定量构效关系模型分析氯代烯烃中氯原子对其分子描述符的影响

定量构效关系(QSAR)模型在研究饮用水消毒副产物(DBPs)中氯原子数量与毒性的关系方面有一定进展,然而,能够反映DBPs毒理性的分子描述符和氯原子数量之间的相关性却从未被系统地和定量的研究.分子描述符的计算是QSAR研究的基础,其中分子轨道能,如最低空轨道能量(ELUMO)是应用最广的量化参数之一.基于QSAR方法建模筛选氯代烯烃同系物的相关量子化学参数,检验最高占据轨道能级(EHOMO)、碳原子数(NC)、氯原子数(NCl)对ELUMO的贡献作用.并通过统计学方法进行模型开发和内外交叉法验证发现,NCl和NC是预测氯代烯烃分子特性较重要的两个化学参数,即较稳健的模型为ELUMO=-0.0205NCl+0.0059NC+0.1641(n=11, R2=0.9956, F=102.8569, RMSE=0.0019).此外,为了提高模型的准确性,使用蒙特卡罗法对模型进行不确定性分析,来进一步评估这些参数的误差源传输到ELUMO计算时,对ELUMO的影响.     

Occurrence and fate of PPCPs and correlations with water quality parameters in urban riverine waters of the Pearl River Delta, South China

The occurrence and fate of eight PPCPs was studied in river waters from upstream to downstream of the three rivers in the Pearl River Delta, China. The correlations of PPCP levels and water quality parameters were also investigated. The analytes of the highest concentrations were caffeine, acetaminophen, and ciprofloxacin. Carbamazepine and erythromycin-H₂O were detected at the lowest concentrations. The highest concentrations of PPCPs were found in the Shijing River, with 865 ng/L caffeine, 339 ng/L acetaminophen, and 304 ng/L ciprofloxacin. In general, the levels of PPCPs in the Zhujiang River were higher at sites where the metropolitan city Guangzhou is located and decreased from the epicenter along the river. Low levels of PPCPs were generally found in the Beijiang River. Positive correlations were found between PPCP levels, total nitrogen, ammonium nitrogen, and cumulative fluorescence excitation-emission matrix (EEM) volume. Among the four PPCPs evaluated (caffeine, acetaminophen, ciprofloxacin, and sulfamethoxazole), caffeine had the best correlations with the correlation coefficients ranging from 0.62 to 0.98. The prediction of PPCP concentrations at specified locations can be substantially simplified.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater

This study aimed to provide the first and comprehensive data on the occurrence of 17 target pharmaceuticals and personal care products (PPCPs) in urban water environment in Singapore. Meanwhile, this study also verified the suitability of these PPCPs as specific markers of raw wastewater contamination in receiving water bodies in highly urbanized areas where both surface water and groundwater are not impacted by the discharge of treated wastewater effluents. Analytical results of wastewater showed that among 17 target PPCPs examined, only 5 PPCPs were detected in 100 % of raw wastewater samples, including acetaminophen (ACT), carbamazepine (CBZ), caffeine (CF), diethyltoluamide (DEET), and salicylic acid (SA). Similarly, these PPCPs were found in most surface water and groundwater. Interestingly, the three PPCPs (ACT, CBZ, and SA) were only detected in surface water and groundwater in the sampling sites close to relatively older sewer systems, while they were absent in background samples that were collected from the catchment with no known wastewater sources. This suggests that ACT, CBZ, and SA can be used as specific molecular markers of raw wastewater in surface water and groundwater. This study also confirmed that CF and DEET were not really associated with wastewater sources, thus cannot serve well as specific molecular markers of wastewater contamination in receiving water bodies. To the best knowledge of the authors, the use of ACT and SA as specific molecular markers of raw wastewater contamination in urban surface waters and groundwater was first reported. Further studies on the use of ACT, CBZ, and SA along with other chemical/microbial markers are recommended to identify and differentiate contamination sources of surface waters/groundwater.     

中型污水处理厂中药物和个人护理品的分布与去除

为了解15种药物及个人护理用品(PPCPs)在中小型污水处理厂中的分布及其去除效果,采用液相色谱-串联质谱(LC-MS/MS)技术对3座A2/O工艺的污水处理厂水样进行分析研究。结果显示,除普萘洛尔、吉非罗平和吲哚美辛在3座中小型污水处理厂各个工艺单元中均未被检出外,其余12种目标化合物的检出频率在90%~100%之间。进水水样中PPCPs的平均检出浓度为2 285.4 ng/L,其中咖啡因(CF)的平均检出浓度最高为973.3 ng/L,酮洛芬(KP)的平均检出浓度次之为844.7 ng/L,两者之和占进水水样中PPCPs平均含量的79.5%,表明污水处理厂的主要污染物为CF和KP。3座污水处理厂对CF的去除效果最为显著,平均去除率为95.3%,对15种PPCPs总去除效率在39.3%~82.8%之间。     

Degradation of chelating agents in aqueous solution using advanced oxidation process (AOP)

This article presents an overview with critical analysis of technical applicability of advanced oxidation process (AOP) in removing chelating agents from aqueous solution. Apart from the effect of metals for chelating agents as a major influencing factor, selected information such as pH, oxidant’s dose, concentrations of pollutants and treatment performance is presented. The performance of individual AOP is compared. It is evident from our literature survey that photocatalysis with UV irradiation alone or coupled with TiO₂, ozonation and Fenton’s oxidation are frequently applied to mineralize target pollutants. Overall, the selection of the most suitable AOP depends on the characteristics of effluents, technical applicability, discharge standard, regulatory requirements and environmental impacts.     

微气泡催化臭氧化深度处理制药废水的效果及DOM组分特性的变化

采用镁铝层状双氢氧化物(MAL)微气泡催化臭氧化(MAL/MB/O₃)体系深度处理实际制药废水,考察了该体系对溶解性有机物(DOM)的深度去除性能及DOM组分的变化特性,并与普通气泡臭氧化(CB/O₃)、普通气泡催化臭氧化(MAL/CB/O₃)、微气泡臭氧化(MB/O₃)工艺进行了比较。结果表明,MAL/MB/O₃处理性能优于CB/O₃、MAL/CB/O₃和MB/O₃,在臭氧投加总量与处理废水初始COD值之比为0.6、气流量0.5 L·min⁻¹、催化剂投加量0.5 mg·L⁻¹的条件下,整体COD去除率可达49.79%,COD去除量与臭氧消耗量的比值为0.83,废水的可生化性得到了一定改善,生物毒性显著下降。废水DOM中疏水性组分氧化去除率高于亲水性组分。臭氧直接氧化可去除疏水性组分,而亲水性组分去除主要依赖HO·氧化。MAL/MB/O₃对DOM的去除效率最高,可达到52.51%,其中疏水性组分整体去除率56.67%,亲水性组分整体去除率46.93%。废水DOM在氧化处理中存在官能团向酸性基团转化、类腐殖质向类富里酸和类胡敏酸转化、其他组分向亲水性酸(HIA)组分转化的趋势。MAL/MB/O₃强氧化能力对于DOM组分不饱和结构和荧光结构的破坏作用最为显著。以上研究结果可为制药废水深度处理提供参考。     

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.