Concentrations and bioaccessibility of polycyclic aromatic hydrocarbons in wastewater-irrigated soil using in vitro gastrointestinal test

BACKGROUND, AIM, AND SCOPE: Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of soil environment. Soil ingestion is of increasing concern for assessing health risk from PAH-contaminated soils because soil ingestion is one of the potentially important pathways of exposure to environmental pollutants, particularly relevant for children playing at contaminated sites due to their hand-to-mouth activities. In vitro gastro-intestinal tests imitate the human digestive tract, based on the physiology of humans, generally more simple, less time-consuming, and especially more reproducible than animal tests. This study was conducted to investigate the level of PAH contamination and oral bioaccessibility in surface soils, using physiologically based in vitro gastro-intestinal tests regarding both gastric and small intestinal conditions. MATERIALS AND METHODS: Wastewater-irrigated soils were sampled from the metropolitan areas of Beijing and Tianjin, China, which were highly contaminated with PAHs. Reference soil samples were also collected for comparisons. At each site, four soils were sampled in the upper horizon at the depth of 0-20 cm randomly and were bulked together to form one composite sample. PAH concentrations and origin were investigated and a physiologically based in vitro test was conducted using all analytical grade reagents. Linear regression model was used to assess the relationship between total PAH concentrations in soils and soil organic carbon (SOC). RESULTS: A wide range of total PAH concentrations ranging from 1,304 to 3,369 mug kg(-1) in soils collected from different wastewater-irrigated sites in Tianjin, while ranging from 2,687 to 4,916 mug kg(-1) in soils collected from different wastewater-irrigated sites in Beijing, was detected. In general, total PAH concentrations in soils from Beijing sites were significantly higher than those from Tianjin sites, indicating a dominant contribution from both pyrogenic and petrogenic sources. Results indicated that the oral bioaccessibility of PAHs in small intestinal was significantly higher (from P < 0.05 to P < 0.001) than gastric condition. Similarly, the oral bioaccessibility of PAHs in contaminated sites was significantly higher (from P < or = 0.05 to P < 0.001) than in reference sites. Individual PAH ratios (three to six rings), a more accurate and reliable estimation about the emission sources, were used to distinguish the natural and anthropogenic PAH inputs in the soils. Results indicated that PAHs were both pyrogenic and petrogenic in nature. DISCUSSION: The identification of PAH sources and importance of in vitro test for PAH bioaccessibility were emphasized in this study. The oral bioaccessibility of individual PAHs in soils generally decreased with increasing ring numbers of PAHs in both the gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric conditions to that in the small intestinal condition generally increased with increasing ring numbers, indicating the relatively pronounced effect of bile extract on improving the bioaccessibility of PAHs with relatively high ring numbers characterized by their high K ( ow ) values. Similarly, total PAH concentrations in soils were strongly correlated with SOC, indicating that SOC was the key factor determining the retention of PAHs in soils. CONCLUSIONS: Soils were contaminated with PAHs due to long-term wastewater irrigation. PAHs with two to six rings showed high concentrations with a significant increase over reference soils. Based on the molecular indices, it was suggested that PAHs in soils had both pyrogenic and petrogenic sources. It was also concluded that the oral bioaccessibility of total PAHs in the small intestinal condition was significantly higher than that in the gastric condition. Furthermore, the bioaccessibility of individual PAHs in soils generally decreased with the increasing ring numbers in both the gastric and small intestinal conditions. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that more care should be given while establishing reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-to-mouth activities.     

Bioaccessibility of polychlorinated biphenyls in different foods using an in vitro digestion method

Bioaccessibility of organic pollutants in food is important for exposure estimation and risk assessment. An in vitro enzyme digestion experiment was carried out to analyze the bioaccessibility of PCBs in different foods including freshwater fish (bighead carp and oriental weather fish) and vegetables (spinach and cabbage). The results indicated that the bioaccessibility of PCBs in freshwater fish (3%) was much lower than that in leafy vegetables (25%). Based on field survey, the daily exposure TEQ value from these two types of food was 17.9 pg/kg bw/day. However, when bioaccessibility was taken into consideration, the value decreased to 0.61 pg/kg bw/day. Therefore, the forms of PCBs existing in food strongly influenced the bioavailability for humans, which may have important implications on dietary exposure. To our knowledge, this is the first paper to illustrate the bioaccessibility of PCBs in different foods using an in vitro digestion method.     

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

Plant Bioassays for an in Situ Monitoring of Air Near an Industrial Area and a Municipal Solid Waste – ŽILINA (SLOVAKIA)

The process of a bioindication of genotoxic effects of complex mixtures on the environment using higher plants is very appropriate and effective. We present the results of an in situ indication of the genotoxic effects of polluted environment near Žilina city. For a more complex monitoring we used: the Tradescantia micronucleus (Trad-MCN) assay, the Tradescantia microspore test and an evaluation of the abortivity of the pollen grains of native plant species. We found significant differences in the frequency of the micronuclei when using the Trad-MCN test in local of Dubeň. The Tradescantia pollen abortivity test showed significant differences in the frequency of the abortive pollen grains between the exposed groups and the control group. By using native plant species in the pollen abortivity test we found significant differences in both of the two locations for the four following species during two consecutive years: Artemisia vulgaris, Melilotus albus, Trifolium pratense, Typha latifolia.     

超临界二氧化碳萃取环境样品中金属离子的研究进展

原位络合的超临界萃取技术开辟了超临界二氧化碳（ＳＣ－ＣＯ２）萃取金属离子的新途径。本文综述国外有关ＳＣ－ＣＯ２萃取环境样品中金属离子的原理、流程、应用及影响因素等方面的研究进展,并相信随着研究工作的不断深入,更加理想的络合剂和ＳＣ－ＣＯ２携带剂的发现,必将使ＳＣ－ＣＯ２萃取金属离子的技术在环境样品中痕量金属离子的前处理和分析以及有害金属离子的处理等方面的应用前景更为广阔     

A simple and reliable method of chromosome banding for prenatal cytogenetics using a bromodeoxyuridine pulse

An extremely simple, fully defined and reliable technique for banding chromosomes in situ is described. The method uses a pulse of bromodeoxyuridine to produce replication pattern banding complete with G- and C-type banding in the same karyotype. This enables immediate resolution of problems otherwise requiring extra subculturing and the application of conventional banding techniques. The value of routine chromosome banding in prenatal cytogenetics using such an economical technique is discussed.     

A 10-year survey, 1980–1990, of prenatally diagnosed small supernumerary marker chromosomes,identified by fish analysis. Outcome and follow-up of 14 cases diagnosed in a series of 12 699 prenatal samples

A cytogenetic survey and follow-up studies were made of 14 cases with supernumerary marker chromosomes, identified among 12 699 prenatal samples, investigated at our institution over a 10-year period from 1980 to 1990. FISH (fluorescence in situ hybridization) techniques were employed to identify the chromosomal origin of the marker chromosomes. Five cases were familial, all derived from acrocentric chromosomes, and all without apparent phenotypic effects in the children. Nine cases represented de novo aberrations. In two cases (one with a marker from chromosome 14 or 22, the other with a ring-like marker derived from chromosome 17), the pregnancies continued and apparently normal babies were delivered at term, but the child with a marker derived from chromosome 17 showed slight psychomotor retardation at 2 years of age. All other pregnancies with de novo markers were terminated. In three cases, significant abnormalities were found at autopsy. One of these had an isochromosome 12p and the phenotype was consistent with Pallister-Killian syndrome. In conclusion, marker chromosome identification, as well as clinical follow-up, is essential for the purpose of improving genetic counselling.     

磁性吸附剂CeO2/MZFS去除水中盐酸四环素

利用废碱性电池制备得到尖晶石结构的锰锌铁氧体Mn_0.6Zn_0.4Fe₂O₄（MZF）,利用原位聚合制备得到硅包覆的磁性纳米复合物MZF@SiO₂（MZFS）,采用浸渍法制备得到集磁分离、吸附与类Fenton催化活性于一体的CeO₂/MZFS磁性吸附剂,并对其形貌和磁性能等进行了表征.结果表明,CeO₂/MZFS对水中盐酸四环素（TH）表现出良好的吸附性能,160 min吸附过程可达平衡,TH的去除率达到95%.吸附过程可用准二级动力学方程描述,化学吸附为速控步骤;Freundlich等温吸附模型能较好地描述该吸附过程,热力学计算结果表明,CeO₂/MZFS对TH的吸附是以物理吸附为主的自发吸热过程;利用红外光谱初步揭示了吸附机制.吸附TH后的CeO₂/MZFS可利用其非均相类Fenton催化活性以H₂O₂作为再生剂进行原位再生,6次循环使用后,CeO₂/MZFS对TH仍能保持较高的平衡吸附量.研究结果可为抗生素废水的治理提供理论指导和技术支持.     

Fe改性原位Cu/SSZ-13催化剂柴油车尾气脱硝性能研究

以廉价的铜四乙烯五胺(Cu-TEPA)为模板剂,采用水热法原位合成Cu/SSZ-13分子筛,进一步经过浸渍铁对其改性制备Fe-Cu/SSZ-13催化剂.考察铁盐种类及浸渍铁量对其柴油车尾气脱硝活性及水热稳定性的影响.使用XRD、N_2吸附-脱附、H_2-TPR、NH_3-TPD对样品进行表征测试,并分析影响样品脱硝活性以及水热稳定性的原因.结果表明:浸渍量为1.0%时,以Fe(NO_3)_3为铁盐改性得到的Fe-Cu/SSZ-13分子筛催化剂柴油车尾气脱硝效果最佳,在160～530℃温度范围内,NO的转化率能到达90%以上,并且具有优异的N_2选择性和水热稳定性.由分析结果推测,以Fe(NO_3)_3为铁源时,负载在Cu/SSZ-13分子筛上的铁更为牢固,使其抗老化性能提高,且在脱硝过程中铁物种和铜物种同时起到对NO的还原作用.