粉末活性炭对水中氯酚的吸附

2,4-二氯酚、2,4,6-三氯酚、五氯酚是氯酚类污染物的典型代表,鉴于其对人类身体健康的危害和对环境所造成的污染,已被很多国家列为环境优先控制污染物。研究粉末活性炭(PAC)对该3种氯酚的吸附过程以及投炭量、pH值和水质对PAC吸附性能的影响。结果表明:粉末活性炭可以有效去除水中的80%以上的氯酚;吸附行为符合Freundlich吸附等温线和Langmuir吸附等温线;以分子状态存在的氯酚比电离状态更容易被活性炭所吸附。     

Impact of UV-irradiation on the formation of odorous chloroaldimines in drinking water

In order to explain some of the possible origins of an odor episode which took place in a drinking water supply in the region of Paris (France), the impact of disinfection on the formation of odorous by-products was investigated. We have previously established that very odorous and stable chloroaldimines are formed during amino acid chlorination in conditions relevant to those of drinking water treatment. As chlorination is preceded by a UV-irradiation step, we examined here the impact of this irradiation on the formation of chloroaldimines. Irradiation (30 m W cm(-2)) of various amino acids (glycine, valine, phenylalanine) and peptides (Phe-Gly-Gly-Phe, Phe-Ala) led to a degradation of the compounds but it was negligible at the doses applied in drinking water supplies. As peptides were concerned, contrary to what we previously expected, the degradation did not involve the peptidic bond breaking: irradiation induces therefore no increase in the quantity of free amino acids, precursors of odorous chloroaldimines. However chlorination of peptides (Phe-Ala-Ala-Val, Phe-Gly-Gly-Phe and Ala-Phe) showed that chloroaldimines are also probably formed during combined amino acids chlorination.     

固相微萃取-气相色谱法测定饮用水及其水源水中的氯酚

利用固相微萃取(SPME)-气相色谱法(GC)联用技术测定饮用水及其水源水中的氯酚．优化萃取温度、萃取平衡时间、酸度、离子强度等实验条件．所建方法简便、精确,自来水和太湖水中均检测到氯酚。     

Anaerobic transformation of chlorophenols in methanogenic sludge unexposed to chlorophenols

Transformation of all 19 chlorophenol (CP) isomers was investigated in a laboratory anaerobic methanogenic sludge that had not been exposed to synthetic chemicals. Concentration of CP was analyzed over time to calculate disappearance rate constants using first-order reaction kinetics and all possible CP degradation pathways were estimated. The rate constants ranged between 0.46 x 10(-3) and 0.161 day(-1). CPs were transformed via dechlorination. The chlorine atom at the ortho-position was the most easily dechlorinated, whereas dechlorination rate at the para-position was lowest. The overall pathways of CP transformation were much less diverse than that we previously found for contaminated sediment. The Dolfing hypothesis of microbial selection of the most thermodynamically favorable pathways was not applicable for CP transformation in this study as well as previous study performed by our group.     

沈阳市黑臭水体表层水DOM紫外光谱特征分析

为识别黑臭水体中DOM组成、结构及腐殖化水平,运用UV-vis(紫外-可见吸收光谱)与多元统计相结合的方式,对沈阳市5条黑臭水体的27个表层水样中DOM的UV-vis特征及9个紫外光谱指数进行研究。研究表明：27个表层水样中DOM的UV-vis吸收系数的变异系数在30%~80%之间,轻度黑臭水体相对于重度黑臭水体的紫外吸收峰在356、487、657 nm处分别发生了1、2、2 nm的蓝移;轻度黑臭水体紫外光谱指数SUVA254、S275~295、S350~400、A2/A1、A3/A1、A3/A2均高于重度黑臭水体,而E2/E3、E4/E6、E2/E4低于重度黑臭水体,轻度黑臭水体的腐殖化水平与腐殖化趋势高于重度黑臭水体。进一步分析得出：苯酚基(木质素和奎宁基团)决定了黑臭水体中DOM腐殖化进程,不同黑臭水体DOM的组分存在明显差异;轻度黑臭水体中DOM的腐殖化水平、芳香化程度、木质素与其他物质在腐殖化开始的比例、分子质量等均高于重度黑臭水体。多元统计与UV-vis技术对黑臭水体中DOM的组成及结构进行了定性,为黑臭水体的溯源和整治工作提供理论基础。     

Synergistic effects of combination of photolysis and ozonation on destruction of chlorophenols in water.

Synergistic effects including TOC elimination, ozone consumption and microtoxicity reduction for combination of photolysis and ozonation compared to those of direct photolysis and ozonation alone on destruction of chlorophenols including 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol were studied. It was found that the synergistic effects of combination of photolysis and ozonation increased obviously with increasing initial pH of solution to basic pH levels. Results showed that the synergistic effects of photolytic ozonation under the conditions imposed was notable with mineralization rate enlarging more than 100%, oxidation index (OI) decreasing 50%, and microtoxicity being reduced by 30%, indicating that the potentialities of photolytic ozonation compared to direct photolysis and ozonation alone was remarkable for treatment of industrial wastewater containing chlorophenols.     

饮用水中典型致嗅物质吹扫捕集-气相色谱质谱检测方法及优化

采用吹扫捕集/气相色谱-质谱（GC-MS）法对饮用水中致嗅物质2-甲基异茨醇（2-MIB）和土臭素（GSM）进行测定。通过调整吹扫温度、吹扫时间、吹扫时捕集阱的温度、六通阀温度和传输管线温度,分析吹扫捕集条件对吹扫捕集效率的影响,并确定最佳吹扫捕集条件。2-MIB和GSM的方法检出限（MDL）分别为0.729 ng·L-1和1.037 ng·L-1,方法定量限（MQL）分别为2.187 ng·L-1和3.112 ng·L-1,平均加标回收率分别在92%~108%和88%~104%范围内,相对标准偏差分别小于6.5%和9.0%.在20~300 ng·L-1的范围内,各异嗅化合物浓度与响应值的线性关系均良好,相关系数均大于0.999。该方法具有操作简便、检出限低,相关性良好、灵敏度高、重复性好等优点。     

Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water

A procedure based on solid-phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS) was developed and validated in order to analyse 10 phenols in water samples. The optimised conditions were obtained using polyacrylate fibre (PA), 20ml of sample volume, 10% NaCl, pH 4.0 and direct extraction at 35 degrees C and 1000rpm, for 40min. The linear range and quantification limits for these compounds by SPME-GC-MS were defined. An evaluation of the main uncertainty sources of this method is included, which allows expanded uncertainties in the 9.4-35% range for the majority of the compounds. The main source of uncertainty is associated with matrix effects. The validated method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from water supply system of a large area (Lisbon and neighbour municipalities).     

沈阳市黑臭水体治理进展及典型案例分析

以沈阳市为例,从黑臭水体分布、已完成的整治措施及问题识别与诊断3个方面总结了沈阳市建成区黑臭水体的治理现状及进展,提出了黑臭水体整治的近期目标。基于黑臭水体汇水单元污染负荷的分析结果,明确了沈阳市建成区黑臭水体整治方案与整治措施,并以已完成治理的满堂河和白塔堡河为典型河流,总结分析了黑臭水体治理的经验及成效。     

Sequential UV-biological degradation of chlorophenols

The sequential UV-biological degradation of a mixture of 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP), and pentachlorophenol (PCP) was first tested with each pollutant supplied at an initial concentration of 50 mg l(-1). Under these conditions, the chlorophenols were photodegraded in the following order of removal rate: PCP>TCP>DCP>CP with only CP and DCP remaining after 40 h of irradiation. The remaining CP (41 mg l(-1)) and DCP (13 mg l(-1)) were then completely removed by biological treatment with an activated sludge mixed culture. Biodegradation did not occur in similar tests conducted with a non-irradiated mixture due to the high microbial toxicity of the solution. UV treatment lead to a significant reduction of the phytotoxicity to Lipedium sativum but no further reduction of phytotoxicity was observed after biological treatment. Evidence was found that the pollutants were partially photodegraded into toxic and non-biodegradable products. When the pollutants were tested individually (initial concentration of 50 mg l(-1)), PCP, TCP, DCP, 4-CP were photodegraded according to first order kinetic model (r2>99) with half-lives of 2.2, 3.3, 5.7, and 54 h, respectively. The photoproducts were subsequently biodegraded. This study illustrates the potential of UV as pre-treatment for biological treatment in order to remove toxicity and enhance the biodegradability of organic contaminants. However, it also shows that UV treatment must be carefully optimized to avoid the formation of toxic and/or recalcitrant photoproducts and results from studies conducted on single contaminants cannot be extrapolated to mixtures.     

Sequential photochemical-biological degradation of chlorophenols

UV/TiO₂/H₂O₂, UV/TiO₂ and UV/H₂O₂ were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l⁻¹, UV/TiO₂/H₂O₂ treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO₂ and UV/H₂O₂. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r² > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO₂/H₂O₂ treatment. No pollutant removal was observed in the controls conducted with H₂O₂ or TiO₂ only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO₂/H₂O₂-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l⁻¹. COD and Cl mass balances indicated UV, UV/H₂O₂, and UV/TiO₂ treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.     

Levels and spatial distribution of chlorophenols - 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol in surface water of China

The chlorophenol pollutants (CPs) have been reported to occur at relatively high concentrations in some Chinese waters. To map the distribution of CPs in the surface water throughout China, samples were collected from over 600 sites in the seven major watersheds and three drainage areas. The samples were analyzed for the representative CPs including 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. In general, it was observed that 2,4-dichlorophenol and 2,4,6-trichlorophenol were more frequently detected at higher concentrations in the rivers of North China compared with those of South China. High concentration sites of 2,4-dichlorophenol and 2,4,6-trichlorophenol mainly occurred in the Yellow River, Huaihe River, and Haihe River watersheds, while pentachlorophenol contamination mainly occurred in the Yangtze River watershed. The pentachlorophenol was the most ubiquitous CPs being detected in 85.4% of samples (median=50.0ngl(-1); range <1.1-594.0ngl(-1)), 2,4-dichlorophenol was detected in 51.3% (median=5.0ngl(-1); range <1.1-19960.0ngl(-1)) and the 2,4,6-trichlorophenol was detected in 54.4% of water samples (median=2.0ngl(-1), range <1.4-28650.0ngl(-1)). The results of this investigation indicated that 2,4-dichlorophenol and 2,4,6-trichlorophenol contaminations of Yellow River, Huaihe River, and Haihe River watersheds were of particular concern, while the pentachlorophenol contamination mainly occurred in the Yangtze River watershed. These results showed that CPs contamination in the surface water of China was similar to other places of the world.     

Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

Packing material formulation for odorous emission biofiltration

In biological gas treatment, like biofiltration of volatile organic compounds or odorous substances, the microbial nutritional needs could be a key factor of the process. The aim of this work is to propose a new packing material able to provide the lacking nutrients. In the first part of this study, two kinds of material composed of calcium carbonate, an organic binder and two different nitrogen sources, ammonium phosphate and urea phosphate (UP), were compared. The new supports present bulk densities between 0.88 and 1.15g cm(-3), moisture retention capacities close to 50% and 70%, and water cohesion capacities greater than six months for the material with 20% binder. In the second part, oxygen consumption measurements in liquid experiments show that these packing materials could enhance bacterial growth compared to pine bark or pozzolan and have no inhibitory effect. The biodegradation of different substrates (sodium sulfide and ammonia) and the support colonization by the biomass were evaluated. Finally, UP 20 was chosen and tested in a hydrogen sulfide or ammoniac biofiltration process. This showed that, for H2S concentrations greater than 100mg m(-3), UP 20 has a real advantage over pine bark or pozzolan.     

Relation between odor and odorous components in solid swine manure

Odor similarity of the synthetically prepared solutions and the extract from solid swine manure showed that the main components for odor of solid swine manure are carboxylic acids and sulfides and that p-cresol increases the malodor and skatole modifies the nature of the malodor.     

新型树脂对氯酚类物质的吸附研究

合成了乙酰氯修饰树脂NDA-O,与Purolite公司的MN-200相比,合成的树脂比表面积较小,但酸性官能团较多.用两种树脂吸附2-氯酚、4-氯酚和2,4-二氯酚发现,吸附结果可以用Langmuir和Freundlich等温吸附方程很好地模拟,合成的NDA-O对3种氯酚类物质的吸附能力优于MN-200.两种树脂对氯酚类物质的吸附量随着温度的升高而减少,表明吸附是放热过程,同时对氯酚类物质的吸附焓变随着吸附量的增大而减小.对同一种树脂来说,吸附量随着氯代程度的增加而增加,取代氯数相同的时候,吸附量与吸附质的K..成正相关.进一步研究了pH对吸附的影响,在pH大于9时,3种氯酚类物质的吸附量均急剧减少.