Characterization of dissolved organic carbon and Humic substances in the well water of the Blackfoot disease area in Taiwan

Since the early 1960s, many investigators have reported that blackfoot disease, a peripheral vascular disease, observed in southwestern Taiwan is due to drinking the higher arsenic concentration in well water. However, recent studies indicated that the relationship with blackfoot disease is not only with arsenic but also humic substances. This paper presents some results concerning the characterization (such as fluorescence, elemental composition, molecular weight and carbon distribution) of humic substances isolated from the Fuhsing well water of the blackfoot disease area. For comparison, the dissolved organic carbon (DOC) and humic substances in the normal well water from Chiuying and the Nanwan coastal water were also analyzed. In general, in the well water of the blackfoot disease area, extremely high concentrations of DOC (18.5mg/L) and fulvic acid (7.54mg/L) with high fluorescence intensity (59.1, equivalent to 0.0282uM quinine sulfate solution) and high percentages (over 50%) of low molecular weights of less than 1,000 were obtained compared with those of normal waters. C‐13 Nuclear magnetic resonance spectroscopy showed a high content (37.2%) of aromatic carbon. These higher concentrations of DOC and fulvic acid with the higher content of aromatic carbon in well water might be one of the key factors causing the blackfoot disease in Taiwan.     

焦化厂不同粒径土壤中PAHs的赋存特征

为分析典型焦化污染场地不同粒径土壤中PAHs的累积及其与土壤有机碳含量（TOC）、比表面积（SA）等土壤性质的相关性,对北京焦化厂长期受PAHs污染的土壤进行粒度分级[P1（0.5~1.0 mm）、P2（0.25~0.5 mm）、P3（0.15~0.25 mm）、P4（0.106~0.15 mm）、P5（0.075~0.106 mm）、P6（<0.075 mm）],测定了各粒径土壤的理化性质及土壤中USEPA优先控制的16种PAHs的浓度,探究PAHs在不同粒径土壤中的累积特征,并通过PAHs质量分数及土壤部分理化性质的曲线拟合结果分析PAHs的赋存特征。结果表明：各粒径土壤中16种PAHs均有检出,其最高质量分数大多出现在P1粒径土样,最低质量分数出现在 P4、P5中。各粒径土壤中2~3（低）环 PAHs、ΣPAHs16质量分数变化趋势相似,均为 P1>P2>P3、P4、P6>P5(P<0.05),4（中）、5~6（高）环PAHs趋势类似,均为P1、P2>P3>P6>P4、P5(P<0.05)。比表面积（SA）、总有机碳（TOC）、可溶解性有机碳（DOC）与各类PAHs的质量分数呈现一定的相关性,各类PAHs质量分数随SA的增大呈先增大随后减小趋势,最大质量分数所对应的SA为38~41 m2·g-1,随TOC的增加呈先减小随后增大趋势,最小质量分数所对应的TOC为7.0~8.7 g·kg-1。不同粒径土壤颗粒中,基于污染物毒性当量因子（TEF）的等效质量分数与污染物实际质量分数变化趋势并不相同,ΣPAHs16实际质量分数变化趋势为P1>P2、P3、P4、P6>P5(P<0.05),而其等效质量分数则为P1、P2、P3、P4、P6>P5(P<0.05)。     

Ozonation of aromatic monomer compounds in water: factors determining reaction outcomes

● p- CNB and IBP were selected, to explore factors determining ozonation outcomes. ● •OH contributed only 50 % to IBP removal, compared to the 90 % for p -CNB removal. ● IBP achieved fewer TOC removal and more by-product types and quantities. ● A longer ring-opening distance existed during the degradation of IBP. ● Multiple positions on both branches of IBP were attacked, consuming more oxidants. For aromatic monomer compounds (AMCs), ozonation outcomes were usually predicted by the substituents of the benzene ring based on the electron inductive effect. However, the predicted results were occasionally unreliable for complex substituents, and other factors caused concern. In this study, p-chloronitrobenzene (p-CNB) and ibuprofen (IBP) were selected for ozonation. According to the electron inductive theory, p-CNB should be less oxidizable, but the opposite was true. The higher rates of p-CNB were due to various sources of assistance. First, the hydroxyl radical (•OH) contributed 90 % to p-CNB removal at pH 7.0, while its contribution to IBP removal was 50 %. Other contributions came from molecular O₃ oxidation. Second, p-CNB achieved 40 % of the total organic carbon (TOC) removal and fewer by-product types and quantities, when compared to the results for IBP. Third, the oxidation of p-CNB started with hydroxyl substitution reactions on the benzene ring; then, the ring opened. However, IBP was initially oxidized mainly on the butane branched chain, with a chain-shortening process occurring before the ring opened. Finally, the degradation pathway of p-CNB was single and consumed fewer oxidants. However, both branches of IBP were attacked simultaneously, and three degradation pathways that relied on more oxidants were proposed. All of these factors were determinants of the rapid removal of p-CNB.     

水环境中多环芳烃的污染现状及研究进展

概述了多环芳烃(PAHs)的属性和主要来源,介绍了其在不同环境介质中的分析方法、污染状况、迁移转化及风险评估现状,提出了进一步加强复杂环境基质中PAHs分析方法、不同环境介质中PAHs迁移转化特征,以及PAHs环境生态风险和人体健康风险等方面研究的建议。     

炼钢厂炼焦车间土壤中PAHs的超临界流体萃取-色质联用分析方法研究

超临界流体萃取炼钢厂炼焦车间土壤中多环芳烃的最佳萃取条件为４０ＭＰａ，８０℃，０．５％甲醇动态改性液体ＣＯ２１０ｍＬ时，对土样进行超临界流体萃取，色质联用分析，并与索氏萃取法进行比较。土样中能准确定性的多环芳烃４４种，其中能定量分析的３１种。色谱定量的回收率均值为７８．５％￣１０４．１％，相对标准偏差为５．０％￣１５．６％。     

Toxicological and biochemical responses of the earthworm Lumbricus rubellus to pyrene, a non-carcinogenic polycyclic aromatic hydrocarbon

The effects of the polycyclic aromatic hydrocarbon (PAH) pyrene on earthworms were investigated in contact and soil tests. In addition to measuring toxic effects on survival and reproduction, Ethoxyresorufin-o-deethylase (EROD) activity and catalase activity were also studied as possible biomarkers of toxic stress. The survival data indicated that LC₅₀ values were 0.0068 mg/ml for the contact test, and 283 mg/kg in the soil test. Cocoon production rate was significantly reduced compared to controls at 160, 640 and 2560 mg/kg in the soil test. No EROD activity could be detected in preliminary studies using control and exposed animals from the contact test, so this assay was not used to the soil test. Catalase activity was shown to be significantly lower at 640 mg/kg in the soil test compared to all other treatments and the control. When compared to toxicological data for other soil invertebrates, Lumbricus rubellus has an intermediate sensitivity in respects of survival and a lower sensitivity for reproductive effects, although the soil used in this study had a higher organic content than previous studies, meaning that the sensitivity of this species may be underestimated in comparison to previous published data for other soil invertebrates.     

HQSAR and CoMFA approaches in predicting reactivity of halogenated compounds with hydroxyl radicals

Two quantitative structure–activity relationship (QSAR) methods: hologram QSAR (HQSAR) and comparative molecular field analysis (CoMFa) were evaluated for predicting half-lives of the hydroxyl radicals reaction with substituted aromatic compounds. The HQSAR approach, which is topological in nature, results in a mathematical model which was more stable and has a greater predictive ability than the model derived on the 3-D CoMFA approach. Interpretations of the colour coded results of both methods are in good agreement with the proposed mechanism of the hydroxyl radical oxidation of halogenated aromatic compounds in the atmosphere.     

Behavior of PAHs during cold storage of historically contaminated soil samples

The stability of historically polycyclic aromatic hydrocarbon (PAH)-contaminated soils during cold storage was investigated. Samples from two former manufactured gas plants exhibited quantitative recoveries of PAHs over the whole period of sample holding at 4 °C in the dark (8–10 months), whereas significant losses of PAHs were observed for soils received from a former railroad sleeper preservation plant with low molecular weight compounds being notably more affected compared to heavier PAHs. Already after 2 weeks of holding time, 3-ring PAHs in one of theses samples were down to 29–73% of the initial concentration and significant losses were observed for up to 5-ring compounds. Dissipation of PAHs was found to be predominantly due to aerobic microbial metabolism since sodium azide poisoned samples showed quantitative recoveries for all PAHs over the entire storage time of 3 months. A similar stabilizing effect was observed for freezing at −20 °C as means of preservation. Except for acenaphthene, no significant loss for any of the PAHs was observed over 6 weeks of holding time. Eventually, selected chemical, physical, and biological parameters of two soils were investigated and identified as potential indicators for the stability of PAH-contaminated soil samples.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Subsurface sediment contamination during borehole drilling with an air-actuated down-hole hammer

Drilling methods can severely alter physical, chemical, and biological properties of aquifers, thereby influencing the reliability of water samples collected from groundwater monitoring wells. Because of their fast drilling rate, air-actuated hammers are increasingly used for the installation of groundwater monitoring wells in unconsolidated sediments. However, oil entrained in the air stream to lubricate the hammer-actuating device can contaminate subsurface sediments. Concentrations of total hydrocarbons, heavy metals (Cu, Ni, Cr, Zn, Pb, and Cd), and nutrients (particulate organic carbon, nitrogen, and phosphorus) were measured in continuous sediment cores recovered during the completion of a 26-m deep borehole drilled with a down-hole hammer in glaciofluvial deposits. Total hydrocarbons, Cu, Ni, Cr and particulate organic carbon (POC) were all measured at concentrations far exceeding background levels in most sediment cores. Hydrocarbon concentration averaged 124 +/- 118 mg kg(-1) dry sediment (n = 78 samples) with peaks at depths of 8, 14, and 20 m below the soil surface (maximum concentration: 606 mg kg(-1)). The concentrations of hydrocarbons, Cu, Ni, Cr, and POC were positively correlated and exhibited a highly irregular vertical pattern, that probably reflected variations in air loss within glaciofluvial deposits during drilling. Because the penetration of contaminated air into the formation is unpreventable, the representativeness of groundwater samples collected may be questioned. It is concluded that air percussion drilling has strong limitations for well installation in groundwater quality monitoring surveys.