溢油指示物(指标)的HPLC-FLD-GM(1,1)研究

通过对油种、风化和HPLC-FLD实验条件的模糊最大矩阵元评价,确定表征溢油指示物(指标)的HPLC-FLD-GM(1,1)的建模数据信息点.结果表明,溢油风化GM(1,1)模式的预测精度较高,可用于溢油风化预测研究.     

溢油指示物(指标)HPLC-UVD研究

建立了溢油指示物（ 指标）ＨＰＬＣ—ＵＶＤ 相似性模式，给出了溢油指示物（ 指标）ＨＰＬＣ—ＵＶＤ 相似性的择近原则，指出溢油指示物（ 指标）ＨＰＬＣ—ＵＶＤ相似性主要受控于油种、风化和实验误差等因素的影响。结果表明，ＨＰＬＣ—ＵＶＤ 相似性模式可作为溢油指示物（ 指标） 。     

溢油指示物（指标）PLC—UVD研究

建立了溢油指示物（指标）ＨＰＬＣ－ＵＶＤ相生模式，给出了溢油指示（指标）ＨＰＬＣ－ＵＶＤ相似性的择近原则，指出溢出油指示物（指标）ＨＰＬＣ－ＵＶＤ相似性主要受控于油种、风化和实验误差等因素的影响。结果表明，ＰＨＬＣ－ＵＶＤ相似性模式可作为溢油指示物（指标）。     

模糊最大矩阵元鉴别海面溢油

建立了模糊最大矩阵元的海面溢油鉴别模式,提出了油种鉴别的置信水平λ_i的模糊区概念,给出了常见的14种油、两种风化油和海面溢油的模糊动态聚类图。油种鉴别的置信水平λ_i主要受风化的影响,风化30天,任丘原油和30~#重柴油同其它13种油可分类的置信水平范围分别为:0.99939>λ_i>0.99725和0.99791>λ_i>0.99026。海面溢油鉴别结果表明,本法较指纹谱图辨识法的准确度高。     

气相色谱氢火焰/火焰光度双检测器鉴别海上溢油

本文用气相色谱氢火焰—火焰光度双检测器(GC—FID/FPD)、SE—30玻璃填充柱对常见的几种油品及其风化前后的油样进行了色谱分析,并对海上溢油进行了监别,其结果准确可靠,说明了本法的可行性。     

模糊隶属度鉴别海面溢油

建立了海面溢油鉴别的模糊隶属度模式，给出了海面溢油鉴别的最大隶属度规则，指出海面溢油鉴别主要受油种、风化和实验误差的影响。实验结果表明，本方法可鉴别风化一个月的海面溢油。     

溢油外观和碳稳定同位素比率随风化变化实验研究

溢油风化研究对于提升溢油防备和应急响应的效率非常重要。本文采用一种自行设计的用氯丁二烯橡胶围成水池并配有气动推板造波造流的新型溢油风化模拟装置,来模拟燃料油、柴油、涠洲原油、阿曼原油的风化过程,并对溢油样品的外观和碳稳定同位素比率δ13C的动态变化进行研究分析。结果显示,四类油品的外观随风化过程的变化具有显著差别,而且柴油的风化会导致形成球状下沉油块;阿曼原油δ13C与涠洲原油δ13C明显不同,而涠洲原油δ13C却与产自涠洲原油的燃料油颇为相似;四种试验油品在经过长时间风化之后,其δ13C均趋近于溢油刚开始时值,其中,涠洲原油的δ13C在风化过程中的变化幅度最大,大约为其他三种油品的7倍。本项研究的成果可应用于水上溢油的品种及其环境归宿的鉴别分析。     

海洋污染损害碳稳定性同位素比值差异性溯源分析实验技术——以船舶溢油污染事故为例

现行油指纹鉴别技术主要以溢油的化学组成及分布特征为依据进行溢油种类和油源鉴别。本文对于采集的来自不同油品及不同风化程度、沾污不同环境介质的样品,进行总组分的碳稳定性同位素比值（δ13C）测定,有针对性地分析具有时空关联性的样品测定结果的差异性,为溢油鉴别提供一种新的溯源技术方法,为海事主管机关开展海上船舶溢油污染事故调査处理提供多元化的证据支持。针对4种溢油风化实验样品、来自东海“桑吉”轮溢油事故、福建福清江阴港“正力洛杉矶”轮燃料油泄漏事故、福建平潭看澳锚地“鑫海盛168”轮燃料油泄漏事故的源项样品和现场污染样品,进行了总组分δ13C测定及其基于差异性分析的溯源技术研究。结果表明,不同油品的溢油风化样品δ13C随风化时间的增加而具有类似趋势的差异性变化,可用于说明相应油种的同源相关性;利用溢油事故船载货油和燃料油的δ13C差异性,能够鉴别事故海域采集溢油样品的种类;溢油事故船舶燃油舱油样和清污现场采集的溢油样品可用于与受污染环境介质采集油样的δ13C差异性溯源比对;通常环境条件下,同源相似度较高的差异性限值为两倍平行样分析误差。     

海洋污染及其防治

价。结果表明,廉州湾水质较差,受无机氮污染较重,廉州湾的营养水平明显高于南部近岸海域,部分海域属富营养类型。图1表2参4x55 200100246溢油指示物(指标)的HPLC一FLD一GM(1,l)研究/徐恒振…(国家海洋环境监测中心)//海洋环境科学/国家海洋环境监测中心一20(刃,l9(2)一54一57环图X一14 通过对油种、风化和HPLC一FLD实验条件的模糊最大矩阵元评价,确定表征溢油指示物(指标)的HPLc一FLD一GM(1,l)研究的建模数据信息点。结果表明,溢油风化GM(I,l)模式的预测精度较高,可用于溢油风化预测研究。表6参7X55 20()100247锦州湾近岸海域富…     

短期风化对渤海原油正构烷烃组分的影响

溢油风化信息是认识海洋溢油事故发生中溢油行为归宿的必要条件,而油品组分含量等数据是衡量油品风化状况的重要指标。本研究以渤海产轻质、中质和重质3种类型原油为对象,开展实验室原油风化模拟实验,以GC/MS为主要测试手段,探讨短期风化作用对不同类型渤海原油组成的影响。研究得到不同风化程度下各类型原油中正构烷烃组分含量,并以中质油为例对正构烷烃组分变化与蒸发损失间的关系进行了探讨。研究表明,风化作用对不同原油及油品组分含量影响程度存在差异。在24 h风化时间内,渤中28-1轻质原油风化最为严重,最大蒸发损失约为22%;常青号中质原油次之;绥中36-1重质原油受风化作用影响最小,蒸发损失不足1%。3种油品正构烷烃组分含量分别为70.28×10-3、38.19×10-3和0.42×10-3,并随风化时间增加呈降低趋势,且不同C数正构烷烃组分含量降低程度不同。常青号原油中C13~C26正构烷烃组分含量变化与蒸发率呈显著相关关系,可以作为溢油风化程度的评价指标。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.