典型有机磷酸酯阻燃剂分析方法研究进展

有机磷酸酯(OPEs)是一类重要的有机磷阻燃剂,近些年逐渐取代了溴代阻燃剂,广泛应用于各行各业,也因此导致在多种环境介质中有较高的暴露量和潜在风险。已有研究表明,OPEs具有一定的毒理效应,对人体及其他生物均有潜在危害。本文综述了近年来国内外OPEs的检测技术,详述了不同环境介质OPEs的前处理方法。结果表明,目前固相萃取(SPE)和固相微萃取(SPME)仍是水样前处理的主要方法;对于固体样品,加速溶剂萃取/加压液相萃取(ASE/PLE)和微波辅助萃取(MAE)应用较多;虽然大气样品仍以固体吸附剂方式为主,但已向在线一体化方向发展;而生物样品的前处理方法多与水样和固体样品方法相似;但是对于复杂环境介质中OPEs样品的前处理较为困难,方法有待改善;气相色谱-质谱联用(GC-MS)和气相色谱-氮磷检测器(GC-NPD)对弱极性和易挥发的OPEs分析效果好,而强极性和难挥发的OPEs多用液相色谱-质谱联用(LCMS);气相色谱-质谱串联(GC-MS/MS)、液相色谱-质谱串联(LC-MS/MS)和高效液相色谱-质谱串联(UPLC-MS/MS)等对多种复杂的环境介质中的OPEs均有较好的检测分析效果,但并未普及。最后,对OPEs分析测试方法的发展趋势提出了展望。     

Photosynthesis and related metabolic mechanism of promoted rice (Oryza sativa L.) growth by TiO2 nanoparticles

• The rice growth was promoted by nano-TiO₂ of 0.1–100 mg/L. • Nano-TiO₂ enhanced the energy storage in photosynthesis. • Nano-TiO₂ reduced energy consumption in carbohydrate metabolism and TCA cycle. Titanium dioxide nanoparticle (nano-TiO₂), as an excellent UV absorbent and photo-catalyst, has been widely applied in modern industry, thus inevitably discharged into environment. We proposed that nano-TiO₂ in soil can promote crop yield through photosynthetic and metabolic disturbance, therefore, we investigated the effects of nano-TiO₂ exposure on related physiologic-biochemical properties of rice (Oryza sativa L.). Results showed that rice biomass was increased >30% at every applied dosage (0.1–100 mg/L) of nano-TiO₂. The actual photosynthetic rate (Y(II)) significantly increased by 10.0% and 17.2% in the treatments of 10 and 100 mg/L respectively, indicating an increased energy production from photosynthesis. Besides, non-photochemical quenching (Y(NPQ)) significantly decreased by 19.8%–26.0% of the control in all treatments respectively, representing a decline in heat dissipation. Detailed metabolism fingerprinting further revealed that a fortified transformation of monosaccharides (D-fructose, D-galactose, and D-talose) to disaccharides (D-cellobiose, and D-lactose) was accompanied with a weakened citric acid cycle, confirming the decrease of energy consumption in metabolism. All these results elucidated that nano-TiO₂ promoted rice growth through the upregulation of energy storage in photosynthesis and the downregulation of energy consumption in metabolism. This study provides a mechanistic understanding of the stress-response hormesis of rice after exposure to nano-TiO₂, and provides worthy information on the potential application and risk of nanomaterials in agricultural production.     

饮用水中三卤甲烷的生成机理与影响因素研究进展

在饮用水消毒过程中,氯会与天然有机物(NOM)等反应生成消毒副产物(DBPs),三卤甲烷(THMs)是一种主要的DBPs,长期低浓度的THMs暴露对人体有一定的健康风险。THMs和其前驱物种类繁多、生成机理复杂且影响因素诸多,如何抑制消毒过程中THMs的形成是饮用水安全领域的研究热点。通过查阅大量文献,从THMs形成机理及影响因素等方面归纳了目前THMs研究现状,总结了甲基酮、腐殖酸、氨基酸、β-二酮等重要前驱物生成THMs的反应途径,探讨了操作条件以及离子对THMs生成的影响,对该领域未来研究方向进行了展望。     

Robust Regression with Data-Dependent Regularization Parameters and Autoregressive Temporal Correlations

We introduce robust procedures for analyzing water quality data collected over time. One challenging task in analyzing such data is how to achieve robustness in presence of outliers while maintaining high estimation efficiency so that we can draw valid conclusions and provide useful advices in water management. The robust approach requires specification of a loss function such as the Huber, Tukey’s bisquare and the exponential loss function, and an associated tuning parameter determining the extent of robustness needed. High robustness is at the cost of efficiency loss in parameter loss. To this end, we propose a data-driven method which leads to more efficient parameter estimation. This data-dependent approach allows us to choose a regularization (tuning) parameter that depends on the proportion of “outliers” in the data so that estimation efficiency is maximized. We illustrate the proposed methods using a study on ammonium nitrogen concentrations from two sites in the Huaihe River in China, where the interest is in quantifying the trend in the most recent years while accounting for possible temporal correlations and “irregular” observations in earlier years.     

我国东部轻度富营养化湖泊（元荡湖）介形类组成及其生态意义

元荡湖是我国东部平原的一个浅水湖泊,原系淀山湖的一个湖湾,后因芦滩封淤而成,其形成历史短,是探讨动物类群组成与湖泊生态系统演化间关系的理想场所。近年由于人类活动频繁,该湖已处于轻度富营养化状态。研究首次对该湖泊中的介形类进行了研究,共发现9种,它们分别是Cypretta turgida、Cypria kraepelini、Cypridopsis vidua、Cypris subglobosa、Dolerocypria taalensis、Fabaeformiscandona myllaina、F. subacuta、Fabaeformiscandona sp.和Ilyocypris salebrosa。这些介形类均非地方性物种,且都对生态环境有较强的耐受性。结合元荡湖母体湖泊-淀山湖水动力大、无介形类生存的实际情况,研究认为元荡湖中的介形类应由周边迁移而来,且其组成已受到人类活动的干扰。优势度（Y）分析结果也显示,C. kraepelini、F. myllaina、F. subacuta和Fabaeformiscandona sp.共4种出现频率相对较高的介形类中,以富营养化指示物种C. kraepelini的优势度最高。而典型对应分析结果（Canonical correspondence analyses,CCA）发现,自然环境因素水深仍是影响介形类分布的主要环境因子,其次是总氮、叶绿素a、水体透明度和溶解氧。通过分析介形类动物的生活习性和摄食方式发现,元荡湖的介形类分属于底栖动物栖息类型中的游泳型（如C. kraepelini和C. vidua）、攀爬型（如C. subglobosa和C. turgida）和蔓生型(其他5种),其中蔓生型介形类占比最高,达56%,这也解释了为什么在元荡湖这样一个浅水湖泊中水深却成为影响介形类分布的主要环境因素。总结发现,元荡湖中的介形类组成和丰度分布受到湖泊形成时间的长短、自然环境因素和人类干扰等方面的共同影响,这为今后深入开展介形类组成与湖泊演化间的关系提供了理论证据。此外,研究首次报导了F. myllaina在中国的分布。 关键词： 元荡湖;介形类;水深;人为干扰;优势度Y;栖息类型     

3种大型海藻对含铅废水的生物吸附研究

运用批吸附技术研究了海带、裙带菜和条斑紫菜对水溶液中Pb2+的吸附特性。结果表明:pH是影响生物吸附的重要因素,海带和裙带菜吸附Pb2+的适宜pH在3~5之间,紫菜吸附Pb2+的最佳pH为4;在20~40℃范围内,3种海藻对Pb2+的生物吸附非常快,40 min达到吸附平衡,动力学数据符合准二级动力学模型;Langmuir和Freundlich模型成功地拟合了平衡数据。热力学分析表明吸附能够自发进行。红外光谱分析表明,羧基是海带和裙带菜吸附Pb2+的主要官能团。实验结果表明,用这3种海藻吸附剂对水溶液中Pb2+具有较好的吸附性能,海带和裙带菜的吸附容量相近,优于紫菜。     

医疗废物焚烧处理核心技术的开发及应用

国内已建成的医疗废物焚烧设施目前普遍存在进料系统不稳定、玻璃结渣和高浓度HCl气体的排放的问题。这些技术难点已成为医疗废物焚烧处置行业发展的瓶颈。本文介绍了可解决上述问题的"可调节医疗废物恒流量进料技术"、"医废焚烧防玻璃结渣技术"和"含高浓度氯化氢医废尾气处理技术"三项医疗废物焚烧处理核心技术的主要特点及技术指标与应用实例。     

建坝对下游河道水文情势影响RVA评价方法的改进

研究水库下游河道中水文情势的变化是研究水利工程对河流生态系统胁迫的一种新途径。RVA（Range of Variability Approach）方法基于32个参数从水流的等级、频率、历时、发生时间、变化率5个方面的水文特征对建坝后河道水流情势的变化进行定量分析,并给出各个参数确定的满足河道生态要求的流量特征变化范围。将该方法运用于位于浙江省飞云江上的珊溪水库,以其下游的峃口水文站为观测点,分析了该站52a的日流量资料,计算出了河道水流参数满足生态系统要求的可控制范围。并在原RVA评价各参数水文变化度的基础上进行了改进,利用改进的方法对32个参数的变化情况以及整个河流水流情势的变化情况进行了评价。通过与原方法的比较,结果表明改进后的RVA方法更为客观。根据计算结果,建坝后该河流的整体水流情势变化度为中度,流量的频率和历时指标变化最大,低流量事件的持续时间减少,出现次数增多,严重影响了河流的生态功能     

Quantifying interactions between propranolol and dissolved organic matter (DOM) from different sources using fluorescence spectroscopy

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log K _oc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log K _oc and HA having the highest log K _oc. Log K _oc is negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P _i,n) of protein-like region (P _I,n) and the P _i,n of microbial byproduct-like region (P _II,n) of DOM EEMs, while it is correlated positively with humification index and the P _i,n of UVC humic-like region (P _III,n). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.     

Estimation of the environmental risk posed by landfills using chemical, microbiological and ecotoxicological testing of leachates

The leachates from 22 municipal solid waste (MSW) landfill sites in Southern Poland were characterized by evaluation of chemical, microbiological and ecotoxicological parameters. Chemical analyses were mainly focused on the identification of the priority hazardous substances according to Directive on Priority Substances, 2008/105/EC (a daughter directive of the WFD) in leachates. As showed, only five substances (Cd, Hg, hexachlorobutadiene, pentachlorobenzene and PAHs) were detected in the leachates. The compounds tested were absent or present at very low concentrations. Among them, only PAHs were found in all samples in the range from 0.057 to 77.2 μg L⁻¹. The leachates were contaminated with bacteria, including aerobic, psychrophilic and mesophilic bacteria, coliform and fecal coliforms, and spore-forming-bacteria, including Clostridium perfringens, and with filamentous fungi. From the analysis of specific microorganism groups (indicators of environmental pollution by pathogenic or opportunistic pathogenic organisms) it can be concluded that the landfill leachates showed sanitary and epidemiological hazard. In the ecotoxicological study, a battery of tests comprised of 5 bioassays, i.e. Microtox®, Spirotox, Rotoxkit F™, Thamnotoxkit F™ and Daphtoxkit F™ magna was applied. The leachate samples were classified as toxic in 13.6%, highly toxic in 54.6% and very highly toxic in 31.8%. The Spirotox test was the most sensitive bioassay used. The percentage of class weight score was very high - above 60%; these samples could definitely be considered seriously hazardous and acutely toxic to the fauna and microflora.No correlations were found between the toxicity values and chemical parameters. The toxicity of leachate samples cannot be explained by low levels of the priority pollutants. It seems that other kinds of xenobiotics present in the samples at subacute levels gave the high aggregate toxic effect.The chemical, ecotoxicological and microbiological parameters of the landfill leachates should be analyzed together to assess the environmental risk posed by landfill emissions.