Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Biomonitoring of pyrethroid exposure among rural and urban populations in northern Poland

The aim of this study was to determine for the first time in Poland, levels of exposure to synthetic pyrethroids in preschool and school age children and their parents living in urban and rural areas. For this purpose concentrations of pyrethroid metabolites: 3-phenoxybenzoic acid (3-PBA), 2,2-dibromovinyl-2,2-dimethylcyclopropanecarboxylic acid (Br₂CA), cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (cis-Cl₂CA) and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (trans-Cl₂CA) were determined in 374 urine samples using a validated GC–MS method.     

Ti（Ⅳ）催化臭氧／过氧化氢预处理酸性难降解废水

在Ti（Ⅳ）和过氧化氢存在条件下,考察了臭氧化酸性苯乙酮溶液、硝基苯溶液和垃圾渗滤液（浙江衢州某垃圾填埋场）的预处理效能。结果表明,在pH2．86条件下,单独臭氧化处理对苯乙酮、硝基苯和垃圾渗滤液的COD去除率分别为10．1％、44％和28．6％。BOD,／COD值分别从原来的0．039、0．060和0．085提高到了0．130、0．158和0．174,仍属生化难降解废水。当体系加入Ti（Ⅳ）后,臭氧化苯乙酮和硝基苯的COD去除率分别达到了75．5％和65％,BOD;／COD则提高到了0．679和0．314,可生化性提升明显。对于垃圾渗滤液,只有当体系加入Ti（Ⅳ）和H22后,臭氧化COD的去除率达到66．6％,BOD、／COD提高至0．425。上述结果对酸性难降解废水的处理实际意义非常突出。     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

改进的TLI指数法及其在巢湖营养状态评价中的应用

对巢湖2000—2008年的监测数据运用SPSS做统计分析,得出叶绿素a与总氮、总磷和透明度的相关系数。通过得出的权重结果,分析出与26个湖泊的差异性,构建了改进的综合营养状态指数(TLI)评价方法,并提出评价的4个步骤。以巢湖为例,运用该方法对湖泊的营养状态进行评价,且对巢湖的富营养化程度做了年际和年内变化的综合评价,评价结果显示各营养物指标的相关关系在近30年有了较大变化,巢湖的富营养化现象已日益严重,已从轻度富营养化状态转变为中度富营养化状态。     

MFC-MBR耦合系统运行效果

膜生物反应器(MBR)是一种高效的污水处理工艺,而微生物燃料电池(MFC)能有效降解污泥中的胞外生物有机质(EBOM)并回收电能.将MFC与MBR联用,建立了一套能够有效抑制膜污染同时回收电能的新系统——MFC-MBR耦合系统,MBR的剩余污泥经MFC处理后回流.以传统MBR为对照,对耦合系统中污水处理效果、膜污染情况和污泥混合液的性质进行研究.研究表明,耦合系统的污水处理效果没有明显恶化,COD去除率为94％,NH4+-N的去除率为92％.耦合系统能够有效减缓膜污染的发生,清洗周期延长了28％.污泥混合液的MLVSS/MLSS稳定在80％ ～ 88％,系统内几乎没有无机颗粒积累.松散结合态胞外聚合物(LB-EPS)降低了48％,使污泥混合液性质得到改善.较低的污泥比阻(2.69×1012m/kg)和标准化毛细吸水时间(1.67 s·L/g MLSS),证明耦合系统污泥混合液脱水性能提高了.     

4种人工湿地基质对马拉硫磷的吸附特性

通过基质对马拉硫磷的等温吸附和吸附动力学实验,研究天然土壤、煤渣、沸石、砾石对马拉硫磷的吸附特性,为人工湿地处理含马拉硫磷废水提供理论依据.结果表明:马拉硫磷浓度为2.25 ～ 90 mg/L条件下,Langmuir和Freundlich方程均能较好地拟合4种基质对马拉硫磷的等温吸附过程,并且Freundlich方程的拟合效果要好于Langmuir方程.马拉硫磷的理论饱和吸附量大小依次为天然土壤(9.9304 mg/g)＞煤渣(1.6173 mg/g)＞沸石(0.6039 mg/g)＞砾石(0.3965 mg/g).4种基质对马拉硫磷的缓冲能力大小依次为天然土壤＞煤渣＞沸石＞砾石,即当进水马拉硫磷浓度波动较大时,作为湿地基质天然土壤使人工湿地系统维持稳定出水水质的能力最强.马拉硫磷浓度为4.5 mg/L条件下,吸附动力学模型Elovich方程能较好地拟合4种基质对马拉硫磷的吸附动力学特征,说明4种基质对马拉硫磷的吸附是表面吸附和内部扩散吸附共同作用的结果.因此,天然土壤和煤渣适宜作为处理含马拉硫磷废水的人工湿地基质.     

Phthalate exposure in pregnant women and their children in central Taiwan

Phthalate exposure was found to be associated with endocrine disruption, respiratory effects, reproductive and developmental toxicity. The intensive use of plastics may be increasing the exposure to phthalates in Taiwanese population, particularly for young children.We studied phthalate metabolites in pregnant women and their newborns in a prospective cohort from a medical center in Central Taiwan. One hundred maternal urine samples and 30 paired cord blood and milk samples were randomly selected from all of participants (430 pregnant women). Eleven phthalate metabolites (MEHP, 5OH-MEHP, 2cx-MEHP, 5cx-MEPP, 5oxo-MEHP, MiBP, MnBP, MBzP, OH-MiNP, oxo-MiNP, and cx-MiNP) representing the exposure to five commonly used phthalates (DEHP, di-isobutyl phthalate (DiBP), DnBP, BBP, DiNP) were measured in urine of pregnant women, cord serum and breast milk after delivery, and in urine of their children. Exposure was estimated with excretion factors and correlation among metabolites of the same parent compound. Thirty and 59 urinary samples from 2 and 5 years-old children were randomly selected from 185 children successfully followed.Total urinary phthalate metabolite concentration (geometric mean, μg L⁻¹) was found to be higher in 2-years-olds (398.6) and 5-years-olds (333.7) than pregnant women (205.2). Metabolites in urine are mainly from DEHP. The proportion of DiNP metabolites was higher in children urine (4.39 and 8.31%, ages 2 and 5) than in adults (0.83%) (p < 0.01). Compared to urinary levels, phthalate metabolite levels are low in cord blood (37.45) and milk (14.90). DEHP metabolite levels in women’s urine and their corresponding cord blood are significantly correlated. Compared to other populations in the world, DEHP derived metabolites in maternal urine were higher, while phthalate metabolite levels in milk and cord blood were similar. The level of phthalate metabolites in milk and cord blood were comparable to those found in other populations. Further studies of health effects related to DEHP and DiNP exposure are necessary for the children.     

Does monensin in chicken manure from poultry farms pose a threat to soil invertebrates?

Monensin is a carboxylic polyether ionophore used in the poultry industry as a coccidiostat. It enters the environment via manure from broiler farms. In spite of its potential presence in the environment, information concerning monensin residues in manure and soil and its toxicity to soil organisms are insufficient. In the present study, two beneficial soil invertebrate species, earthworms (Eisenia andrei) and woodlice (Porcellio scaber), were used to assess the toxicity of monensin. Animals were exposed to a range of monensin concentrations via soil or food. Earthworm reproduction was found to be the most susceptible endpoint (NOEC=3.5 mg kg(-1) dry soil; EC(50)=12.7 mg kg(-1) dry soil), while no adverse effects were recorded in isopods (NOEC?849mgkg(-1) dry soil, NOEC?357mgkg(-1) dry food). The obtained toxicity data were compared with potential concentrations of monensin in soil. In view of this, manure from broiler chickens treated with monensin at a poultry farm was sampled. According to monensin and nitrogen concentrations in the chicken manure and the degradation time of monensin, the predicted environmental concentration (PEC) was calculated. PEC of monensin is around 0.013 mg kg(-1) soil if manure is used after 3 months of composting and 0.05 mg kg(-1) soil if used without storage. Data for earthworm reproduction was used to estimate the predicted no-effect concentration (PNEC). If fresh chicken manure is applied to terrestrial ecosystems, the risk quotient (PEC/PNEC ratio) is above 1, which indicates that monensin might pose an environmental risk under certain conditions. To prevent this, it is strongly recommended to compost chicken manure for several months before using it as fertiliser.