应用概率物种敏感度分布法研究太湖重金属水生生物水质基准

目前广泛使用的水质基准推导方法—物种敏感度分布法存在曲线拟合模型不确定、曲线拟合效果不佳、种内差异欠考虑、基准值不准确等诸多问题,概率物种敏感度分布法可有效解决上述问题。应用概率物种敏感度分布法构建了太湖水体中5种重金属Ag、Pb、Cd、Hg和Zn的概率物种敏感度分布曲线,在此基础上得到了保护水生生物的急性水质基准分别为1.079μg·L~(-1)、637.973μg·L~(-1)、19.465μg·L~(-1)、8.729μg·L~(-1)和105.506μg·L~(-1),慢性水质基准分别为0.108μg·L~(-1)、63.797μg·L~(-1)、1.947μg·L~(-1)、2.340μg·L~(-1)和52.753μg·L~(-1);不同类群间生物对重金属的敏感度存在差异,不同重金属对同一类群生物的毒性也存在差异;通过与国内外已有的重金属水质基准值比较,发现水质基准具有明显的区域性,目前基于国外水质基准或我国整体水域特点来制定的太湖水质标准,往往造成对太湖水生生物欠保护或过保护的状况。     

PBDEs的来源特征、环境分布及污染控制

多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)生产应用、环境分布与生态风险之间的关系将如何影响我国的未来,具体涉及到工业、环境、健康、人类繁衍等的社会问题.由于PBDEs阻燃效率高,热稳定性好,价格便宜,作为添加剂被广泛应用在电子、电器、化工、交通、建材、纺织、石油等领域的阻燃产品中.PBDEs进入环境后迁移扩散并富集于沉积物和生物体内,进入人体后引起肝脏毒性、内分泌干扰、神经毒性和生育能力下降等而危害人类的健康.基于此,从生产应用、品种生产量、分子的物理化学特性以及毒性等的文献数据分析了PBDEs的来源特征与环境危害,分析这些性质对环境分布与污染控制的基础支持关系;从沉积物、水体、大气、水生生物、人体5个方面考察了PBDEs的环境本底浓度变化、分配关系、迁移规律、时间效应,分析了生产、应用与扩散的多因素影响关系,发现全球性PBDEs污染物蔓延的现象,沉积物是主要的归趋场所,室内空气中的浓度远高于室外,水中浓度较低,水生生物和人体均能富集PBDEs,通过饮食、母乳和呼吸摄入,可实现代际传播,污染的分布呈现介质与区域的不同特征;污染控制需要考虑点源技术与面源修复的联合,结合PBDEs的物理性质、分子结构及其化学特性,统计分析了微生物法、光化学降解法和零价铁还原法的原理及其有效性,根据PBDEs在产品中存在与分布的特点,提出收集-分离-富集-超临界催化还原和氧化毁毒的工艺,针对实际环境(以电子垃圾塑料和流域水体及沉积物为对象)中的PBDEs进行回收或处理,结合材料如催化剂的应用,从动力学和热力学方面提高PBDEs无害化的效率.最后,从生产管理、环境监测、风险评价、技术集成等方面提出了未来的努力方向.     

水环境中不同形态氮对甲芬那酸光降解影响机制的研究

研究了紫外光照射下水环境中不同形态的无机氮(NO-3、NO-2和NH+4)对甲芬那酸(MEF)光解的影响.NO-3与NO-2均促进MEF的光解,NH+4对MEF的光解基本无影响;在NO-3、NO-2存在下添加适量异丙醇,显著抑制MEF的降解,实验表明NO-3、NO-2在光照下产生了·OH并参与对MEF的氧化降解.同时模拟研究了水体处于不同p E值下,水中存在的不同形态的无机氮对MEF光解的复合影响,其对MEF光解促进作用不是简单的叠加关系,增大p E值,MEF的光解速率先增大后减小.当NO-2和NH+4共存时,对MEF的光解主要表现为NO-2的影响;当NO-2和NO-3共存时,两者对MEF的光解存在拮抗作用.     

磁微球负载硝基锌卟啉光催化剂的制备及催化性能研究

以氯化血红素为原料,制备了磁负载的硝基锌卟啉光催化剂.同时,利用热重分析仪(TG)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)和振动磁强计(VSM)对催化剂进行了表征,发现制备的催化剂负载率为32.06%,催化剂为粒径均一的球形壳-核结构,具有良好的磁性.其次,研究了催化剂的催化降解性能.结果表明,磁负载硝基锌卟啉光催化剂在可见光下,对水中的双酚A(BPA)、对硝基苯酚(PNP)等均有90%以上的去除率;对于活性红染料废水的降解也取得了83.67%的降解率.自由基捕获实验证明,电子(e-)、羟基自由基(·OH)、空穴(h+)和氧自由基(O-·2)是降解反应中重要的活性物种.最后通过GC-MS等手段对降解机理进行了研究.     

Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (·OH) and singlet oxygen (¹O₂) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of UOH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and ¹O₂. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.     

Pollution levels and characteristics of phthalate esters in indoor air of offices

The pollution status and characteristics of PAEs (phthalate esters) were investigated in indoor air of offices, and PAEs of both gas-phase and particulate-phase were detected in all the samples. The concentration (sum of the gas phase and the particulate phase) was 4748.24 ng/m³, ranging between 3070.09 and 6700.14 ng/m³. Diethyl phthalate, dibutyl phthalate, and di(2-ethylhexyl) phthalate were the most abundant compounds, together accounting for 70% of the Σ6PAEs. Dividing the particulate-phase PAEs into four size ranges (<2.5, 2.5-5, 5-10, >10 μm), the result indicated that PAEs in PM_2.5 were the most abundant, with the proportion of 72.64%. In addition, the PAE concentration in PM_2.5 correlated significantly with the total particulate-phase PAEs (R² = 0.85). Thus, the amount of PAEs in PM_2.5 can be estimated from the total amount of particulate-phase PAEs using this proportion. In a comparison between the offices and a newly decorated study room, it was found that pollution characteristics were similar between these two places. Thus, it is implied that the PAE concentration decreased by 50% 2 yr after decorating.     

Pollution levels and characteristics of phthalate esters in indoor air of offices

The pollution status and characteristics of PAEs(phthalate esters) were investigated in indoor air of offices, and PAEs of both gas-phase and particulate-phase were detected in all the samples. The concentration(sum of the gas phase and the particulate phase) was4748.24 ng/m3, ranging between 3070.09 and 6700.14 ng/m3. Diethyl phthalate, dibutyl phthalate, and di(2-ethylhexyl) phthalate were the most abundant compounds, together accounting for 70% of the ∑ 6PAEs. Dividing the particulate-phase PAEs into four size ranges( 2.5, 2.5–5, 5–10, 10 μm), the result indicated that PAEs in PM2.5were the most abundant,with the proportion of 72.64%. In addition, the PAE concentration in PM2.5correlated significantly with the total particulate-phase PAEs(R2= 0.85). Thus, the amount of PAEs in PM2.5can be estimated from the total amount of particulate-phase PAEs using this proportion. In a comparison between the offices and a newly decorated study room, it was found that pollution characteristics were similar between these two places. Thus, it is implied that the PAE concentration decreased by 50% 2 yr after decorating.     

东江流域表层土中全氟化合物的空间分布及来源解析

为探究东江流域土壤中全氟化合物(perfluorinated compounds,PFCs)分布特征和潜在来源,2013年8月采集东江流域19份表层土样品,利用高效液相色谱-串联质谱联用(HPLC-MS/MS)技术分析了16种PFCs的含量。结果表明,东江流域表层土总PFCs(∑PFCs)含量范围在2.15~5.49μg/kg dw。所采集的表层土样品中,东江东莞段土壤∑PFCs含量明显高于惠州段,全氟辛烷磺酸(0.65~1.28μg/kg dw)为最主要的污染物。与国内相关研究数据相比,东江流域土壤PFCs含量水平整体较高,这可能与流域产业结构和经济活动有关。主成分分析结果表明,电镀防雾剂、食品包装和全氟羧酸的生产过程、大气沉降、电化学氟化过程为东江流域土壤中PFCs的主要来源。与土壤有机质含量相关性研究表明,PFCs更容易分配到有机质含量高的土壤中,且随着PFCs分子碳链的增加,这种趋势更加显著。     

某农药厂废弃场地土壤中甲拌磷垂向分布特征

为了解废弃农药厂土壤中甲拌磷的垂向分布特征,在前期表层土壤筛查的基础上,进一步在原甲拌磷生产车间开展了钻孔取样工作,布置了3个钻孔,钻孔深度43.0、41.0和45.0m,根据土壤颜色、岩性、电导率和pH的变化,共采集土壤样品39个,利用高效液相色谱仪对土壤中的甲拌磷进行了定量分析,同时测试了总有机碳、阳离子交换量、土壤粘粒含量、土壤含水率和温度等土壤的理化性质参数。测试结果显示,甲拌磷主要富集在表层土壤中,随着深度的增加,甲拌磷含量逐渐降低。根据相关性分析,土壤中甲拌磷含量和总有机碳含量有着显著的相关性,R分别为0.767、0.893和0.917,这表明土壤总有机碳含量对甲拌磷垂向分布有着非常重要的影响。     

鄱阳湖及周边经济区土壤镉的含量与分布

采用双层网格布点法,在研究区分别采集表层和深层土壤样品9829和2467个,测定了样品的镉含量和pH值。表层土壤镉含量呈对数正态分布,含镉范围0.024~4.619mg/kg,宜用几何平均值0.157mg/kg表征其平均含量。深层土壤镉含量显著低于表层,含量范围0.010~1.982mg/kg,算术平均值和几何平均值分别为0.098mg/kg和0.080mg/kg。研究区7地市表层土壤镉含量几何平均值较30年前上升34.6%~165%。据《土壤环境质量标准GB15618-1995》,以镉为评价指标时,研究区以Ⅰ类土壤为主,分布面积占总面积的78.36%,次为Ⅱ类土壤、分布面积占总面积的15.92%,Ⅲ类和劣Ⅲ类土壤仅占总面积的5.72%,显示土壤环境质量良好,但仍须采取有效措施遏制镉污染的迅猛发展。