水溶液中氯代烷烃的催化还原脱氯研究

研究了氯代甲烷系列和氯代乙烷系列的各种氯代烷烃在铁、铜二相金属体系中的还原脱氯反应,分析了氯代有机物结构性质对还原脱氯反应的影响和规律性,探讨了氯代烷烃在金属还原作用下的还原脱氯机理．     

硝基苯类化合物在铜电极上的电还原特性和还原机理

采用循环伏安法,对硝基苯类化合物在铜电极表面上的电还原特性进行了研究,评价了它们在铜电极上的电还原反应活性,分析了此类化合物在铜电极上的还原机理,并且讨论了电还原反应活性和此类化合物结构之间的关系．结果表明,硝基苯类化合物在铜电极表面有还原电位,也就是说,能在铜电极表面被直接还原．     

京津潮白河多环芳烃及其衍生物分布

采用固相萃取-气相色谱质谱联用仪测定京津潮白河中的多环芳烃(PAHs)及其衍生物(SPAHs)的污染水平,并采用絮凝法分析水样中自由态PAHs/SPAHs和结合态PAHs/SPAHs的分布。结果表明,京津潮白河中PAHs和SPAHs总质量浓度分别为55.06～215.02 ng·L~(-1)和92.37～227.33 ng·L~(-1),上游河段PAHs和SPAHs质量浓度均低于下游河段。7种致癌PAHs占比为22%～41%,需引起重视。本研究中的SPAHs包括三类物质:氧化PAHs(OPAHs)、甲基PAHs(MPAHs)和氯代PAHs(Cl PAHs)。其中,OPAHs对SPAHs贡献最大(59%～71%),其次是Cl PAHs(22%～32%)和MPAHs(7%～14%)。京津潮白河中PAHs和SPAHs主要以自由态形式存在,总浓度可以准确估计污染物的环境风险。     

Contaminants in Muscle of Plaice and Halibut Collected From the St. Lawrence Estuary and Northwest Atlantic

Levels of aromatic hydrocarbons in muscle or plaice and halibut were determined by fluorescence, using the chrysene standard, as recommended by the International Oceanographic Commision, for the analysis of PAH in environmental extracts. Concentrations were highest in muscle of halibut collected at the most contaminated, nearshore site, in the Saguenay Fjord of the St. Lawrence Estuary, compared to other locations further from shore. Although concentrations of fluorescing compounds were not statistically different in plaice, the saturated hydrocarbons displayed unquestionably more biodegradation, with a decrease of n-alkanes and increase of branched aliphatics, at the less contaminated site. Synchronous fluorescence indicated the presence of benzenoid and biphenyl hydrocarbons in the extracted mixtures, while GC-MS-TIC analysis tentatively identified the presence of a series of benzenoid (alkyl benzenes), chlorinated (PCB and DDE), N (trialkylamines) and O (phenols) hydrocarbons. These anthropogenic compounds could derive from petroleum products, surfactants and common products used in industry and households. This study emphasizes the importance of a multispectroscopic approach when investigating complex environmental mixtures.     

氯代多环芳烃的污染现状及毒性研究进展

氯代多环芳烃(chlorinated polycyclic aromatic hydrocarbons,Cl-PAHs)是一种多环芳烃的氯代衍生物,具有与二噁英相似的毒性效应,并且在各种环境介质中广泛存在。Cl-PAHs已成为一种新型有机污染物,对生态环境和人体健康造成潜在的威胁。本文从Cl-PAHs的来源、污染现状、毒性效应与人体健康风险评价等几个方面对国内外有关Cl-PAHs的研究现状和最新进展进行了系统综述。     

Project tocoen. The fate of selected organic pollutants in the environment—iv. soil,earthworms and vegetation 1988

The samples of soils, earthworms and vegetation (needles, lichens, mosses) were collected for the realization of Project TOCOEN (Toxic Organic Compounds in the ENvironment). The samples were collected from three TOCOEN model areas in Czechoslovakia—one city and two rural areas. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs), chlorinated pesticides (C1‐PEST) and polychlorinated biphenyls (PCBs).     

Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

Iron-carbon composite microspheres prepared through a facile aerosol-based process for the simultaneous adsorption and reduction of chlorinated hydrocarbons

Iron-carbon (Fe-C) composite microspheres prepared through a facile aerosol-based process are effective remediation agents for the simultaneous adsorption and reduction of chlorinated hydrocarbons. Complete dechlorination was achieved for the class of chlorinated ethenes that include tetrachloroethylene (PCE), trichloroethylene (TCE), cis- and trans-1,2-dicloroethylene (c-DCE, t-DCE), 1,1-dichloroethylene (1,1-DCE) and, vinyl chloride (VC). The Fe-C particles potentially provides multi-functionality with requisite characteristics of adsorption, reaction, and transport for the effective in situ remediation of chlorinated hydrocarbons. The carbon support immobilizes the ferromagnetic iron nanoparticles onto its surface, thereby inhibiting aggregation. The adsorptive nature of the carbon support prevents the release of toxic intermediates such as the dichloroethylenes and vinyl chloride. The adsorption of chlorinated ethenes on the Fe-C composites is higher (>80%) than that of humic acid (<35%) and comparable to adsorption on commercial activated carbons (>90%). The aerosol-based process is an efficient method to prepare adsorptive-reactive composite particles in the optimal size range for transport through the porous media and as effective targeted delivery agents for the in situ remediation of soil and groundwater contaminants.     

Air monitoring of solvent exposed workers with passive samplers in comparison to “biological monitoring (BM)"†

A study was performed comparing ambient air monitoring (AM) and biological monitoring (BM) in order to evaluate the reliability of passive sampling (PS) in occupational medicine.

Five groups of persons (total number = 188) exposed to tetrachloroethene, isopropanol, toluene, xylene and styrene at the workplace were examined.

AM was performed over several hours using one or two brands of passive samplers (Monitor 3500 and/or ORSA 5). BM includes the determination of the solvent and specific metabolites resp. in blood or urine samples taken at the end of workshift. On the basis of our results we recommend that PS can supply relevant data for the estimation of external exposure to several solvents like chlorinated‐ and aromatic‐hydrocarbons.     

Effects of organic contaminants on reproduction of the starry flounder Platichthys stellatus in San Francisco Bay

Gonadally mature Platichthys stellatus (Pallas) were captured at two localities in San Francisco Bay in 1983–1985 and were induced to spawn in the laboratory; they were evaluated for relationships between several measures of survival through successive early life-history stages, chlorinated hydrocarbon concentrations in maternal liver and spawned eggs, and maternal hepatic mixed-function oxidase (MFO) activity. The effect of laboratory holding on hepatic aryl hydrocarbon hydroxylase (AHH), a particular MFO activity, and concentrations of chlorinated hydrocarbons were also evaluated. Significant negative correlations were found between maternal hepatic AHH activity at the time of spawning and percent viable (floating) eggs, fertilization success, and embryological success. Embryological success was also negatively correlated with concentrations of polychlorinated biphenyls (PCBs) in eggs. Laboratory holding for 45d, about twice the mean time to spawning, resulted in no significant changes in chlorinated hydrocarbon concentrations, but significant decreases in liver concentrations of phthalate esters and hepatic AHH activity. Females captured at the more urbanized central bay site, Berkeley (Bk), had a lesser proportion of floating eggs, poorer fertilization success, and higher hepatic AHH activities than those captured at a site in northern San Pablo Bay (SP). These results indicate the potential for a serious effect of lipophilic neutral organic contaminants on reproduction of an important estuarine flatfish species. Several mechanisms of toxic action are suggested to account for the observed effects, including the binding of toxic metabolites of contaminants to macromolecules and the alteration of sex steroids in females with contaminant-induced P-450 isozyme(s).Some preliminary findings included in this study were presented at the Third International Symposium on Responses of Marine Organisms to Pollutants (Spies et al. 1985 a)     

Application of permanganate in the oxidation of micropollutants: a mini review

As a green oxidant, permanganate has received considerable attention for the removal of micropollutants in drinking water treatment. To provide a better understanding of the oxidation of organic micropollutants with permanganate, the oxidation kinetics of 32 micropollutants were compiled. The pollutants include algal toxins, endocrine disrupting chemicals (EDCs), and pharmaceuticals. The oxidation kinetics of micropollutants by permanganate were found to be first order with respect to both contaminant and permanganate concentrations from which second-order rate constants (k″) were obtained. Permanganate oxidized the heterocyclic aromatics with vinyl moiety (i.e., microcystins, carbamazepine, and dichlorvos) by the addition of double bonds. For the polycyclic aromatic hydrocarbons (PAHs) with alkyl groups, permanganate attacked the benzylic C-H through abstraction of hydrogen. The mechanism for the oxidation of phenolic EDCs by permanganate was a single electron transfer and aromatic ring cleavage. The presence of background matrices could enhance the oxidation of some phenolic EDCs by permanganate, including phenol, chlorinated phenols, bisphenol A, and trichlosan. The toxicity of dichlorvos solution increased after permanganate oxidation, and the estrogenic activity of bisphnol A/estrone increased significantly at the beginning of permanganate oxidation. Therefore, the toxicity of degradation products or intermediates should be determined in the permanganate oxidation processes to better evaluate the applicability of permanganate. The influence of background ions on the permanganate oxidation process is far from clear and should be elucidated in the future studies to better predict the performance of permanganate oxidation of micropollutants. Moreover, methods should be employed to catalyze the permanganate oxidation process to achieve better removal of micropollutants.     

Control of chlorinated aromatic compounds from a municipal solid waste incinerator using limestone addition

In this study, limestone powder was directly added to synthetic MSW, which was fed into a small‐scale fluidized bed incinerator. The concentration of CBzs and CPs in the flue gas were measured before and after a secondary combustion air injection. Finally, the PCDDs and PCDFs concentrations were also measured in the flue gas after the secondary combustion zone. The CaCO₃ added to synthetic MSW not only controls HCl in the flue gas, but suppresses the formation of chlorinated aromatic compounds like CBzs, CPs, PCDDs, and PCDFs. The main mechanisms to control the formation of chlorinated aromatic compounds was more likely related to the suppression of catalytic capability of flyash than the HCl reduction in the flue gas. However, the NO concentration was increased by catalytic reaction of limestone in the fluidized bed.     

Bioenergetics and survival of the marine snail Thais lima during long-term oil exposure

The carnivorous snail Thais lima was fed Mytilus edulis during a 28-d exposure to the water soluble fraction (WSF) of Cook Inlet crude oil. The LC-50 of T. lima declined from >3000 ppb aromatic hydrocarbons on Day 7 to 818±118 ppb on Day 28. The LC-50 of M. edulis declined from >3 000 ppb aromatic hydrocarbons on Day 7 to 1 686±42 ppb on Day 28. Predation rate declined linearly with increasing aromatic hydrocarbon concentration up to 302 ppb; little predation occurred at 538 ppb and none at 1 160 or 1 761 ppb. Snail absorption efficiency averaged 93.5% and did not vary as a function of WSF dose. Total energy expenditure (R+U) increased at 44 ppb aromatics and declined at lethal WSF exposures. At sublethal WSF exposures, percentages of total energy expenditure were: respiration (87%), ammonia excretion (9%) and primary amine loss (4%). These percentages did not vary as a function of WSF dose or time. Oxygen:nitrogen ratios were not affected by WSF concentration or time and indicated that T. lima derived most of its energy from protein catabolism. The uptake of aromatic hydrocarbons into the soft tissues of snails and mussels was directly related to the WSF concentration. Naphthalenes accounted for 67 to 78% of the aromatic hydrocarbons in T. lima and 56 to 71% in M. edulis. The scope for growth was negative above 150 ppb WSF aromatic hydrocarbons and above 1 204 ppb soft-body aromatic hydrocarbons. These snails were physiologically stressed at an aromatic hydrocarbon concentration which was 19% of the 28-d WSF LC-50 (818±118 ppb) and/or 48% of the 28-d LC-50 of soft tissue aromatics (2 502 ppb).     

Isolation of petroleum and chlorinated hydrocarbons from the same extract

Sequential analysis is an extremely powerful technique for complex samples analysis. For determination of petroleum and chlorinated hydrocarbons, the same sample is divided into two parts. One part is utilized to extract the petroleum hydrocarbons and the second part is used to extract the organochlorine compounds because petroleum hydrocarbons usually appear in higher concentrations and interfering with organochlorine compounds. This analysis method required more solvent, time, and more sample volume. The analytical strategy, in this paper, involves the use of effective and efficient but simple techniques for petroleum hydrocarbons and chlorinated hydrocarbons separation. A clean‐up procedure is presented, by which these compounds are isolated from aliphatic as well as polyaromatic hydrocarbons through a combination of HPLC and adsorption chromatography on a florisil microcolumn. Mass spectrometric identification was used as confirmation method. GLC equipped with ECD and FID for organochlorine and petroleum compounds analysis, respectively.     

Gentoxische Substanzen in Wässern

The contamination of waste waters with genotoxic compounds has raised concern about the toxicological impact on man and ecosystems. Some epidemiological studies showed a correlation between contamination of water with genotoxic compounds and incidence of cancer in man, fish, and mussels. This review of published literature summarizes results of the mutagenic potential of waste water from various industries. The Ames assay is frequently used as test system for mutagenicity of organic and inorganic compounds. Some investigations tried to identify the sources of mutagenic contamination. A variety of organic (e.g. nitroaromatic compounds, polycyclic aromatic hydrocarbons, azo-dyes, chlorinated hydroxyfuranes) and inorganic (e.g. heavy metals) mutagenes were identified but it was not possible to attribute the whole mutagenic potential to analytically identified compounds. Due to the lack of data it is presently not possible to perform a risk assessment for humans.     

徐州市区大气颗粒物中多环芳烃的污染特征

采用高效液相色谱技术（HPLC）对徐州市大气颗粒物中优控的16种多环芳烃（PAHs）进行定量研究。结果表明：萘、芴、苊等低分子量芳烃的含量相对较低;苯并（g,h,i）苝、茚并（1,2,3-cd）芘、苯并（k）荧蒽、苯并（a）芘等高分子量芳烃的含量相对较高;含量最高的单体为荧蒽,占待检的16种PAHs的19%以上。不同环数多环芳烃含量大小顺序为：4环〉5环〉6环〉3环〉2环。可吸入颗粒物（PM10）中苯并（a）芘和∑PAHs在不同功能区的分布特征大体上一致,并呈现一定规律性：交通干线区〉工业区〉风景文化区〉居民区〉新城区。由此可以初步认为徐州市区PM10中的PAHs主要来源于燃煤和汽车尾气。     

有机毒物对水蚤的急性毒性

对水蚤的毒笥试验数据是被广泛用于评价化合物水生生态效应的重要依据，检测有机化合物的毒性时，需特别注意待测物的难溶性，挥发性及易光解性，检测了多种氯代芳烃的ＥＣ５０值，其１８ｈ的结果与２４ｈ的结果相近，检测了２４种硝基芳烃的毒性，不同方法计算的ＥＣ５０值一致。     

Occurrence of and risk posed by highly carcinogenic dibenzo[def,p]chrysene isomers in urban soil

Dibenzopyrene and its isomers are considered the most potent carcinogens of all polycyclic aromatic hydrocarbons tested to date. However, despite public concerns over their deleterious effects, they have not been extensively studied. The occurrence of four highly carcinogenic isomers of dibenzopyrene – dibenzo[def,p]chrysene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene in urban soil samples from Shanghai, China, have been determined in this study, as well as that of benzo[a]pyrene and coronene. A total of 14 peaks with ions at m/z 302 were detected by gas chromatography-mass spectrometry. Although the concentrations of benzo[a]pyrene and the sum of the 16 priority polycyclic aromatic hydrocarbons were greater than that of dibenzopyrene and its isomers, the carcinogenic potency of the latter was higher than that of benzo[a]pyrene. The results also indicate that the relative carcinogenic potency of the four dibenzopyrene isomers in the samples is higher than that of the 16 priority polycyclic aromatic hydrocarbons.     

Free ‐ living animals as indicators of environmental pollution by chlorinated hydrocarbons

As some species of game and free‐living animals promptly respond to ecosystem damage by a reaction that is easy to interpret, they are important ecological indicators in assessing the total contamination of the environment. Consumers of the highest order like predators, predatory and fish‐eating birds are among the most important bioindicators of environmental contamination by chlorinated hydrocarbons and PCB.

Data on chlorinated hydrocarbons and PCB levels were collected throughout 1988–1992 and obtained from 16 species of free‐living animals from 9 protected areas of Slovakia. Muscle tissue, liver, kidney and egg samples were examined for HCB, HCH isomers, DDT and its analogues, and PCB.

Levels of organic chlorinated contaminants reveal a decreasing tendency and thus cease to be a toxicologically important risk factor in game, with the exception of predatory birds, as significant values have been recorded in their eggs and reproductive organs.     

Accumulation,fractionation and release of oil by the intertidal clam Macoma balthica

The bivalve mollusc Macoma balthica accumulated hydrocarbons during 180 days of continuous exposure to Prudhoe Bay crude oil in seawater dispersions with nominal concentrations of 0.03, 0.3 and 3.0 mg l^-1. The mollusc's ability to concentrate oil from seawater increased with decreasing oil-in-water concentration. Decreases in oil burden began after 30 to 120 days (depending on the oil concentration) and continued for at least 60 days after exposure to oil ceased. Aliphatic and aromatic hydrocarbons were fractionated in markedly different ways by the bivalve. Branched and cyclic aliphatics in the molecular weight-range dodecane through hexadecane were preferentially retained over straightchain and their higher homologs. Larger and more substituted aromatic compounds were selectively concentrated. There appeared to be no selective concentration of aromatic sulphur compounds.Please address requests for reprints to Dr. D. G. Shaw at the Institute of Marine Science