae decreased from 80.5% in the control group to 71.5% when treated with the lowest concentration of paraquat. Similarly, the life span of parasitoids that emerged from the mummy treated with paraquat also decreased significantly. Oviposition capability and ovipositor thrusting frequency of D. rapae also treated with sublethal dose paraquat decreased significantly along with a shortened patch residence time in the foraging area.     

Phototransformation of herbicide metsulfuron methyl

Phototransformation of the herbicide metsulfuron methyl was investigated on glass surface under sunlight and ultraviolet (UV) light and compared with dark condition. The half-lives of metsulfuron methyl under UV light and sunlight were found to be 0.5 and 7.8 days respectively. Rate of phototransformation followed first order kinetics with significant correlation coefficient. The major photoproducts were identified as methyl-2-sulfonyl-amino-benzoate, 2-amino-6-methoxy-4-methyltriazine and saccharin (O-sulfobenzoimide). Various metabolites from this study were identified by high performance liquid chromatography (HPLC). Authentic samples required for HPLC comparison were prepared in laboratory and characterized on the basis of nuclear magnetic resonance (NMR) and infra red (IR) spectral data. These metabolites were also identified from metsulfuron methyl treated wheat field soil.     

生物有机除草剂防除水田杂草试验研究

采用田间试验方法,进行了生物稻壳粉、生物稻草粉2种生物有机除草剂对水田杂草的防效试验。结果表明,2种生物有机除草剂对水田杂草均有不同程度的防效,其中生物稻壳粉防效最好、经济效益最高,生物稻草粉防效和经济效益次之。该试验研究为生产有机水稻提供了新的除草方法。     

Characterizing sources of nitrate leaching from an irrigated dairy farm in Merced County, California

Dairy farms comprise a complex landscape of groundwater pollution sources. The objective of our work is to develop a method to quantify nitrate leaching to shallow groundwater from different management units at dairy farms. Total nitrate loads are determined by the sequential calibration of a sub-regional scale and a farm-scale three-dimensional groundwater flow and transport model using observations at different spatial scales. These observations include local measurements of groundwater heads and nitrate concentrations in an extensive monitoring well network, providing data at a scale of a few meters and measurements of discharge rates and nitrate concentrations in a tile-drain network, providing data integrated across multiple farms. The various measurement scales are different from the spatial scales of the calibration parameters, which are the recharge and nitrogen leaching rates from individual management units. The calibration procedure offers a conceptual framework for using field measurements at different spatial scales to estimate recharge N concentrations at the management unit scale. It provides a map of spatially varying dairy farming impact on groundwater nitrogen. The method is applied to a dairy farm located in a relatively vulnerable hydrogeologic region in California. Potential sources within the dairy farm are divided into three categories, representing different manure management units: animal exercise yards and feeding areas (corrals), liquid manure holding ponds, and manure irrigated forage fields. Estimated average nitrogen leaching is 872 kg/ha/year, 807 kg/ha/year and 486 kg/ha/year for corrals, ponds and fields respectively. Results are applied to evaluate the accuracy of nitrogen mass balances often used by regulatory agencies to assess groundwater impacts. Calibrated leaching rates compare favorably to field and farm scale nitrogen mass balances. These data and interpretations provide a basis for developing improved management strategies.     

Long-term depletion of calcium and other nutrients in eastern US forests

Both harvest removal and leaching losses can deplete nutrient capital in forests, but their combined long-term effects have not been assessed previously. We estimated changes in total soil and biomass N, Ca, K, Mg, and P over 120 years from published data for a spruce-fir site in Maine, two northern hardwood sites in New Hampshire, central hardwood sites in Connecticut and Tennessee, and a loblolly pine site in Tennessee. For N, atmospheric inputs counterbalance the outputs, and there is little long-term change on most sites. For K, Mg, and P, the total pool may decrease by 2%–10% in 120 years depending on site and harvest intensity. For Ca, net leaching loss is 4–16 kg/ha/yr in mature forests, and whole-tree harvest removes 200–1100 kg/ha. Such leaching loss and harvest removal could reduce total soil and biomass Ca by 20%–60% in only 120 years. We estimated unmeasured Ca inputs from rock breakdown, root-zone deepening, and dry deposition; these should not be expected to make up the Ca deficit. Acid precipitation may be the cause of current high leaching of Ca. Although Ca deficiency does not generally occur now in acid forest soils, it seems likely if anthropogenic leaching and intensive harvest removal continue.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Impacts of agri-environmental policy on land use and nitrogen leaching in Finland

Agri-environmental policies are challenging to be evaluated since they are often implemented in combination with other policies and regulations affecting agriculture. Also input and output markets affect agriculture. We provide impact assessment of agri-environmental scheme implemented in Finland 2007–2013 based on integrated economic and hydrological modelling and counterfactual scenarios. Development of crop specific fertilisation and land use changes, simulated using a multi-regional economic sector model, is included in a nutrient leaching model implemented in a typical agricultural region. Our results on agricultural production, land use, and nitrogen leaching show that the agri-environmental policy successfully mitigates nutrient leaching in intensive production regions but some mitigation potential is lost in less intensive regions.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.