四川省不同地区自来水中全氟化合物的污染特征及健康风险评估

采用超高效液相色谱-质谱联用仪分析了四川省10个地区自来水中12种全氟化合物(perfluoroalkyl substances, PFASs)的含量,其中全氟化合物浓度水平最高的是宜宾地区,∑PFASs为41.2 ng·L~(-1),浓度水平最低的是绵阳地区,为4.17 ng·L~(-1).全氟辛烷羧酸(perfluroroocantanoic acid,PFOA)是四川地区自来水中主要的PFASs,占总全氟化合物的28%～89%(宜宾地区8.6%),其次为全氟己酸(perfluorohexanoate,PFHxA)、全氟辛烷磺酸(perfluorooctane sulfonate, PFOS)和全氟壬酸(perfluorononanoate,PFNA),这表明自来水中的主要污染物为中短碳链(C≤10)的全氟化合物.另外,通过计算PFASs的危险商值(risk quotients, RQ),发现四川地区自来水中PFOA、PFOS、PFHxS、PFBS和PFHxA的风险商值均小于1,不会对当地居民带来直接的健康风险.     

PM2.5中类腐殖质表面活性测定方法与实例分析

建立了大气细粒子中类腐殖质（HULIS）表面活性的动态表征方法,并以华北平原乡村站点冬季大气PM_2.5样品为例,对PM_2.5中HULIS的表面活性进行表征.HULIS碳质组分（HULIS-C）浓度为2.0~4.6μg C/m³,占水溶性有机碳和总有机碳的比例分别为31%~40%和20%~26%.浓度为88~200mg C/L的HULIS水溶液,其表面张力相对于纯水降低了18%~22%.HULIS-C浓度在低于70mg C/L时表面张力降低显著,在88~320mg C/L之间降低相对缓慢.动态表面张力随着时间变化逐渐降低,在液滴形成后200s以内表面张力下降迅速,之后趋于平缓,说明表面活性分子在液滴中扩散趋于稳定需要一定的时间,该特征时间可能影响表面活性物质在云凝结核活化时的作用.证实了在污染地区的大气PM_2.5中含有一定量的表面活性物质,这些物质可能对颗粒物活化为云滴、雾滴过程产生显著影响;表面活性物质的存在可能在外界湿度变化过程中导致颗粒物发生液-液相分离现象,在颗粒物表面形成有机膜,影响活性分子摄取以及半挥发性物质的气-粒分配过程,从而影响大气非均相反应过程.     

氧化石墨烯对淡水微藻生长及生物活性物质的影响

为掌握氧化石墨烯（GO）的水环境风险,以斜生栅藻（Scenedesmus obliquus）和湖泊微拟球藻（Nannochloropsis limnetica）为研究对象,探究了GO对淡水微藻生长及其生物活性物质（碳水化合物、总蛋白质、总脂）的影响.结果表明,GO对2种微藻具有中等毒性,72h EC₅₀值分别为25.63和48.44mg/L.透射电镜（TEM）观察发现,GO纳米片层既能附着于藻细胞表面也能进入藻细胞内部,造成藻细胞超微结构明显变化,包括：质壁分离;叶绿体收缩;淀粉粒数量减少甚至消失.较低浓度（10mg/L）GO会促进微藻中光合色素（叶绿素a、叶绿素b、类胡萝卜素）合成;而较高浓度（100mg/L）GO暴露下,2种微藻的类胡萝卜素和斜生栅藻叶绿素a的含量显著降低.2种浓度的GO总体上刺激了藻细胞内生物活性物质的合成,这是污染胁迫下的一种主动防御机制;而较高浓度GO造成碳水化合物含量显著降低,可能原因是细胞中储能物质由淀粉向中性脂转化.     

信号分子在好氧颗粒污泥形成过程中的作用

采用人工配水成功培养好氧颗粒污泥,针对絮状污泥颗粒化过程中污泥的理化性质、污染物去除效率、胞外聚合物和信号分子变化进行相关分析.结果发现,在好氧颗粒污泥的形成过程中,污泥对污染物去除能力明显提高.与接种污泥相比,成熟的好氧颗粒污泥对COD、NH₄⁺-N和PO₄^3--P去除率分别提高20%、36%和57%.好氧颗粒污泥中胞外蛋白质和多糖含量分别增加了116和31mg/gMLVSS.采用激光共聚焦扫描显微镜对接种污泥和好氧颗粒污泥进行空间表征,发现后者蛋白质含量明显增加,说明蛋白质在污泥颗粒化过程中具有重要作用;磷酸二酯酶活性总体呈现上升趋势,第二信使环二鸟苷酸（cyclic diguanylic,c-di-GMP）含量先增加后降低,与胞外聚合物中蛋白质和多糖的变化规律相似.通过SPSS软件进一步分析得知,c-di-GMP与蛋白质相关系数R²=0.92871,呈极显著相关性;与紧密结合型胞外聚合物中蛋白质相关系数R²=0.89025,呈显著相关性,推测c-di-GMP可能是通过指导紧密结合型胞外聚合物中的蛋白质合成以促进好氧颗粒污泥的形成.     

广州冬季气溶胶中水溶性有机物和类腐殖质的吸光性和荧光光谱特性

利用紫外-可见光谱与三维荧光-平行因子分析法(EEM-PARAFAC),研究了广州市2014年12月～2015年1月大气气溶胶中水溶性有机物(WSOC)和类腐殖质(HULIS)的吸光性和荧光光谱特征.结果表明,广州冬季气溶胶中HULIS的芳香性(SUVA254)、腐殖化程度(HIX)和光吸收效率(MAE365)均高于WSOC.利用EEM-PARAFAC从WSOC和HULIS解析出了类富里酸(C1)、类腐殖酸(C2)和类蛋白(C3)这3种荧光组分.其中类腐殖质组分(C1+C2)分别占WSOC和HULIS中总荧光组分的78%和85%,说明类腐殖荧光组分是WSOC和HULIS的最主要组成,且HULIS富集了更多的WSOC中主要的类腐殖组分.另外,灰霾期的WSOC和HULIS表现出更高的芳香性、腐殖化程度和C2组分,说明灰霾期有助于大分子量吸光性有机质的形成.相关性分析结果显示,WSOC和HULIS的C1组分相对含量与HIX、MAE365、OCsec、K+、SO_4~(2-)和NH_4~+呈现极显著的负相关关系,而C2与它们之间存在极显著的正相关关系.由此说明,WSOC和HULIS中C1的降低和C2的增加会引起它们的腐殖化程度和光吸收能力的增强;同时生物质燃烧排放和二次气溶胶过程可能有助于C2组分的增加.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

防护鞋靴有害物质限量值研究

本文对防护鞋靴有害物质限量值研究进行了阐述。参考国内外标准,设定防护鞋靴有害物质限制项目和限量值。在检测分析我国具有市场代表性的16个防护鞋靴产品中有害物质含量数据基础上,判断设定限制项目及限量值的可行性。检测结果表明我国防护鞋靴生产技术水平基本能够达到限量要求,设定的限量值可以作为制定国家标准的参考依据。     

Comparison of CNT-PVA membrane and commercial polymeric membranes in treatment of emulsified oily wastewater

CNT-PVA membrane was fabricated and compared with polymeric membranes. The separation performance was evaluated by homemade and cutting fluid emulsions. The three membranes show similar oil retention rates. CNT-PVA membranes have higher permeation fluxes compared with polymeric membranes. CNT-PVA membrane shows higher fouling resistance. Membrane separation is an attractive technique for removal of emulsified oily wastewater. However, polymeric membranes which dominate the current market usually suffer from severe membrane fouling. Therefore, membranes with high fouling resistance are imperative to treat emulsified oily wastewater. In this study, carbon nanotube-polyvinyl alcohol (CNT-PVA) membrane was fabricated. And its separation performance for emulsified oily wastewater was compared with two commercial polymeric membranes (PVDF membrane and PES membrane) by filtration of two homemade emulsions and one cutting fluid emulsion. The results show that these membranes have similar oil retention efficiencies for the three emulsions. Whereas, the permeation flux of CNT-PVA membrane is 1.60 to 3.09 times of PVDF membrane and 1.41 to 11.4 times of PES membrane, respectively. Moreover, after five consecutive operation circles of filtration process and back flush, CNT-PVA membrane can recover 62.3% to 72.9% of its initial pure water flux. However, the pure water flux recovery rates are only 24.1% to 35.3% for PVDF membrane and 6.0% to 26.3% for PES membrane, respectively. Therefore, CNT-PVA membrane are more resistant to oil fouling compared with the two polymeric membranes, showing superior potential in treatment of emulsified oily wastewater.     

Degradation of extracellular genomic,plasmid DNA and specific antibiotic resistance genes by chlorination

Extracellular DNA structure damaged by chlorination was characterized. Integrity of extracellular ARG genetic information after chlorination was determined. Typical chlorine doses will likely effectively diminish extracellular DNA and ARGs. Plasmid DNA/ARGs were less readily broken down than genomic DNA. The Bioanalyzer methodology effectively documented damage incurred to DNA. There is a need to improve understanding of the effect of chlorine disinfection on antibiotic resistance genes (ARGs) in order to advance relevant drinking water, wastewater, and reuse treatments. However, few studies have explicitly assessed the physical effects on the DNA. Here we examined the effects of free chlorine (1–20 mg Cl₂/L) on extracellular genomic, plasmid DNA and select ARGs. Chlorination was found to decrease the fluorometric signal of extracellular genomic and plasmid DNA (ranging from 0.005 to 0.05 mg/mL) by 70%, relative to a no-chlorine control. Resulting DNA was further subject to a fragment analysis using a Bioanalyzer, indicating that chlorination resulted in fragmentation. Moreover, chlorine also effectively deactivated both chromosomal- and plasmid-borne ARGs, mecA and tetA, respectively. For concentrations >2 mg Cl₂//L × 30 min, chlorine efficiently reduced the qPCR signal when the initial concentration of ARGs was 10⁵ copies/mL or less. Notably, genomic DNA and mecA gene signals were more readily reduced by chlorine than the plasmid-borne tetA gene (by ~2 fold). Based on the results of qPCR with short (~200 bps) and long amplicons (~1200 bps), chlorination could destroy the integrity of ARGs, which likely reduces the possibility of natural transformation. Overall, our findings strongly illustrate that chlorination could be an effective method for inactivating extracellular chromosomal- and plasmid-borne DNA and ARGs.     

Reduction of Cr(VI) by peat and coal humic substances

The reduction of Cr(VI) by humic substances from leonardite and peat was investigated by capillary zone electrophoresis at various pHs. Both humic materials reduced Cr(VI) at pH 5.4, but not at basic pH. The capacity of leonardite humic substances to reduce Cr(VI) was lower than that of peat humic substances. Fe(III) accelerated the reduction of Cr(VI) by peat humic substances, but not by leonardite humic substances. Cr(VI) reduction mechanisms are proposed. The coal humic substances seem more suitable for remediation of Cr(VI)-contaminated sites.