农药优先监测品种的筛选研究

本文对我国目前正在广泛使用的几百个农药品种,从其产量,田间的施用量以及环境毒理学,环境化学,环境生物学的角度进行了系统的研究。在对各种农药进行环境风险性评价的基础上,筛选出目前在我国使用量大,毒性高,环境危害严重的10个农药品种,作为我国近期内应执行的环境优先监测品种。可以认为,若能控制了这些优先监测农药的环境污染,那么,也就在总体上控制了农药的污染问题。     

Biodegradation during contaminant transport in porous media: 4. Impact of microbial lag and bacterial cell growth

Miscible-displacement experiments were conducted to examine the impact of microbial lag and bacterial cell growth on the transport of salicylate, a model hydrocarbon compound. The impacts of these processes were examined separately, as well as jointly, to determine their relative effects on biodegradation dynamics. For each experiment, a column was packed with porous medium that was first inoculated with bacteria that contained the NAH plasmid encoding genes for the degradation of naphthalene and salicylate, and then subjected to a step input of salicylate solution. The transport behavior of salicylate was non-steady for all cases examined, and was clearly influenced by a delay (lag) in the onset of biodegradation. This microbial lag, which was consistent with the results of batch experiments, is attributed to the induction and synthesis of the enzymes required for biodegradation of salicylate. The effect of microbial lag on salicylate transport was eliminated by exposing the column to two successive pulses of salicylate, thereby allowing the cells to acclimate to the carbon source during the first pulse. Elimination of microbial lag effects allowed the impact of bacterial growth on salicylate transport to be quantified, which was accomplished by determining a cell mass balance. Conversely, the impact of microbial lag was further investigated by performing a similar double-pulse experiment under no-growth conditions. Significant cell elution was observed and quantified for all conditions/systems. The results of these experiments allowed us to differentiate the effects associated with microbial lag and growth, two coupled processes whose impacts on the biodegradation and transport of contaminants can be difficult to distinguish.     

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.     

利用有机基质厌氧生物产氢的试验研究

对利用有机基质厌氧生物产氢过程进行了试验研究 ,结果表明 ,污泥种类、基质种类、基质浓度和起始 p H对厌氧产氢反应有显著影响。当校河底泥在以 2 0 g COD/L的果糖为基质 ,起始 p H为 6.5时 ,产氢效果最佳 ,停滞期仅为 5 h,产气速率高达5 0 .1m L/g VSS·h,且可持续 12 h,累积产气量高达 60 4.9m L/g VSS,其中氢气含量约为 5 0 %。半连续试验的结果表明 ,若及时更换和补充基质 ,适当调节 p H,就可实现持续产氢 ,在 16h内平均产气速率可达 60 .0 m L /g VSS· h,氢气含量约为 45 %。     

Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir

For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis^® HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70–103% and 71–103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0–7.0%, 4.0–8.0% for water and sediment, respectively. Thirty one pesticides (-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p′-DDD, o,p′-DDT, p,p′-DDT, p,p′-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, -chlordane, γ-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g⁻¹ on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l⁻¹ for pore waters and from 48.8 to 890 ng l⁻¹ for water samples, respectively, with a mean concentration of 10.7 ng g⁻¹ in sediment, 735 ng l⁻¹ in pore water and 295 ng l⁻¹ in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.     

Characterization of submicron particles during autumn in Beijing, China

In this study, we performed a highly time-resolved chemical characterization of nonrefractory submicron particles(NR-PM_1) in Beijing by using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer(HR-ToF-AMS). The results showed the average NR-PM_1 mass concentration to be 56.4 ± 58.0 μg/m~3, with a peak at 307.4 μg/m~3. Due to the high frequency of biomass burning in autumn, submicron particles significantly increased in organic content, which accounted for 51% of NR-PM_1 on average. Secondary inorganic aerosols(sulfate + nitrate + ammonium) accounted for 46% of NR-PM_1, of which sulfate,nitrate, and ammonium contributed 15%, 20%, and 11%, respectively. To determine the intrinsic relationships between the organic and inorganic species, we used the positive matrix factorization(PMF) model to merge the high-resolution mass spectra of the organic species and NO+and NO_2~+ions. The PMF analysis separated the mixed organic and nitrate(NO+and NO_2~+) spectra into four organic factors, including hydrocarbon-like organic aerosol(HOA), oxygenated organic aerosol(OOA), cooking organic aerosol(COA), and biomass burning organic aerosol(BBOA), as well as one nitrate inorganic aerosol(NIA) factor. COA(33%) and OOA(30%) contributed the most to the total organic aerosol(OA) mass, followed by BBOA(20%) and HOA(17%). We successfully quantified the mass concentrations of the organic and inorganic nitrates by the NO+and NO2+ions signal in the organic and NIA factors. The organic nitrate mass varied from 0.01-6.8 μg/m~3, with an average of 1.0 ±1.1 μg/m~3, and organic nitrate components accounted for 10% of the total nitrate mass in this observation.     

厌氧/好氧SPNDPR系统实现低C/N城市污水同步脱氮除磷的优化运行

为了解同步短程硝化内源反硝化除磷(SPNDPR)系统的脱氮除磷特性,以低C/N城市污水为处理对象,采用延时厌氧(180 min)/好氧运行的SBR反应器,通过联合调控曝气量和好氧时间,考察了该系统启动与优化运行特性.结果表明,当系统好氧段曝气量为0. 8 L·min~(-1),好氧时间为150 min时,出水PO_4~(3-)-P浓度约为1. 5 mg·L~(-1)左右,出水NH_4~+-N和NO_3~--N浓度由10. 28 mg·L~(-1)和8. 14 mg·L~(-1)逐渐降低至0 mg·L~(-1)和2. 27 mg·L~(-1),出水NO_2~--N浓度逐渐升高至1. 81 mg·L~(-1);当曝气量提高至1. 0 L·min~(-1)且好氧时间缩短至120min后,系统除磷、短程硝化性能逐渐增强,但总氮(TN)去除性能先降低后逐渐升高,最终出水PO_4~(3-)-P、NH_4~+-N分别稳定低于0. 5 mg·L~(-1)和1. 0 mg·L~(-1),好氧段亚硝积累率和SND率分别达98. 65%和44. 20%,TN去除率达79. 78%. SPNDPR系统内好氧段好氧吸磷、反硝化除磷、短程硝化、内源反硝化同时进行保证了低C/N污水的同步脱氮除磷.     

臭氧-生物活性炭对微污染原水中典型持久性有机物的去除效果

以长三角地区J市典型有机微污染水源P水厂为研究对象,考察了臭氧-生物活性炭深度处理工艺对微污染水源水中有机物的去除效果.结果表明,臭氧-生物活性炭深度处理使高锰酸盐指数、总有机碳(TOC)和UV254的平均去除率分别提升19. 2%、10. 4%和23. 0%.水厂原水中检出8种多环芳烃(polycyclic aromatic hydrocarbon,PAHs)、16种有机氯农药(organochlorine pesticides,OCPs)、5种卤乙酸(haloacetic acids,HAAs),其总浓度分别为53. 9~100. 0、6. 5~41. 8、2. 5×103~1. 1×104ng·L~(-1),臭氧-生物活性炭深度处理对多环芳烃和有机氯农药的平均去除率分别为32. 5%和25. 9%,比常规处理工艺出水的水质有显著提升.卤乙酸的去除率为33. 8%~87. 0%,主要通过常规处理工艺去除;臭氧-生物活性炭深度处理对氯代乙酸略有去除,溴代乙酸有少量生成.     

天津主要纳污及入海河流中有机氯农药的污染现状及特征

对天津地区永定新河、北排污河和大沽排污河表层水、悬浮物、间隙水样品中的六六六、滴滴涕、七氯等13种有机氯农药进行了分析检测.结果表明,河流中有机氯农药的高污染区主要为天津几大化工厂附近河段,而纪庄子污水处理厂的出水对大沽排污河中的七氯等有机氯农药的含量有所贡献.样品t检验分析表明,秋季和冬季河流中有机氯农药的来源不存在重大差异.不同介质中有机氯农药的组成特征不同,表层水中主要以溶解性较大的六六六为主,而悬浮物中则以滴滴涕、七氯、环氧七氯和异狄氏剂为主.3条河流中的4种不同HCHs异构体以β-HCH的比例最大,说明河流中的HCHs的存在主要是来自于历史遗留;而DDT/DDE和DDT/∑DDTs的比值高于0.5说明近期存在新的DDT使用.     

珠江三角洲4种代表性土壤/沉积物中自由态与结合态有机氯农药的含量与分布特征

有机氯农药在土壤/沉积物中主要以自由态和结合态存在.本研究选取珠江三角洲地区4种代表不同沉积环境的典型土壤/沉积物样品,先采用碱萃取、盐酸/氢氟酸去矿物等方法对样品进行了组分分离,再采用有机溶剂萃取法对不同组分中自由态和结合态有机氯农药进行了系统分析.结果显示,4种土壤/沉积物总有机氯农药含量为20.96～134.22 μg·kg^-1,其中HCHs总含量为5.66～22.87　μg·kg^-1,DDTs总含量为1.51～11.70　μg·kg^-1,β-HCH、七氯、艾氏剂、异狄氏剂、硫丹硫酸盐和甲氧滴滴涕等6种农药为主要成分,占总有机氯农药的53.56%～77.26%.自由态有机氯农药含量为8.46～88.45　μg·kg^-1,占总有机氯农药的40.37%～65.90%.结合态有机氯农药含量为11.46～45.77　μg·kg^-1,占总有机氯农药的34.10%～59.63%,主要存在于土壤/沉积物的腐殖酸和胡敏素组分,反映了环境中结合态有机氯农药的大量存在.自由态DDT和HCH类有机氯农药的分布情况表明,4种样品均没有新鲜HCH类农药输入而部分样品仍有新鲜DDT类农药输入.结合态有机氯农药在腐殖酸和胡敏素间的分布与有机质碳含量相关,占总有机碳57.71%～80.55%的胡敏素结合了94.78%～97.48%的结合态有机氯农药.风险评价结果表明,部分游离态有机氯农药如γ-HCH、艾氏剂、异狄氏剂、DDT类农药可能存在一定的生态风险.由于单个化合物的总量要比自由态高出约1～30倍,同时结合态农药在一定条件下有释放到环境的可能,因此有机氯农药的环境风险评价和环境标准建立均需考虑结合态有机氯农药.