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。     

Effects of Acid Rain on Competitive Releases of Cd, Cu, and Zn from Two Natural Soils and Two Contaminated Soils in Hunan, China

Leaching experiments of rebuilt soil columns with two simulated acid rain solutions (pH 4.6–3.8) were conducted for two natural soils and two artificial contaminated soils from Hunan, south-central China, to study effects of acid rain on competitive releases of soil Cd, Cu, and Zn. Distilled water was used in comparison. The results showed that the total releases were Zn>Cu>Cd for the natural soils and Cd>Zn≫Cu for the contaminated soils, which reflected sensitivity of these metals to acid rain. Leached with different acid rain, about 26–76% of external Cd and 11–68% external Zn were released, but more than 99% of external Cu was adsorbed by the soils, and therefore Cu had a different sorption and desorption pattern from Cd and Zn. Metal releases were obviously correlated with releases of TOC in the leachates, which could be described as an exponential equation. Compared with the natural soils, acid rain not only led to changes in total metal contents, but also in metal fraction distributions in the contaminated soils. More acidified soils had a lower sorption capacity to metals, mostly related to soil properties such as pH, organic matter, soil particles, adsorbed SO₄ ²⁻, exchangeable Al³⁺ and H⁺, and contents of Fe₂O₃ and Al₂O₃.     

The Fernow Watershed Acidification Study: Ecosystem Acidification, Nitrogen Saturation and Base Cation Leaching

In 1989, a watershed acidification experiment was begun on the Fernow Experimental Forest in West Virginia, USA. Ammonium sulfate fertilizer (35.5 kg N ha⁻¹ yr⁻¹and 40.5 kg S ha⁻¹ yr⁻¹) was applied to a forested watershed (WS3) that supported a 20-year-old stand of eastern deciduous hardwoods. Additions of N and S are approximately twice the ambient deposition of nitrogen and sulfur in the adjacent mature forested watershed (WS4), that serves as the reference watershed for this study. Acidification of stream water and soil solution was documented, although the response was delayed, and acidification processes appeared to be driven by nitrate rather than sulfate. As a result of the acidification treatment, nitrate solution concentrations increased below all soil layers, whereas sulfate was retained by all soil layers after only a few years of the fertilization treatments, perhaps due to adsorption induced from decreasing sulfate deposition. Based on soil solution monitoring, depletion of calcium and magnesium was observed, first from the upper soil horizons and later from the lower soil horizons. Increased base cation concentrations in stream water also were documented and linked closely with high solution levels of nitrate. Significant changes in soil chemical properties were not detected after 12 years of treatment, however.     

用烧结法从沸腾炉渣中提取铝和铁的研究

把沸腾炉渣和石灰及精煤混合制成小球,然后在大约1 000 ℃下烧结.取不同烧结时间的样品用硫酸浸取,得到含有铝离子和铁离子的溶液.试验表明,采用浓度为4 mol/l的硫酸,在80 ℃下浸取烧结球样品(50%沸腾炉渣∶40%精煤∶10%石灰)24 h,可以得到铝和铁的最大提取率,分别为86.50%和94.60%.滤渣可以作为固化材料用于高速公路的路基建设或水泥生产中的添加剂.     

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.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

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).     

盐析分相微萃取—高效液相色谱法测定水中含氯除草剂

采用盐析分相微萃取—高效液相色谱法同时测定水中3种含氯除草剂，建立并优化了反相离子对液相色谱条件，考察了萃取剂种类、盐析剂的种类和加入量及试样pH对萃取效果的影响。对氯苯氧乙酸、2，4-二氯苯氧乙酸和2，4-滴丁酯的质量浓度在0.1~100.0mg/L内与色谱峰面积呈良好的线性关系，相关系数不低于0.9992。平均回收率分别为96.29%、79.16%和70.21%，相对标准偏差小于5.3%。该方法操作简便、绿色环保，适合于水中含氯除草剂的测定。     

Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.     

Spatial and temporal small-scale variability of nitrogen mobilization in a forest ecosystem with high N deposition in NW-Germany

For conifer stands in NW-Germany with high DIN load (23-35 kg N ha⁻¹ a⁻¹) and a long history of nitrogen export the risk of N mobilization were investigated. Ammonium is the most mobilized N species, pointing towards either conditions not favoring nitrification or, more likely - under the dominant aerobic conditions - a very high amount of ammonium in the forest floor. Independence of net nitrification and net ammonification from each other indicates the existence of two separate systems. The nitrifying system depends very much on biotic conditions - as a function of energy and moisture - and seems not to be directly related to N deposition. In contrast, for the ammonification system (Oe horizon) a correlation with the sum of ammonium deposition three months prior to sampling was found. However, the role of disturbance, i.e. nitrogen export, during the last centuries and the role of recovery of the N balance during the last 150 years is still not clear.