氯胺消毒对三卤甲烷生成影响因素研究

采用腐殖酸模拟天然水体中消毒副产物前体物,探求了氯氨比、氯胺投加量、总有机碳(TOC)浓度和Br-浓度在氯胺消毒过程中对消毒副产物——三卤甲烷(THMs)生成量的影响。结果表明:(1)随着氯氨比的降低,THMs及各组分的生成量显著减少。(2)THMs的生成量均随着氯胺投加量的增加而增加,且都呈现出了良好的线性关系。当氯胺投加量大于7.0mg/L时,氯代卤化物成了优势产物。(3)随着TOC浓度的增加,THMs生成量增加,且具有一定的线性关系;三氯甲烷和一溴二氯甲烷生成量均增加,氯氨比为3∶1(质量比,下同)时三氯甲烷和一溴二氯甲烷生成量增加了9.86、7.80μg/L,氯氨比为5∶1时则分别增加了15.21、13.62μg/L;三溴甲烷和二溴一氯甲烷生成量均呈现先增加后减少的趋势。(4)随着Br-浓度的增加,THMs、一溴二氯甲烷、二溴一氯甲烷和三溴甲烷生成量均增加,三氯甲烷生成量减少。溴化物的存在会促进THMs的产生。     

湿法净化黑烟中添加剂对炭黑沉降性能的影响

湿法净化黑烟中炭黑颗粒物的关键在于降低吸收液的表面张力并以高性能絮凝剂使其从溶液中絮凝、沉降以利于分离。选用十六烷基三甲基溴化胺(CTAB)为主要表面活性剂,使之与十二烷基苯磺酸钠(SDBS)和月桂醇聚氧乙烯(9)醚(AEO-9)进行复配实验,研究了复配液的表面张力,再向最低表面张力的复配表面活性剂溶液中投加絮凝剂聚合氯化铝(PAC)和聚丙烯酰胺(PAM),探讨絮凝剂的添加对黑烟颗粒沉降和絮凝的影响.实验结果表明:同时添加表面活性剂CTAB,SDBS和PAC,并使之浓度分别为0.5 mmol/L,0.4 mmol/L和200 mg/L时,炭黑颗粒的沉降效果最好,沉降率高达94%,且絮凝体较大,沉降时间仅为2 min。     

高效苯降解菌的筛选鉴定及其在生物过滤塔处理苯的填料选择

从污水处理厂曝气池的活性污泥筛选出1株苯的高效降解真菌HD-3,经形态特征、ITS基因序列系统学分析,确定HD-3为杂色曲霉Aspergillus versicolor,该菌株8 d内对初始浓度439.3 mg/L和4 393 mg/L的苯的降解率分别为78.56%和33.96%。当苯的初始浓度为439.3 mg/L,HD-3降解苯的最适温度为30℃,最适pH为4.5。在此基础上,提出了采用不同填料生物过滤塔处理苯废气的工艺,并进行了实验研究,实验结果表明:(1)随着苯的浓度提高,苯的降解率逐渐降低。当苯的浓度为200 mg/m3时,煤质柱状活性炭生物过滤塔、生物陶粒生物过滤塔、竹材生物过滤塔的苯平均去除率(REave)分别为93.63%、93.16%和82.38%;当苯的进口浓度增加到3 000 mg/m3时,3种生物过滤塔的苯平均去除率(REave)分别为78.89%、68.43%和51.87%。(2)不同填料对苯的去除能力不同,煤质柱状活性炭>生物陶粒>竹材。     

硝酸盐还原条件下对氯硝基苯的生物还原转化

针对对氯硝基苯和硝酸盐复合污染问题,以乙醇作为共基质,通过间歇式实验,在基质充足和不足2种条件下考察了NO3-对对氯硝基苯还原过程影响。实验结果表明,在基质充足条件下,对氯硝基苯和NO3-还原过程不互相产生抑制作用。当初始COD浓度为100 mg/L,由于基质不足,NO3-对对氯硝基苯还原过程产生竞争性抑制作用,且抑制作用随着NO3-浓度升高而增强,当NO3-浓度为150 mg/L和300 mg/L时,与空白样相比对氯硝基苯还原速率分别下降20%和54%,且溶液中出现NO2-积累,浓度分别为33.68 mg/L和44.92 mg/L。当采用生物法修复氯硝基苯化合物和硝酸盐复合污染水体时,应考虑基质的供给和硝酸盐的影响。     

不同消毒剂对饮用水中可同化有机碳的影响

以某地表水为原水（TOC为5．3mg／L），研究了氯、氯胺和臭氧3种消毒剂对可同化有机碳（AOC）的影响。结果表明，投加1mg／L氯氧化30min就会使AOC升高近3倍。投加3种剂量（1、2、3mg／L）的氯胺，氧化30min时AOC增加不到1倍；氧化24h时AOC浓度均比30min时的高，这说明氯胺的作用机理与氯不同。投加臭氧2．0mg／L氧化30min时可使AOC增加2．4倍；当臭氧质量浓度大于2．0mg／L时，AOC开始下降，这说明一部分中间产物进一步被氧化成了二氧化碳和水。     

生物与化学表面活性剂协同洗脱土壤中PCBs的研究

通过序批实验和土柱淋洗实验研究了由生物表面活性剂鼠李糖脂(RL)与非离子化学表面活性剂十二烷基醇聚氧乙烯(6)醚(POE(6))混合得到的复配试剂洗脱污染土壤中多氯联苯(PCBs)的作用效果及其作用机理。结果表明,同一土样中,从批实验得到的PCBs洗脱率略高于土柱淋洗实验。RL与POE(6)两种单一试剂对人工污染土样中的PCBs洗脱率均大于60%,而对陈化土样中的洗脱率均不到20%,且土壤中的TOC含量越高,PCBs的洗脱率越低。在质量浓度为301 mg/L(10 CMC)及1 505 mg/L(50 CMC)的RL-POE(6)复配试剂中,RL与POE(6)对人工污染土壤中PCBs的洗脱具有一定的协同作用。当复配试剂的浓度为301 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱没有协同作用;但当RL-POE(6)的浓度增加到1 505 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱具有明显的协同作用。     

消毒剂和溶解氧对管网铁释放影响的中试研究

针对南水北调中线水源地丹江口水库水调入受水区城市后,可能引起管网铁腐蚀产物释放的问题,从北方某受水区城市的实际管网中挖取了原通地下水的3个地点的铸铁管道,在丹江口搭建了中试模拟系统,开展水源切换以及消毒剂和溶解氧对管网铁释放影响的中试研究。结果表明,实验管道管垢较薄且稳定性较差,在水源切换初期有"黄水"现象发生;增加进水硫酸根浓度,管网系统出水总铁浓度和浊度均有所增加;在0.3~3.6 mg/L的范围内改变进水自由氯浓度对实验系统铁释放的影响没有明显的规律;但进水氯胺浓度从1.3 mg/L增加到2.0 mg/L时,YS系统的铁释放有所升高;进水溶解氧浓度从8 mg/L增加到15 mg/L时,实验系统的铁释放都有明显的降低,但再增加到20 mg/L时,铁释放反而有所升高。     

添加剂对炭黑颗粒润湿和沉降性能的影响

为提高湿式除尘装置对炭黑颗粒物的去除效率，通过向吸收液中添加复配表面活性剂以提高吸收液对炭黑的润湿性，投加絮凝剂使进入吸收液的炭黑颗粒发生凝聚和沉降，从而使吸收液得以循环利用。其中表面活性剂的复配以非离子表面活性剂月桂醇聚氧乙烯（9）醚（AEO-9）为主，与十二烷基苯磺酸钠（SDBS）、十六烷基三甲基溴化胺（CTAB）和壬酚基聚氧乙烯醚（TX-10）分别复配，筛选出复配效果最好的一组复配液；然后投加絮凝剂，探讨絮凝剂的加入对吸收液中炭黑颗粒物絮凝沉降的影响。结果表明，在AEO-9浓度为0．05mmol／L，TX-10浓度为0．09mmol／L时，吸收液的表面张力最小，为36．75mN／m；投加无机絮凝剂聚合氯化铝（PAC）浓度为100mg／L时，经15min沉降，炭黑的沉降率可达88．1％，上清液中悬浮颗粒的平均粒径为6．36μm。     

MBR出水氯、紫外、臭氧单独与组合消毒

采用氯、紫外和臭氧单独与2种组合工艺对MBR工艺中试出水进行了消毒实验,研究了不同消毒方式对指示性微生物的去除效果以及消毒副产物三卤甲烷(THMs)生成量随有效氯投加量的变化。结果表明,组合工艺消毒效果明显优于单独消毒效果,紫外剂量为25 mJ/cm2与有效氯投加量为3 mg/L的紫外与氯组合、臭氧投加量为6 mg/L与有效氯投加量为4 mg/L的臭氧与氯组合2种工艺消毒后出水中的总大肠菌群指标均满足《污水再生利用城市杂用水水质》(GB/T 18920-2002)的要求。THMs生成量随着有效氯投加量的增加而增加。相对紫外与氯组合消毒,臭氧与氯组合消毒可以大幅度降低THMs生成量,有效氯投加量为4 mg/L时,THMs生成浓度为14.11μg/L,比氯单独消毒过程降低了37.19%。     

胺化麻黄废渣生物吸附剂对水中阳离子染料的吸附

以麻黄废渣为原料,采用环氧氯丙烷和二乙烯三胺对其进行化学改性,得到麻黄废渣的改性产物。将其应用到中性红和亚甲基蓝2种染料模拟废水的吸附实验,并研究了p H值、吸附剂用量、吸附时间等因素对吸附的影响。结果表明,在p H值为5.5,吸附温度为25℃的条件下,用4 g/L的胺化麻黄废渣生物吸附剂吸附初始浓度为1 000 mg/L的中性红溶液0.5 h,去除率为99.89%;用10 g/L的胺化麻黄废渣生物吸附剂吸附初始浓度为500 mg/L的亚甲基蓝溶液1 h,去除率为99.38%。改性吸附剂对中性红和亚甲基蓝的吸附可以用准二级动力学方程描述,吸附等温线符合Langmuir和Freundlich模型,根据Langmuir方程,25℃时胺化麻黄废渣生物吸附剂对中性红和亚甲基蓝的最大吸附量分别为362.3 mg/g和152.7 mg/g。实验结果显示,胺化麻黄废渣生物吸附剂是一种吸附性能优异的吸附剂,用于处理染料废水有较好的应用前景。     

Risk assessment of biocides in roof paint

BACKGROUND, AIM AND SCOPE: Many surface coatings, including roof paints, contain biocides. It is generally not known to what extent roof paint biocides leach from the paint, and consequently, what concentration the biocide may attain in a rainwater collection system. To this end the leaching of specific biocides from a variety of German roof paints was investigated and the resulting concentrations in collected rain water were estimated. MATERIALS AND METHODS: A laboratory simulation was used to determine the time dependant leaching rate of the biocide from the paint into synthetic rainwater. The concentrations of biocide in the leachate were quantified using HPLC. The course of the leachate concentrations over time was fitted using a simple mathematical model. This was then used to estimate concentrations of biocides in a typical household rainwater collection system over time. RESULTS: Surprisingly, the biocides found in the paints did not always concur with the declared biocides. Concerning the modelling of runoff concentrations, it was found that--under the model assumptions--the rain intensity and cumulative raining time after application are the dominant factors influencing the concentration of the biocide. At the highest modelled rain intensity of 40 mm/hour it only takes about 2 hours to reach peak concentrations lower than 0.1 mg/L, at 0.3 mm/hour it takes about 10 hours to reach peak concentrations of 1.3, 0.9, 5.2 and 1.1 mg/L for terbutryn from Emalux paint, terbutryn from Südwest paint, carbendazim from Emalux paint, and carbendazim from MIPA paint, respectively. DISCUSSION: The results confirm that biocides leached from roof paint will be present in roof runoff. The highest estimated peak concentrations are close to the water solubility of the respective biocides. This indicates that the model assumption of a concentration independent leaching rate will tendentially lead to an overestimation of the leached concentrations under these circumstances. However, under most circumstances such as higher rain intensities, and longer time after peak concentrations have been reached, the runoff concentrations are far from the solubility limit, and therefore it is proposed that the model assumptions are tenable. CONCLUSIONS: The leaching of biocides from roof paints can be roughly assessed using a relatively simple approach. The declaration of biocidal ingredients in roof paints should be improved and information on their biocide leaching behaviour should be made available. Furthermore, the estimations should be evaluated by a field study. RECOMMENDATIONS AND PERSPECTIVES: The leaching study indicated that the concentrations of selected biocides can reach significant levels, especially after low intensity rainfall. Taking into account the inherent biological activity of the substances under scrutiny, it can already be concluded that it is not advisable to use runoff water from roofs freshly painted with biocide containing roof paints. These results have been complemented by a literature search of biological effects of the investigated biocides, ecotoxicological tests with several species and a risk analysis for organisms exposed to runoff water. This will be presented in Part 2 of this contribution.     

Occurrence of imidacloprid,carbendazim, and other biocides in Italian house dust: Potential relevance for intakes in children and pets

The occurrence of pesticides intended for non-agricultural use was investigated in 206 dust samples drawn from vacuum-cleaner bags from residential flats in Italy. The multi-residue analysis targeted on 95 different active principles was performed with UPLC-MS/MS, with a Limit of Quantification (LOQ) of 0.008 μg/g dry weight. The results indicated the presence of imidacloprid (IMI) and carbendazim (CARB) in 30% and 26% of the samples, with a mean and P95 concentration between 1.6 and 39 and between 0.08 and 4.9 μg/g, respectively. Combined presence of two biocides was noted in 19.4% samples, of three biocides in 9.2% samples, of four biocides in 3.4% samples, and of five and six biocides in 0.5% and 1% samples, respectively. According to the estimated dust intake in infants/toddlers aged 6–24 months (16–100 mg d^?1) and cats (200 mg d^?1), it was possible to obtain risk characterization with respect to the Acceptable Daily Intake (ADI) for IMI of 0.060 mg/kg body weight (bw) proposed by the European Food Safety Authority (EFSA) and the chronic Population Adjusted Dose (cPAD) of 0.019 mg/kg bw d^?1 by US-EPA. Under the worst-case scenario, the presence of IMI in dust indicates potential exceedance of the cPAD in kittens, to be considered as sentinel also accounting for combined exposure. This study highlights the relevance of consumer empowerment about the responsible use of pesticides as biocidal products in indoor environment.     

有机污染胁迫对人工湿地中浮萍抗氧化系统的影响

湿地植物在处理高负荷有机废水时会受到不同程度的氧化胁迫。本研究基于对浮萍的有机污染胁迫模拟系统,通过对浮萍脂质过氧化和抗氧化防御系统的监测与分析,研究了浮萍对有机污染胁迫的耐受能力及胁迫去除后浮萍的恢复规律。结果表明,浮萍对有机污染胁迫具有较高的耐受性,在胁迫去除后,具有一定的恢复能力。在COD小于400mg/L时,浮萍并未受到氧化胁迫;当COD达到800 mg/L时,浮萍体内ROS含量上升,细胞膜脂过氧化加剧,但抗氧化酶活性升高,抗氧化物质含量增加,浮萍可保持生长,胁迫去除后,抗氧化防御系统可恢复到对照水平;当COD过高（≥1 000mg/L）,ROS急剧上升,抗氧化防御系统遭受破坏,造成不可逆伤害,胁迫去除后不能恢复正常生长。     

Little effect of excessive biofouling on the uptake of organic contaminants by semipermeable membrane devices

The effects of water flow rate and antifouling agents on the extent of biofouling and on the uptake of non-polar organic contaminants by semipermeable membrane devices (SPMDs) were studied during four field experiments in the Western Wadden Sea. Biofouling densities on the sampler surface ranged from 0.3 to 16 g dry weight dm⁻². Water sampling rates were estimated from the dissipation rates of performance reference compounds (PRCs). The antifouling agents Irgarol and capsaicin (33 mg per ml triolein) had no noticeable effect on the extent of fouling, and caused only a 5–10% increase in the absorbed amounts. Enhanced flow rates had only a minimal effect on the amount of biofouling, but caused the water sampling rates to increase by a factor of 1.2–2. Increases in PRC-derived sampling rates were reflected by increases in the absorbed amounts for compounds that were in the linear uptake stage of the sampling process. The results imply (1) that extreme biofouling does not always result in reduced sampling rates, (2) that extreme biofouling does not preclude the existence of flow effects on the sampling rates, and (3) that differences in uptake rates are quantitatively reflected by the dissipation rates of PRCs.     

Bioassays and selected chemical analysis of biocide-free antifouling coatings

Over the years several types of biocide-free antifouling paints have entered the market. The prohibition of biocidal antifouling paints in special areas of some European countries such as Sweden, Denmark and Germany has favoured the introduction of these paints to the market.

Several types of biocide-free antifouling paints were subjected to bioassays and selected chemical analysis of leachate and incorporated substances. Both non-eroding coatings (silicones, fibre coats, epoxies, polyurethane, polyvinyl) and eroding coatings (SPCs, ablative) were tested to exclude the presence of active biocides and dangerous compounds. The paints were subjected to the luminescent bacteria test and the cypris larvae settlement assay, the latter delivering information on toxicity as well as on efficacy.

The following chemical analyses of selected compounds of dry-film were performed:

• leaching-rate of organotin compounds from silicones and of nonylphenol and bisphenol A from epoxy and vinyl based coatings,

• concentration and leaching rate of selected organic compounds in polyurethane,

• concentration of heavy metals in eroding coatings.

The results of the bioassays indicated that none of the coatings analysed contained leachable biocides. Nevertheless, some products contained or leached dangerous compounds. The analyses revealed leaching of nonylphenol (up to 74.7 ng/cm²/d after 48 h) and bisphenol A (up to 2.77 ng/cm²/d after 24 h) from epoxy resins used as substitutes for antifouling paints. The heavy metal, zinc, was measured in dry paint film in quantities up to 576 000 ppm in erodable coatings, not incorporated as a biocide but to control the rate of erosion. Values for TBT in silicone elutriates were mostly below the detection limit of 0.005 mg/kg. Values for DBT ranged between <0.005 and 6.28 mg/kg, deriving from catalysts used as curing agents. Some biocide-free paints contained leachable, toxic and dangerous compounds in the dry film, some of which may act as substitutes for biocides or are incorporated as plasticizers or catalysts. Implications to environmental requirements and legislation are discussed.     

Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae)

Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC50s values for perchlorate and chromium were 74+/-8.0 mg/L and 0.41+/-0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC50 values for perchlorate and Cr (VI) were 17,000+/-3200 and 38+/-1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes.     

Biofiltration pretreatment for reverse osmosis (RO) membrane in a water reclamation system

Biofouling control is considered as a major challenge in operating membrane systems. A lab-scale RO system was setup at a local water reclamation plant to study the feasibility of using biofiltration as a pretreatment process to control the biofouling. The biological activity in the RO system (feed, product, reject streams) was tested using the standard serial dilution plating technique. Operational parameters such as differential pressure (DP) and permeate flowrate of the system were also monitored. Effects of biofilter on AOC and DOC removals were investigated. Biofiltration was found to be a viable way of assimilable organic carbon (AOC) and dissolved organic carbon (DOC) removals, with removal efficiencies of 40-49% and 35-45% at an empty bed contact time (EBCT) of 30 min. It was also found that using the biofiltration as a pretreatment reduced the rate of biofouling. It took only about 72 h for biofouling to have a significant impact on the performance of the RO membrane, when the system was operated without using biofiltration as pretreatment. There was, however, a five times increase in operational length to more than 300 h when biofiltration was used. This study presented the suitability of the biofilter as an economical and simple way of biofouling control for RO membrane.     

物化-生化组合工艺处理火炸药废水中试研究

针对火炸药废水毒性大、硝基化合物浓度高、COD浓度高、可生化性差的特点,采用"三维电极(TDE)-铁屑内电解-厌氧-曝气生物滤池"工艺对火炸药废水进行中试研究。结果表明,在进水初始浓度COD为3 330～5 330 mg/L,硝基化合物为200～300 mg/L情况下,此工艺不但能够稳定去除COD,去除率达到96.9%,且能高效去除硝基化合物,去除率高达99.6%。出水水质完全符合《兵器工业水污染物排放标准(火炸药)》(GB14470-2002)要求,系统运行稳定。     

Toxicity of anti-fouling biocides to encysted metacercariae of Echinoparyphium recurvatum (Digenea: Echinostomatidae) and their snail hosts

The toxicity of the anti-fouling biocides tributyltin (TBTO), copper, and Irgarol 1051 (irgarol) at a nominal concentration of 10 microg/l over a 30 day period were investigated against the viability of metacercarial cysts of the digenean parasite Echinoparyphium recurvatum resident within the body of two common freshwater snails, Lymnaea peregra and Physa fontinalis. Reduced parasite viability was found under most exposures in both snail species. However a greater effect of toxicant exposure was found in cysts within P. fontinalis compared to those in L. peregra. This was associated with an increased mortality of the host snail. Among all tested biocides, TBTO exposures induced the highest mortality to both the parasite and their hosts. These results suggest that parasite viability is interlinked with survival of the host snail. The mechanisms of differing toxicity between host species and its relevance to successful parasite transmission to the next host are discussed.     

Nitrate-contaminated groundwater remediation by combined autotrophic and heterotrophic denitrification for sulfate and pH control: batch tests

Groundwater remediation was evaluated for combined autotrophic and heterotrophic denitrification under high (154 mg/L as CaCO₃) and low (95 mg/L as CaCO₃) alkaline conditions. Two levels of acetate (47 and 94 mg/L) and ethanol (24 and 48 mg/L) were added to the reactors. Obtained denitrification rates were 2.89, 2.58, 3.55, 1.96, and 2.0 mg-N/L?·?h for high alkaline conditions, whereas under low alkaline conditions has given 2.36, 1.94, 2.47, 2.74, and 2.29 mg-N/L?·?h for control, 47 and 94 mg/L acetate, and 24 and 48 mg/L ethanol, respectively. Nitrite was accumulated for controls but reactors with acetate and ethanol did not accumulate nitrite. Acetate and ethanol addition decreased sulfate to nitrate ratios in the range of 4.5–7.58 for high alkaline conditions (12.77 for control) and 4.43–6.78 for low alkaline conditions (7.90 for control). Acetate was more efficient compared with ethanol in controlling sulfate production and pH maintenance.