光催化降解有机磷农药中甲胺磷的降解效率的测定

采用纳米TiO2光催化降解甲胺磷农药，分别测定分析了PO^3-4,有机磷农药，COD等，以说明光催化降解甲胺磷的情况，结果说明纳米TiO2光催化降解甲胺磷是可行的，根据我们及他人光催化降解有机磷农药的实验结果，比较了分别通过测定TOC，CO2，PO^3-4，有面农药，COD等各种不同的分析方法来衡量光催化降解效率，以评定催化剂的活性及光催化法的可行性的优缺点，以便根据样品的实际情况以及实验室所具备的仪器设备，选择合适的分析方法。     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

骆马湖地区水体、沉积物中农药筛查和分布特征

采用气相色谱/质谱（GC/MS）非靶向筛查技术,分别于2019年11月5—7日（枯水期）、2020年4月24—26日（平水期）和2020年7月15—16日（丰水期）对骆马湖地区水体和沉积物中的农药残留进行了筛查并对其空间分布特征进行研究。结果表明,水中筛查出主要农药13种,除草剂占比62%,检出率＞95%的农药有丁草胺、环嗪酮、异丙甲草胺、多效唑、噻氟菌胺、稻瘟灵、毒死蜱、阿特拉津、避蚊胺和莠灭净,阿特拉津检出质量浓度最高（ND～10 599 ng/L,平均值为725.5 ng/L）,其次为多效唑（ND～2 089 ng/L,平均值为237.0 ng/L）和噻氟菌胺（ND～1 991 ng/L,平均值为237.2 ng/L）。与国内其他地区相比,骆马湖地区水中农药污染处于中等水平,其中阿特拉津、稻瘟灵和毒死蜱的生态风险值得重点关注。骆马湖及入湖河流水中农药总质量浓度呈现丰水期＞平水期＞枯水期的特点,与地表径流、农药的性质及其在水体中的释放等因素有关,丰水期入湖口和省界来水中农药对饮用水水源地的影响较大。沉积物中筛查出9种农药,总体含量不高,且仅扑灭净和避蚊胺检出率>95%,其余<20%。     

SBR技术在有机农药废水处理中的应用

采用中和微碱解－厌氧水解－SBR好氧生化工艺处理氧化乐果，久效磷有机农药废水，与国内同类其它处理技术相比较，其COD、BOD5、P等主要污染物去除率以及处理成本，工程投资，占地面积等项技术经济指标优势明显，可在同行业中推广应用。     

Pollution of surface waters with pesticides in Germany: modeling non-point source inputs

Pesticide pollution of surface waters represents a considerable hazard for the aquatic environment. However, the mean amount of pesticides reaching the water resources varies considerably between regions and depends highly upon application rates, chemical characteristics of pesticides and natural conditions during application. In this study a model was developed which estimates loss of 42 active ingredients applied to 11 field crops, vineyards and orchards along each non-point source path of entry (subsurface drains, runoff and spray drift). A spatially and temporally differentiated data set of application rates and periods was compiled for each active ingredient and target culture to enable the modeling of pesticide transport. The model results are provided in digital raster format (100 m×100 m) within a geographic information system (GIS). The calculated pesticide loads in surface waters were compared with measured loads from different catchments in Germany. Both data sets agreed as to the order of magnitude, nevertheless due to the scale of the study the estimated loads cannot be interpreted as absolute values and only differences between active ingredients, regions and application periods should be assessed.     

Electrochemical analysis of endosulfan using a C18-modified carbon-paste electrode

Successful applications of different analytical procedures to determine quantitatively endosulfan and its metabolites in aqueous media can be found in recent literature. Fundamentally, they have made use of solid-phase extraction (SPE) and gas (GC) or liquid chromatography (LC), sometimes coupled to mass spectrometry (MS). In this paper, a new and alternative methodology to determine quantitatively endosulfan in aqueous media is reported. A C18-modified carbon-paste electrode has been used to determine voltammetrically endosulfan, despite its unfavourable electrochemical properties and behaviour. The methodology proposed is based on the decrease experienced by the peak intensity corresponding to voltammetric signals of Cu(II) when successive and constant additions of endosulfan are carried out. This decrease is directly proportional to the concentration of endosulfan what allows to perform an indirect quantification of the pesticide. The detection limit obtained is 40 ng l⁻¹, this value being under the limits specified by European norms and EPA reports.     

Degradation of benomyl, picloram, and dicamba in a conical apparatus by zero-valent iron powder

Reduction of some pesticides (benomyl, picloram, and dicamba) was studied in an aerobic batch conical pilot system to investigate the disappearance of these pesticides on contact with iron powder (20 g/l, 325-mesh). Aqueous buffered solutions of the compounds were added to the system followed by zero-valent iron powder (ZVIP), and the decline in the pesticide concentrations was monitored over time. HPLC analyses show a complete disappearance of picloram (1.20 mg/l) after 20 min of reaction. Benomyl (1.00 mg/l) and dicamba (1.25 mg/l) disappear after 25 and 40 min, respectively. The t₅₀ values ranged from 3 to 5.5 min, and were about slightly less than the t_1/2 values reported when the log of the relative HPLC peak area was plotted versus time, where the relative peak area was calculated by dividing the measured peak area by the initial peak area. Pathways for the degradation of the studied pesticides by ZVIP are proposed.     

青岛沿海养殖区贝类体内有机氯农药残留量分布和评价

2005年5月和9月分别在青岛周边的胶州湾、田横湾、鳌山湾、胶南等贝类养殖区的17个站位采集了杂色蛤,竹蛏,栉孔扇贝等三种贝类,采用气相色谱-电子捕获检测器(GC-ECD),外标法定量,对贝类体内有机氯农药(HCHs、DDTs)残留量进行检测.并对不同情况下残留量的分布状况进行研究,结果表明:(1)贝类体内HCHs的检出率为60%,DDTs为100%.均未超过国家标准.(2)5月份农药残留量偏高,9月份残留量偏低.(3)生活在河流入海口处的贝类体内农残含量略有偏高.(4)栉孔扇贝对有机氯的富集尤为显著,残留量高.杂色蛤,竹蛏农药残留量低.     

胶州湾岩心柱状沉积物中有机氯农药的气相色谱法测定

采用气相色谱法(GC)测定了胶州湾中部岩心柱状沉积物中10种常见的有机氯农药,发现狄氏剂、p,p'-DDT、异狄氏剂和β-666等4种是该海域主要的有机氯农药污染物.其中狄氏剂和p,p'-DDT的检出率为100%,其余2种分别为44%和67%.10种有机氯农药在样品中的总含量为(4.2～121.8)×10-12(干重).调查站位上4种主要的有机氯农药在柱状沉积物中的垂直分布特征为表层至20～22 cm层位其含量随深度的增加而增大;在22 cm以深层位,∑OCPs迅速降低,可能与深层沉积物中的氧化-还原条件以及微生物作用等环境因素引起的降解速率增大有关.     

Effects of multiple but low pesticide loads on aquatic fungal communities colonizing leaf litter

In the first tier risk assessment (RA) of pesticides, risk for aquatic communities is estimated by using results from standard laboratory tests with algae, daphnids and fish for single pesticides such as herbicides, fungicides, and insecticides. However, fungi as key organisms for nutrient cycling in ecosystems as well as multiple pesticide applications are not considered in the RA. In this study, the effects of multiple low pesticide pulses using regulatory acceptable concentrations (RACs) on the dynamics of non-target aquatic fungi were investigated in a study using pond mesocosm. For that, fungi colonizing black alder (Alnus glutinosa) leaves were exposed to multiple, low pulses of 11 different pesticides over a period of 60 days using a real farmer''s pesticide application protocol for apple cropping. Four pond mesocosms served as treatments and 4 as controls. The composition of fungal communities colonizing the litter material was analyzed using a molecular fingerprinting approach based on the terminal Restriction Fragment Length Polymorphism (t-RFLP) of the fungal Internal Transcribed Spacer (ITS) region of the ribonucleic acid (RNA) gene(s). Our data indicated a clear fluctuation of fungal communities based on the degree of leaf litter degradation. However significant effects of the applied spraying sequence were not observed. Consequently also degradation rates of the litter material were not affected by the treatments. Our results indicate that the nutrient rich environment of the leaf litter material gave fungal communities the possibility to express genes that induce tolerance against the applied pesticides. Thus our data may not be transferred to other fresh water habitats with lower nutrient availability.