Determination of biodegradation potential by two culture-independent methods in PAH-contaminated soils

Biodegradation potentials of polycyclic aromatic hydrocarbons (PAHs) were determined with soil samples collected from various depths of a PAH-contaminated site and of a site nearby where PAHs were not found. Putative dioxygenase genes were amplified by a primer set specific for initial dioxygenases and identified by web-based database homology search. They were further categorized into several groups of which four dioxygenases were selected as probes for DNA hybridization. The hybridization signals according to the presence of putative dioxygenases were positively related to the extent of PAH contamination. However, the signal intensities varied depending on the probes hybridized and moreover were not consistent with PAH biodegradation activities determined by CO2 evolution. Despite widely accepted advantages of molecular biodegradation assessment, our data clearly present the variations of assessment results depending on the genetic information used and suggest that the methodology may tend to underestimate the real biodegradation capacity of a site probably due to the limited dioxygenase database available at the moment. Therefore, the molecular assessment of biodegradation potential should involve a very careful primer and probe design and an extensive microbiological examination of a site of interest to accurately delineate the biodegradation potential of the site.     

连续流动-固相微萃取方法富集水中多环芳烃的探讨

建立了连续流动-固相微萃取富集、气相色谱测定水中多环芳烃的方法，探讨了流量和溶液体积对萃取效果的影响。方法在0μg／L-40μg／L范围内线性良好，8种多环芳烃的检出限为0．05μg／L-0．5μg／L，样品测定的相对标准偏差〈7％，加标回收率为87．0％～112％。     

1H NMR-based metabolomics of time-dependent responses of Eisenia fetida to sub-lethal phenanthrene exposure

¹H NMR-based metabolomics was used to examine the response of the earthworm Eisenia fetida after exposure to sub-lethal concentrations of phenanthrene over time. Earthworms were exposed to 0.025 mg/cm² of phenanthrene (1/64th of the LC₅₀) via contact tests over four days. Earthworm tissues were extracted using a mixture of chloroform, methanol and water, resulting in polar and non-polar fractions that were analyzed by ¹H NMR after one, two, three and four days. NMR-based metabolomic analyses revealed heightened E. fetida responses with longer phenanthrene exposure times. Amino acids alanine and glutamate, the sugar maltose, the lipids cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. The conversion of succinate to fumarate in the Krebs cycle was also interrupted by phenanthrene. Therefore, this study shows that NMR-based metabolomics is a powerful tool for elucidating time-dependent relationships in addition to the mode of toxicity of phenanthrene in earthworm exposure studies.     

Electrochemical or UV-photochemical oxidation of industrial wastes containing polar aromatic sulphonates

BACKGROUND AND INTENTION: Aromatic sulphonates other than surfactants and their hydroxy and amino-derivatives are important intermediates for the production of azo dyes. Their production on a large scale can be detrimental for the environment, if the by-products of their synthesis are not disposed of appropriately. An industrial waste, the organic components of which were mainly amino and hydroxy-substituted aromatic sulphonates, seriously endangers the environment close to an dismissed Italian industrial site. Inorganic sulphates and chlorides contained in the waste seriously hinder its disposal by incineration, since they corrode furnace walls. In this work, preliminary exploration of aqueous-phase electrochemically and photochemically induced oxidation techniques have been performed as possible alternatives to incineration. METHODS: Electrochemically-induced oxidation was experimented on individual aromatic sulphonates and on an industrial waste by electrolysing them between smooth platinum electrodes at low temperature (5 degrees C) and high current densities (0.4 A/cm2) with aqueous 0.5 M NaHSO4 electrolyte. Photochemically-induced oxidation was performed by irradiating individual aromatic sulphonates or industrial waste with a 500 W mercury lamp in the presence of sodium peroxydisulphate. RESULTS AND DISCUSSION: After 200 min electrodegradation, 90% of the original compounds disappeared, while 50% Total Organic Carbon (TOC) of an industrial waste was removed from solution after 10 hours. After 180 min UV-photodegradation, 90% of two test aromatic sulphonates disappeared, while 65% of TOC of industrial waste was removed after 5 hours. CONCLUSIONS: Two methods, electrochemical and UV-persulphate oxidation of an industrial waste, were used in order to propose a disposal procedure alternative to incineration. Electrodegradation with smooth Pt anode in 0.5 M NaHSO4 at 5 degrees C halved TOC concentration within 10 hours, while persulphate-assisted UV-photochemical oxidation with a 500 W high pressure Hg lamp abated two-thirds of TOC concentration after 5 hours. Energetic consumption of electrodegradation was 0.33 kWh/g TOC, while that of photooxidation was larger than 2 kWh/g TOC. Although both techniques can be considered efficient from a purely chemical point of view, since both are capable of wet-oxidising the aromatic sulphonates and the industrial waste, electrodegradation seems more promising than a photochemical degradation if economical considerations are also taken into account. Considering also that neither cell design nor catalyst were optimised in this preliminary study, the energy yield of electrodegradation seems likely to be largely improved.     

Habitat function of agricultural soils as affected by heavy metals and polycyclic aromatic hydrocarbons contamination

Ecotoxic activity of soils polluted with polycyclic aromatic hydrocarbon (PAH) and heavy metals (HM) was evaluated in pot and laboratory experiments. Plants and soil microorganisms were chosen as test organisms and six different soil materials were used in the study. The applied levels of HM and PAH were aimed to reflect environmental conditions in the "worst case" situation. Zn(2+), Pb(2+) and Cd(2+) were introduced to the soils as an aqueous solution of the mixture of salts at the concentrations corresponding to 1000, 500 and 3 mg kg(-1), respectively. Mixture of four PAH compounds (flourene, anthracene, pyrene and chrysene) as a CH(2)Cl(2) solution was applied at levels of 10-100 mg summation operator 4PAH kg(-1). Population and activity of soil microflora was evaluated as measured of total bacteria counts, intensity of respiration and enzyme activity (dehydrogenases and phosphatases). Effect on plants was evaluated on the base of the growth (plant at an early stage of their development) and yield (mature plant) measurements. The results indicate that combined effect of PAH and heavy metals on soil microorganisms activity and on some plants at an early stage of their development can be stronger than in soils amended with HM or PAH separately. Reaction of tested organisms was related to soil properties, PAH concentration, time and plant species. Mature plants (maize) were insensitive to the applied levels of both group of contaminants.     

杭州市居室空气中芳香族化合物污染现状及其来源解析

用热解吸/气质联用技术研究了杭州市居室空气中芳香族化合物的组成。结果表明,杭州市居室空气中共存在60种芳香族化合物,其中苯系化合物48种,非苯芳香族化合物12种,检出率大于50%的23种;苯、甲苯、乙苯、苯乙烯、邻二甲苯、间(对)-二甲苯等10种化合物的总含量之和大于85.39%,是室内空气中主要的芳香族污染物,除萘外,其他22种污染物的平均浓度值均随装修时间间隔延长而降低;污染物主要来源是室内装修过程中使用的或装修材料中残留的有机溶剂、机动车辆排放的尾气、居民家庭中常用的清洁用品及含萘等成分的防蛀剂。     

水体沉积物中有毒有机污染物的监测研究进展

介绍了水体沉积物中有毒有机污染物监测的预处理技术,重点评述了我国水体沉积物中主要有毒有机污染物多环芳烃、多氯联苯和有机氯农药的监测研究现状,认为水体沉积物中有毒有机污染物研究领域今后发展的重点和方向是广泛开展国内主要河流、湖泊、海洋的监测研究和其在水体环境中的迁移及转化机理、生殖毒性以及污染消减与修复技术研究;加强新型预处理技术及其与大型仪器联用技术的研究;尽早建立水体沉积物中有毒有机污染物的监测方法标准及污染评价标准。     

Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of rivers and an estuary in Shanghai, China

Concentrations, spatial distribution and sources of 17 polycyclic aromatic hydrocarbons (PAHs) and methylnaphthalene were investigated in surface sediments of rivers and an estuary in Shanghai, China. Total PAH concentrations, excluding perylene, ranged from 107 to 1707 ng/g-dw. Sedimentary PAH concentrations of the Huangpu River were higher than those of the Yangtze Estuary. The concentration of the Suzhou River was close to the average concentration of the Huangpu River. PAHs source analysis suggested that, in the Yangtze Estuary, PAHs at locations far away from cities were mainly from petrogenic sources. At other locations, both petrogenic and pyrogenic inputs were significant. In the Huangpu and Suzhou Rivers, pyrogenic input outweighed other sources. The pyrogenic PAHs in the upper reaches of the Huangpu River were mainly from the incomplete combustion of grass, wood and coal, and those in the middle and lower reaches were from vehicle and vessel exhaust.     

Sampling of airborne polycyclic aromatic hydrocarbons with semipermeable membrane devices

Semipermeable membrane devices (SPMDs) are nowadays used as passive samplers of organic pollutants. The knowledge of the sampling rate values (R_S) of each substance trapped on membranes is necessary to calculate their average concentration. Here we calculate R_S values for 16 polycyclic aromatic hydrocarbons using the comparison of active sampling method results and the amounts sequestered by SPMDs at varying exposure times.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organized by Dr. Branimir Jovancicevic.     

Atmospheric deposition of polycyclic aromatic hydrocarbons near New England coastal waters

Wet and dry deposition of polycyclic aromatic hydrocarbons (PAHs) was measured at Nahant, Massachusetts, a peninsula jutting into Massachusetts Bay and Wolf Neck, a peninsula jutting into Casco Bay, Maine. Wet deposition (rain and snow) was collected in a funnel which drains into a shielded, temperature controlled receiving bottle. Dry deposition of gaseous and particulate PAHs was collected onto an exposed water surface. PAHs were analyzed by solid phase extraction and gas chromatography-mass spectrometry. Sixteen PAH species were analyzed, ranging from acenaphthylene to coronene. The mean wet deposition rate of the sum of the 16 species is 720 ng m⁻² cm⁻¹ precipitation at Nahant, and 831 ng m⁻² cm⁻¹ precipitation at Wolf Neck. Wet deposition is attributed to regional PAH emitting sources. Storm patterns appear to bring somewhat higher wet deposition of PAHs to Wolf Neck than to Nahant. The mean dry deposition rate is 95 ng m⁻² h⁻¹ at Nahant and 9.3 ng m⁻² h⁻¹ at Wolf Neck. The large difference is attributed to the fact that Nahant is close to the urban-industrial metropolitan Boston area and Logan International Airport, whereas Wolf Neck has no major PAH-emitting sources nearby. Individual measurements have an error bracket of ±30%. The Chemical Mass Balance model was used to apportion the dry deposition to source categories. At Nahant, nine samples gave valid statistical attributes with a mean apportionment: jet exhaust 35%, gasoline fueled vehicles 32%, diesel fueled vehicles 17%, wood combustion 13%, others 3%. At Wolf Neck, six samples yielded a mean apportionment: jet exhaust 30%, gasoline vehicles 28%, diesel vehicles 18%, wood combustion 16%, others 8%. There is a considerable variation between the samples. The apportionment is greatly dependent on the quality and selection of the model inputs, i.e. source signatures, which for PAHs are questionable.