Formation of chlorinated disinfection by-products in viticulture

Background, aim and scope  The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter ‘adsorbable organic halogens’ (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. Materials and methods  The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography–mass spectrometry. Results  Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. Discussion  The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. Conclusions  The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. Recommendations and perspectives  Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.     

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Cr(Ⅵ)污染土壤的热解还原无害化处理

提出了用热解还原法对含铬土壤进行无害化处理的新技术,研究了热解温度、热解时间及土壤有机质对铬无害化处理的影响,分析了热解前后土壤中铬的元素形态的变化.同时还探讨了热解还原过程中Cr(Ⅵ)的无害化机制.结果表明,土壤中的有机质在热解还原过程中产生的挥发分对Cr(Ⅵ)的无害化起核心作用;在200～600℃范围内,Cr(Ⅵ)的还原量随着热解温度升高而增大,500.0℃最适合于经济有效地实现Cr(Ⅵ)的热解还原处理;Cr(Ⅵ)的热解还原过程较快.铬的形态分析结果表明,热解后可交换态和碳酸盐结合态铬量大大降低,大部分铬转化成了活性低的残渣态,极大地降低了铬的危害.     

铁炭微电解预处理电路板废水

采用铁炭微电解法预处理电路板废水.结果表明,在进水pH为2.00、铁炭质量比为4:1、振荡时间为20 min的铁炭微电解静态实验最佳条件下,絮凝出水COD去除率为30%;在进水pH为2.00、铁炭质量比为4:1、水力停留时间为50 min的铁炭微电解柱动态实验最佳条件下,连续曝气.絮凝出水COD为11021 mg/L,COD去除率约为34%,BOD5/COD从0.12上升到0.32,可生化性提高,Cu2+质量浓度从9.11 mg/L下降至0.76 mg/L,降低了废水的生物毒性,为生化处理创造了条件.     

Screening analysis of volatile organic contaminants in commercial inorganic coagulants used for drinking water treatment

A method for quality screening is suggested to detect volatile impurities in inorganic coagulants that are used for drinking water treatment. Static headspace gas chromatography with mass spectrometry detection (HS–GCMS) is sensitive and selective to detect volatiles in low concentrations. This study has discovered that volatile organic impurities are detectable in ferric and aluminium-based coagulants which are used for drinking water treatment. For ferric chloride, 2-propanol was detected at a level of 17–24 μg ml⁻¹, acetone at 0.7–1.7 μg ml⁻¹, 1,1,1-trichloroacetone at 0.02–0.04 μg ml⁻¹, trichloromethane at 0.01–0.02 μg ml⁻¹ and toluene at 0.01–0.12 μg ml⁻¹. For ferric chloride sulfate, acetone was detected at a level of 0.12 μg ml⁻¹, 1,1,1-trichloroacetone at 0.06–0.08 μg ml⁻¹, trichloromethane at 0.13–0.23 μg ml⁻¹, bromodichloromethane at 0.04–0.06 μg ml⁻¹ and dibromochloromethane at 0.04–0.05 μg ml⁻¹. For aluminium hydroxide chloride, only trichloromethane was detectable, but below the method detection limits (MDL). Although the concentrations of these impurities in commercial coagulants are low, this observation is important and should have impact on water industries for them to pay attention to the chemicals they are using for drinking water production.     

Application of lime and calcium hypochlorite in the dephenolisation and discolouration of olive mill wastewater

The application of hypochlorite for the removal of soluble COD, phenolic and polyphenolic like compounds, and other organic compounds responsible for the olive mill wastewater (OOWW) colour has been experimentally studied. After the OOWW filtration on a sand column, the effluent was subjected to a fast liming under optimal conditions. Lime application reduced polyphenols, COD and SS contents to half of their initial values but an important blackening of the treated OOWW was observed, especially when adding high concentrations of lime (10% (W/V) and 15% (W/V)).A second stage of treatment was applied using calcium hypochlorite. In this stage, removal of the studied compounds reached as much as 95% at higher concentrations, and particularly the colouring of OOWW which is generally difficult to eliminate was greatly reduced. The OOWW hypochloration acted through coagulation–flocculation and a rapid oxidation of the organic matter proceeded from the first 5 min. The kinetic study of the degradation of the waste polluting compounds from liming showed that Ca(ClO)₂ reacts similarly in the elimination of organic compounds, polyphenols, SS and colouration. The analysis of the organochloride compounds generated by the reaction between hypochlorite and the organic compounds showed that DDD, DDT and the heptachlor contents exceeded the values recommended by the International and European drinking water standards.     

Which compounds contribute most to elevated airborne exposure and corresponding health risks in the Western Balkans?

A majority of ongoing monitoring of persistent organic pollutants (POPs) is currently focused on chemicals emphasized in the Stockholm Convention. Quantitative detection of other substances (especially those with numerous anthropogenic sources such as polyaromatic hydrocarbons (PAHs)) is, however, also needed since their concentrations are usually several orders of magnitude higher. A goal of this study was to determine how various groups of compounds contribute to total human health risks at the variety of sampling sites in the region of Western Balkan. Distribution of the risks between the gas and particulate phases was also addressed. Results showed that inhalation exposure to organochlorine pesticides (OCPs) does not represent a significant risk to humans, while polychlorinated biphenyls (PCBs) re-volatilized to the atmosphere from contaminated soils and buildings can pose a problem. PCB evaporation from primary sources (currently used PCB-filled transformers or non-adequate storage facilities) generally resulted in much higher atmospheric concentrations than evaporation from the secondary sources (soils at the sites of war destructions). A majority of the human health risks at the urban sites were associated with PAHs. Between 83 and 94% of the cumulative risk at such sites was assigned to chemicals sorbed to particles, and out of it, PAHs were responsible for 99%.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

The fate of recombinant plasmids during composting of organic wastes

Composting was investigated as a means for safe disposal of organic waste containing bacteria that carry transgenes in recombinant plasmids. To generate model recombinant plasmids, a mobile IncQ plasmid, RSF1010, and a non-mobile plasmid, pGFP, were genetically modified to carry a DNA segment encoding both green fluorescent protein and kanamycin resistance and were designated as RSF1010-GFPK and pGFPK. Escherichia coli (E. coli) C600 harboring these plasmids were inoculated into chicken manure specimens that were placed in compost at 20 and 60 cm from the bottom of a 1.0-m high compost bin. Control specimens were held at ambient temperature. By day 10, compost temperatures at the lower and upper levels of the bin had reached 45.3 and 61.5°C, respectively, and at both levels the target E. coli had been inactivated and the plasmids had lost their capacity to be transformed or mobilized. Furthermore, based on real time Polymerase chain reaction (PCR), the transgene fragments along with the host chromosomal DNA fragment from specimens at the upper level had been degraded beyond the detection limit. However, at the lower level where temperatures remained below 48°C these fragment persisted to day 21. At ambient temperatures (0–8°C), the E. coli, plasmids and the transgene fragments persisted in manure specimens throughout the 21 day test period. The study showed the potential for composting as a safe procedure for disposal of bacteria carrying transgenes in recombinant plasmids.     

光催化氧化降解垃圾渗滤液中溶解性有机物

研究了UV-TiO2光催化氧化降解垃圾渗滤液过程中溶解性有机物(DOM)的变化特征。结果表明:在适宜条件下,UV-TiO2光催化氧化降解垃圾渗滤液的色度、COD和DOC的去除率分别可达97%、72%和60%;紫外光谱分析说明渗滤液DOM中包括多种含有共轭双键、羰基的大分子有机物及多环芳香类化合物,不同光催化处理液中DOM具有基本一致的结构单元和官能团;红外光谱分析说明渗滤液DOM中含有大量包括羟基、羧基、氨基和苯环的芳香族化合物,在光催化处理液中这几种官能团都能被有效降解;GC/MS分析结果表明,渗滤液DOM中含有72种有机污染物,醇类、羧酸和酮类分别为25、14和12种;在光催化72 h处理液中,有机物减少为44种;酯类和醇类较多,分别为12种和16种;酮类8种,羧酸没有检出。