Analyses of phenolic compounds occurring in olive oil mill wastewaters by GC–MS

Phenolic compounds in olive oil mill wastewaters were analysed by HRGC–MS after extracting the acidified solution with ethyl acetate and derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide. Both simple and complex phenols were detected with the latter being the most abundant. 1,2-dihydroxybenzene (catechol), p-hydroxyphenyl ethanol (tyrosol), 3,4-dihydroxyphenyl ethanol (hydroxytyrosol) and 4-hydroxy-3-methoxyphenyl ethanol (homovanillyl alcohol) predominated among the simple phenols using a gas chromatograph coupled with a mass selective detector.     

水中挥发酚检测方法初探

酚类属高毒物质,水中挥发酚的含量直接影响人类健康。近10年来,我国研究人员对水中挥发酚的测定方法开展了很多研究,特别对于采用4-氨基安替比林分光光度法(4-AAP)(GB 7490-1987)测定水中挥发酚的各个环节,如样品的采集、保存、预处理、试剂纯度、反应时间控制等相关因素进行了研究,找到了影响含量准确的因素,为测定水中挥发酚的含量提供了快速、准确、重复性好的方法。对一些非国标法测定水中挥发酚的方法也进行了介绍。文章对这些方法进行了分类总结。希望能对实验人员有所帮助。     

苯酚类化合物对日本长腿蛙蝌蚪的急性毒性与构效关系研究

利用半静态法测定了21种取代苯酚类化合物对日本长腿蛙蝌蚪的24h 急性致死毒性(24h-LC50),并进行了定量结构活性相关研究.研究表明:大部分酚类化合物的毒性表现为极性麻醉作用.影响毒性的因素有化合物的疏水性、电性及离解行为等.     

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.     

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.     

Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

气体扩散电极制备及其对苯酚降解效果的研究

以质量比9∶1的活性炭和乙炔黑制备气体扩散电极,着重研究电流密度、pH值、曝气量等因素对H2O2产生量的影响.结果表明:pH值在较大范围内均适用;电流密度控制在50～75 mA/cm2,曝气量确定为5 L/min时,反应产生H2O2较多.另外,利用该气体扩散电极做阴极,石墨电极做阳极,以Na2SO4为电解质,研究了电解时间、电流密度、pH值、初始苯酚浓度、曝气量等因素对苯酚降解效果的影响.结果表明:在电流密度为75 mA/cm2、曝气量为5 L/min、初始pH=3的条件下,当苯酚的初始浓度为80 mg/L时,1 h后其去除率达77%.     

北黄海近岸海域生物体中酚类内分泌干扰物富集与放大作用研究

在北黄海近岸海域21个典型区域采集了可构成3个营养级的6种生物样品,分别为海带、裙带菜、牡蛎、扇贝、海参和黑鱼.采用HPLC-MS/MS检测6种生物样品中双酚A(BPA)、辛基酚(0P)、壬基酚(NP)、2,4-二氯酚(2,4-DCP)、对叔丁基苯酚(PTBP)和对特辛基苯酚(POP)质量比,并进一步采用生物富集因子(BAF)和生物放大因子(TMF)评价了北黄海近岸海域生物体内酚类内分泌干扰物的富集作用与放大能力.结果表明,北黄海近岸海域生物体中6种酚类内分泌干扰物的质量比范围为检出限(nd)～1 796.26 ng/g,其中2,4-二氯酚具有较强的生物富集效应,辛基酚和壬基酚具有潜在的生物富集效应,同时营养级越高,生物放大作用越明显.研究表明,海洋生物体对酚类内分泌干扰物的富集能力随营养级升高而增大.     

Decolorization of molasses melanoidins and palm oil mill e uent phenolic compounds by fermentative lactic acid bacteria

Lactobacillus plantarum SF5.6 is one of the lactic acid bacteria (LAB) that has the highest ability of molasses melanoidin (MM) decolorization among the 2114 strains of LAB. The strains were isolated from spoilage, pickle fruit and vegetable, soil and sludge from the wastewater treatment system by using technical step of enrichment, primary screening and secondary screening. This LAB strain SF5.6 was identified by 16S rDNA analysis and carbohydrate fermentation (API 50 CH). The top five LAB strains having high MM decolorization (> 55%), namely TBSF5.8-1, TBSF2.1-1, TBSF2.1, FF4A and SF5.6 were selected to determine the optimal condition. It was found that the temperature at 30°C under facultative conditions in GPY-MM medium (0.5% glucose, 0.1% peptone, 0.1% yeast extract, 0.1% sodium acetate, 0.05% MgSO4 and 0.005% MnCl2 in MM solution at pH 6) giving a high microbial growth and MM decolorization for all five strains. It was noticed that the decolorization of MM by LAB strains might be cell growth associated. L. plantarum SF5.6 grew rapidly within one day while the other strains took 2–3 days. This L. plantarum SF5.6 could rapidly decolorize MM to 60.91% without any lag phase, and it also had the ability to remove 34.00% phenolic compounds and 15.88% color from treated palm oil mill e uent.     

Ru/AC催化臭氧氧化难生物降解有机物

研究了臭氧单独氧化和Ru/AC催化臭氧氧化DMP、酚类物质和消毒副产物前体物.结果表明,Ru/AC能显著提高臭氧氧化中有机物的矿化效果.在DMP降解中,反应100 min后TOC的去除率由单独臭氧氧化的28.84%提高到66.13%.在23种酚类物质降解中,反应60min后TOC的去除率由单独臭氧的9.57%~56.08%提高到41.81%~82.32%.相对于单独臭氧,Ru/AC催化臭氧氧化更能有效地降低水源水中消毒副产物的生成势,以卤乙酸生成势的降低最为明显,100 min后卤乙酸生成势由144.02μg/L降到58.50μg/L,低于美国环保局规定的限制浓度60μg/L.而使用单独臭氧处理并不能使卤乙酸生成势降到符合美国EPA的规定.比较了BAC、O3+BAC、O3/AC+BAC以及Ru/AC+O3+BAC工艺处理水源水的效果,TOC平均去除率分别为3.80%、20.14%、27.45%和48.30%;COD平均去除率分别为4.37%、27.22%、39.91%和50.00%;UV254去除率分别为8.16%、62.24%、67.03%和84.95%.Ru/AC+O3+BAC工艺相比其他工艺,更能有效地...