大气持久性有机污染物分析研究进展

对近年来大气持久性有机污染物(POPs)研究中的新污染物、采样方法、检测方法、评价方法进行了扼要的综述,概括总结了大气POPs研究中人们所关注和需要解决的热点问题.     

我国突发性环境污染事故时空格局及影响研究

收集1993～2005年污染事故统计数据,运用GIS和非参数相关分析方法,分析了全国范围内环境污染与破坏事故的动态变化趋势、空间地域分布,探讨了不同的经济条件下影响其发生的外部凶素.结果表明:①13 a中全国每年发生的环境污染与破坏事故总次数最少为1 406次,最多为3 001次,且总体趋势是下降的,水和大气两类环境事故占据了事故总数的绝大部分(83.04%～92.02%).②环境污染与破坏事故空间上主要集中在我国东南和中部地区省份,湖南、四川和广西为环境事故最密集的区域.③人口数、GDP产值、企业个数和工业废水排放量对环境污染与破坏事故的发生次数有正作用.不同的经济水平下环境污染与破坏事故的发牛与影响因素的相关程度不同,发达省份事故数仅与企业数呈现硅著正相关关系.     

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean = 35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.     

PCBs in air, soil and milk in industrialized and urban areas of KwaZulu-Natal, South Africa

Information regarding polychlorinated biphenyls (PCBs) in environmental media in Africa is limited. This paper presents results of a monitoring program conducted in KwaZulu-Natal Province, South Africa designed to characterize levels, trends and sources of airborne PCBs. Particulate and vapor samples were sampled over the 2004-2005 period at three sites. The total PCB concentration averaged 128 ± 47 pg m⁻³, and levels were highest in winter. Tri- through hexa-congeners predominated, and the vapor fraction was predominant. Several tetra- through hexa-chlorinated congeners had levels comparable to those at urban sites in the northern hemisphere, but hepta- through deca-congeners resembled levels at background sites. PCB source areas, deduced using spatial and temporal patterns, compositional information and trajectory analyses, likely included local, regional and global sources. Soils at three rural sites showed high PCB concentrations, and milk from a local dairy showed PCB concentrations comparable to USA levels in year 2000.     

Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO₂ at mild conditions (pH 4-9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg²⁺ or Ca²⁺. Experimental results of TTC indicate that MnO₂ promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO₂ generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO₂, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Sorption of carbamazepine, 17α-ethinylestradiol, iopromide and trimethoprim to biomass involves interactions with exocellular polymeric substances

The sorption of carbamazepine (CBZ), iopromide (IOP), trimethoprim (TMP) and 17α-ethinylestradiol (EE2) was evaluated using four biomass types (pure ammonia oxidizing bacterial culture, two heterotrophic enrichment cultures with varying levels of oxygenase activity, and a full-scale nitrifying activated sludge (NAS) culture). CBZ and IOP did not sorb to the four biomass types. EE2 did not sorb to the pure culture but sorbed significantly to the heterotrophic cultures and NAS. TMP sorbed to the heterotrophic cultures and NAS, and was not evaluated for the pure culture. Three floc characteristics (hydrophobicity, median particle size, organic matter content) correlated moderately well with the EE2 organic matter sorption coefficient (K_OM,EE2). Zeta potential did not correlate well with K_OM,EE2 but did with K_OM,TMP, indicating that TMP sorption is more influenced by electrostatic factors than EE2. Once divalent cation-linked exocellular polymeric substances (EPS) were removed from flocs, EE2 and TMP sorption to the non-EPS (cellular) fraction decreased by approximately 50%. The correlation between K_OM,EE2 for the non-EPS cellular fraction deteriorated while the correlation between K_OM,TMP improved. EE2 seemed to sorb more strongly to EPS protein whereas TMP sorbed equally to polysaccharide and protein EPS. Attempts to develop predictive models were not successful. Pharmaceuticals that sorbed to biomass samples underwent biodegradation whereas those that did not sorb were not biodegraded, suggesting a relationship between sorption and pharmaceutical biotransformation.     

Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain)

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ng L⁻¹ range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals > alkylphenols > pesticides > illicit drugs ? estrogens.     

Cell absorption induced desorption of hydrophobic organic contaminants from digested soil residue

Oral ingestion of contaminated soil is an important pathway of human exposure to hydrophobic organic contaminants (HOCs), particularly for children in developing countries. The mobilization potential of various contaminants from ingested soil is often characterized using an in vitro gastrointestinal model, based on the quantities of contaminants remaining in digestive fluid after digestion and separation. Recently, it was experimentally demonstrated that a large fraction of mobilized contaminants sorbed on the digested residue could be released if the dissolved fraction was removed by intestinal absorption. This hypothesis was further tested in this study. Soil spiked with dichlorodiphenyltrichloroethane and its metabolites (DDXs) and polycyclic aromatic hydrocarbons (PAHs) was digested using an in vitro gastrointestinal model. A human colon carcinoma cell line (Caco-2) was cultured in digestive fluid with or without soil residue (pre-equilibrated with the soil) for 2 h. A large proportion of the contaminants (37-68%) was sorbed on the digested residue. Without this residue, 66 ± 13% of DDXs and 73 ± 14% of PAHs dissolved in the fluid, as means and standard deviations, were absorbed by the cell monolayer after exposure. With both digestive fluid and residue, the sorbed fraction of PAHs and DDXs decreased by 38-92%, while the ratios of the cellular to the dissolved concentrations were 2.7-2.8 times higher than those without the residue. This supported the hypothesis that the cell absorption of dissolved HOCs induces desorption of the sorbed fraction from digestive residue, and the desorbed HOCs can be absorbed as well.     

Nontarget analysis of polar contaminants in freshwater sediments influenced by pharmaceutical industry using ultra-high-pressure liquid chromatography-quadrupole time-of-flight mass spectrometry

A comprehensive analytical procedure for a reliable identification of nontarget polar contaminants in aquatic sediments was developed, based on the application of ultra-high-pressure liquid chromatography (UHPLC) coupled to hybrid quadrupole time-of-flight mass spectrometry (QTOFMS). The procedure was applied for the analysis of freshwater sediment that was highly impacted by wastewater discharges from the pharmaceutical industry. A number of different contaminants were successfully identified owing to the high mass accuracy of the QTOFMS system, used in combination with high chromatographic resolution of UHPLC. The major compounds, identified in investigated sediment, included a series of polypropylene glycols (n = 3-16), alkylbenzene sulfonate and benzalkonium surfactants as well as a number of various pharmaceuticals (chlorthalidone, warfarin, terbinafine, torsemide, zolpidem and macrolide antibiotics). The particular advantage of the applied technique is its capability to detect less known pharmaceutical intermediates and/or transformation products, which have not been previously reported in freshwater sediments.