Environmental occurrence of Q1, a C9H3C17N2 compound,that has been identified as a natural bioaccumulative organochlorine

Environmental appearance of Q1, a natural heptachloro compound with the molecular formula C₉H₃Cl₇N₂, was studied in samples from different sites all over the world. Q1 was expected to have a bipyrrole backbone, similar to other compounds ascribed to natural sources. A method for isolation of Q1 was developed by combination of adsorption chromatography on silica and normal phase HPLC with an amino phase. UV-detection of Q1 supports the aromatic character of the compound.

The high levels detected in samples of marine mammals and birds suggested that Q1 is both a persistent and a bioaccumulative contaminant. This was underscored by calculated log K_OW in the range of other lipophilic organohalogens. In accordance with earlier studies, highest Q1 concentrations were found in the Southern Hemisphere, but with a highly selective GC/ECNI-MS-SIM method, detection of Q1 was also achieved in many samples from the Northern Hemisphere. In addition to marine mammals and birds, Q1 was also detected in fish from the Mediterranean Sea and the Antarctic. Traces were also detected in SRM 1588 certified cod liver oil, but Q1 was not detected in fish from Hong Kong and Lake Baikal.     

Sorption of heterocyclic compounds from a complex mixture of coal-tar compounds on natural clayey till

The sorption and desorption of heterocyclic organic compounds in a complex multisolute system to a natural clayey till was investigated. The composition of the solutes reflect a simplified composition of an aqueous phase in contact with coal tar. Sorption was studied for two ratios (s:l) of clayey till (solid) to aqueous phase (liquid). The effect of the complex mixture of solutes on sorption of the four heterocyclic compounds: benzofuran, dibenzofuran, benzothiophene, and dibenzothiophene is evaluated by comparison with their sorption measured in single-solute systems. Sorption of the four compounds is affected by the complex mixture, with sorption decreases for all four compounds at high s:l ratio indicating competitive sorption. The effect on sorption of the individual compounds is not related to solubility or hydrophobicity of the compounds. Freundlich-type isotherms are observed for all compounds in the high s:l-ratio experiments, but for the most hydrophobic compounds isotherms are close to linear. The sorption of N-compounds and benzofuran is apparently influenced by cation exchange and dipole–dipole attraction to clay minerals. At high concentrations a dramatic increase in the sorption of the most strongly sorbing compounds is observed in the low s:l-ratio experiment. The dramatic increase in sorption appears to be a result of multimolecular layer sorption or condensation on surfaces in the clayey till at high surface density of organic compounds, and the data are fitted by BET (Brunauer, Emmet, and Teller) type 2 isotherms. The increase may or may not be induced by the presence of N-heterocyclic compounds sorbed by cation exchange and dipole–dipole attraction. The desorption of the compounds was studied for the low s:l ratio where multimolecular layer formation apparently had occurred. Partially irreversible sorption, hysteric Langmuir type desorption with isotherms of very high K_l coefficient, or behaviour reflecting dissolution of a condensed phase is observed.     

天然色素生产废水的生物处理研究

天然色素生产废水是一种色度大、难处理的高浓度有机废水，为了寻找该废水的有效处理方法，本文作者采用由升流式厌氧污泥床（UASB）、生物接触氧化、混凝吸附组成的废水处理工艺，对该废水进行了处理试验，结果表明，对稀释4倍的原水，当进水COD为14900mg／L左右时，UASB经过36h的水力停留时间，COD的去除率为58．2％～60．2％、出水色度为180～270倍，SS为119～126mg／L，pH值为6．5～6．8；UASB出水经过24h好氧生物接触氧化反应，COD的去除率超过90％，SS〈70mg／L；最终经过Ca（CIO）2氧化和煤渣吸附深度处理，脱色可至无色，出水COD为200mg／L以下。UASB-生物接触氧化-氧化吸附组合处理工艺处理该类天然色素生产废水是可行的。     

天然色素生产废水的生物处理研究

天然色素生产废水是一种色度大、难处理的高浓度有机废水,为了寻找该废水的有效处理方法,本文作者采用由升流式厌氧污泥床(UASB)、生物接触氧化、混凝吸附组成的废水处理工艺,对该废水进行了处理试验,结果表明,对稀释4倍的原水,当进水COD为14900mg/L左右时,UASB经过36h的水力停留时间,COD的去除率为58.2%～60.2%、出水色度为180～270倍,SS为119～126mg/L,pH值为6.5～6.8;UASB出水经过24h好氧生物接触氧化反应,COD的去除率超过90%,SS<70mg/L;最终经过Ca(ClO)2氧化和煤渣吸附深度处理,脱色可至无色,出水COD为200mg/L以下。UASB生物接触氧化氧化吸附组合处理工艺处理该类天然色素生产废水是可行的。     

含铁化合物对有机氯化物的脱氯处理技术研究

综述了钯 /铁、二硫化铁、硫化铁、三氧化二铁、绿锈等含铁化合物在降解六氯乙烷、四氯化碳、五氯乙烷、四氯乙烷、三氯乙烷、三氯乙烯、四氯乙烯等有机氯化物中的应用以及降解机理     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

The origin of stable halogenated compounds in volcanic gases

BACKGROUND: Halogenated compounds in the atmosphere are of great environmental concern due to their demonstrated negative effect on atmospheric chemistry and climate. Detailed knowledge of the emission budgets of halogenated compounds has to be gained to understand better their specific impact on ozone chemistry and the climate. Such data are also highly relevant to guide policy decisions in connexion with international agreements about protection of the ozone layer. In selected cases, the relevance of specific emission sources for certain compounds were unclear. In this study we present new and comprehensive evidence regarding the existence and relevance of a volcanic contribution of chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), halons (bromine containing halo(hydro)carbons), and fully fluorinated compounds (e.g. CF4 and SF6) to the atmospheric budget. METHODS: In order to obtain new evidence of a volcanic origin of these compounds, we collected repeatedly, during four field campaigns covering a period of two years, gases from fumaroles discharging over a wide range of temperatures at the Nicaraguan subduction zone volcanoes Momotombo, Cerro Negro and Mombacho, and analysed them with very sensitive GC/MS systems. RESULTS AND DISCUSSION: In most fumarolic samples certain CFCs, HFCs, HCFCs, halons, and the fully fluorinated compounds CF4 and SF6 were present above detection limits. However, these compounds occur in the fumarole gases in relative proportions characteristic for ambient air. CONCLUSION: This atmospheric fingerprint can be explained by variable amounts of air entering the porous volcanic edifices and successively being incorporated into the fumarolic gas discharges. Recommendation and Outlook. Our results suggest that the investigated volcanoes do not constitute a significant natural source for CFCs, HFCs, HCFCs, halons, CF4, SF6 and NF3.     

The diffusion and sorption of volatile organic compounds through kaolinitic clayey soils

Laboratory experiments to estimate the effective molecular diffusion coefficient (D(e)) and sorption coefficient (K(d)) for volatile organic compounds through natural clayey soils were conducted using diffusion testing apparatus. The compounds tested were methyl ethyl ketone (MEK), toluene and trichloroethylene (TCE). The D(e) and K(d) values were determined by a curve fitting procedure. The compound losses, and the effects of porous disks used in the apparatus were significant. The transport of MEK was faster than that of TCE and toluene because of the lower sorption to the soils. The D(e) values of all the compounds were of the order of 10(-10) m(2)/s and smaller than the diffusion coefficient in pure aqueous solution at infinite dilution (D(0)), due to the tortuosity of the samples. The effects of the sample thickness on the parameter determination were not significant. Comparison to the K(d) values estimated from batch sorption tests and from organic carbon content (f(oc))-based predictions showed that the diffusion test results were intermediate between those from the other two methods. The diffusion tests use compacted soil samples and should be more relevant to in situ conditions, but the reliability of the tests is affected by large compound losses that cause uncertainties in their interpretation. It is recommended that more than one method be used to assess K(d) values.     

餐厨垃圾处理厂挥发性有机物释放特征

选择目前国内成功运营的餐厨垃圾处理厂为采样点,该厂以利用餐厨垃圾生产生物蛋白饲料和厌氧发酵为主要工艺,采用气相色谱/质谱联用(GC/MS)技术对挥发性有机物(VOCs)浓度较高的工段,如破碎室、湿热反应器、好氧发酵仓进行了定性和定量分析.结果表明,3个采样点共检测出65种物质,包括醇、醛、酮、酯、芳香烃、硫化物、卤代物、烯烃和烷烃9类.湿热反应器排放VOCs浓度最高且包含物质种类最多,其中酮、酯、芳香烃、硫化物、卤代物、烯烃及烷烃类物质浓度均高于其他检测点,需对该工段进行重点监测和控制.     

Generation and analysis of mixed chlorinated/brominated homologs of the halogenated natural product heptachloro-1'-methyl-1,2'-bipyrrole

The 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1, MBP-79) and further halogenated 1′-methyl-1,2′-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was re-newed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br₂ to give 30.5 mg BrCl₆-MBPs along with lower proportions of Br₂Cl₅-, Br₃Cl₄-, Br₄Cl₃- and traces of Br₅Cl₂-MBPs. Longer UV-irradiation in the presence of Br₂ even allowed for the detection of Br₆Cl-MBPs and traces of Br₇-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl₆-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl₆-MBP (∼1.5 mg) was characterized by GC/MS and ¹³C NMR to be 2-bromo-3,3′,4,4′,5,5′-hexachloro-1-methyl-1,2′-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a β-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl₆-MBP enantiomers could be trapped.     

The aerobic soil degradation of spinosad ‐ a novel natural insect control agent

Abstract

Spinosad is a natural product with biological activity against a range of insects including lepidoptera. It is comprised of two major components namely spinosyns A and D. The degradation of spinosad in soil under aerobic conditions was investigated using two U.S. soils (a silt loam and a sandy loam) which were treated with either ¹⁴C‐spinosyn A or ‐spinosyn D at a 2X use rate of 0.4mg/kg soil for spinosyn A and 0.1mg/kg for spinosyn D. Further samples of soil were pre‐sterilised prior to treatment in order to establish whether spinosyns A and D degrade abiotically. Flasks of treated soil were incubated in the dark at 25°C for up to one year after treatment.

HPLC and LC‐MS of soil extracts confirmed that the major degradation product of spinosyn A was spinosyn B, resulting from demethylation on the forosamine sugar. Other dégradâtes were hydroxylation products of spinosyns A and B, with hydroxylation probably taking place on the aglycone portion of the molecule. Half lives were similar for both spinosyns and were in the range 9–17 days, with longer half lives in the pre‐sterilised soils (128–240 days) suggesting that degradation was largely microbial.     

Sorption of polar and nonpolar aromatic compounds to four surface soils of eastern China

Improved predictions on the fate of organic pollutants in surface environments require a better understanding of the underlying sorption mechanisms that control their uptake by soils. In this study, we monitored sorption of nine aromatic compounds with varying physicochemical properties (hydrophobicity, electron-donor/acceptor ability and polarity), including two polycyclic aromatic hydrocarbons, two chlorobenzenes, two nitroaromatic compounds, dichlobenil, carbaryl and 2,4-dichlorophenol in aqueous suspension of four surface soils of eastern China. The tested soils were characterized with respect to organic carbon (OC) content, black carbon content, mineralogy, morphology and size fraction to assess the role of the diverse soil characteristics in sorption. The results of this study show that not only the solute hydrophobicity and the OC content of soil are important to the retention of organic pollutants, but also the solute molecular structure and the soil nature.     

Investigating roles of organic and inorganic soil components in sorption of polar and nonpolar aromatic compounds

The main objective of the present study was to assess the roles of various soil components in sorption of organic compounds differing in polarity. Removal of the whole soil organic matter decreased sorption by approximately 86% for nonpolar 1,3,5-trichlorobenzene (TCB), but only 34-54% for highly polar 1,3,5-trinitrobenzene (TNB); however, removal of the extractable humic/fulvic acids did not much affect sorption of the two sorbates. With normalization of solute hydrophobicity, TNB exhibits several orders of magnitude stronger sorption compared with TCB to maize burn residue (black carbon), extracted humic acid and Na⁺-saturated montmorillonite clay, suggesting specific sorptive interactions for TNB with the individual model soil components. It was proposed that sorption of TCB to the bulk soil was dominated by hydrophobic partition to the condensed, non-extractable fraction of organic matters (humin/kerogen and black carbon), while interactions with soil clay minerals were an important additional factor for sorption of TNB.     

场地污染土壤和地下水修复中受监控的自然修复/恢复技术的应用与研究进展

场地污染土壤和地下水的修复可以分为两个阶段,第1阶段是以消除对人体可能产生的健康风险为主要目标的工程修复,第2阶段是以消除对生态环境的影响为主要目标的自然修复/恢复.受监控的自然修复/恢复技术和强化自然修复/恢复技术具有成本低廉、修复作用持续等优点,在场地污染土壤和地下水的修复中具有广泛的应用潜力,其在消除生态影响和规避修复工程风险方面的作用是工程修复无法取代的.介绍了受监控的自然修复/恢复技术的4种主要途径及其在欧美国家污染土壤和地下水修复中的应用情况,提出了受监控的自然修复/恢复技术的方法步骤,以及这项技术在中国污染土壤和地下水修复中的应用潜力,以期为中国在受监控的自然修复/恢复技术上的科学研究和修复实践提供参考.     

自然循环式污水处理系统及应用实例研究

自然循环污水处理系统(naturalcirculationsystem,NC)是日本研究开发的一种新型的污水人工渗滤处理系统,该技术将落叶、木屑、木炭和石头等自然材料作为填料,并通过各处理单元的有效组合,使该装置内的生物净化功能达到最佳效果。在江苏省宜兴市建立的示范工程显示:NC系统对污水中几个代表性水质指标有较好的去除,CODCr、BOD5、TP和NH+4N等指标基本去除率分别为4951%~9513%、50%~80%、3560%~7813%和7198%~9844%。     

白腐菌对芳香族化合物的降解途径

白腐菌 (Whiterotfungi)是目前所发现的对芳香族化合物有很强降解能力的一类微生物。本文探讨了降解芳香族化合物的白腐菌种及其代谢化合物的主要类型 ,分析了对不同化合物的不同代谢途径 ,同时展望了其应用前景     

利用强化混凝去除水源水中天然有机物的研究进展

总结了近年来利用强化混凝去除水源水中天然有机物的研究,重点讨论了其作用机理和主要影响因素.水源水中天然有机物的含量和成分会因水源地和时间的不同而存在差异,对水源水中天然有机物的了解是保证强化混凝效果的基本前提.不同混凝条件下,强化混凝的主导作用机理不同.铁盐混凝剂、较低pH值、较高混凝剂投量和阳离子有利于提高强化混凝的效果.     

The antiviral activity and cytotoxicity of 15 natural phenolic compounds with previously demonstrated antifungal activity

The present study attempted to evaluate the carcinogenicity of natural phenolic compounds with previously demonstrated antifungal activity, using a computational structure–cytotoxicity approach, namely the quantum structure cytotoxicity relationship model. The cytotoxicity of 15 phenolic compounds with antiviral activity 96?h after treatment was studied using the AdmetSAR computational program. Per the EPA classification, four of the investigated compounds would be included in the second cytotoxicity category, four in the third category, and six showed no toxicity, rendering the studied natural phenolic compounds much less toxic to aquatic life than synthetic pesticides, the organophosphorus compounds, which mostly fall into the first and second categories of toxicity.     

Effects of phenolic compounds on in vivo blood parameters of a fish Notopterus notopterus

Abstract

Effects of phenol (p), dinitrophenol (DNP), pentachloro‐phenol (PCP) and their three combinations, antagonistic [(PCP+DNP)/p], additive [(DNP+P)/pcp] and synergistic [(P+DNP)/PCP], at three subacute concentrations (1/10th, 1/15th and l/20th fractions of 96 h LC₅₀) were determined on several blood parameters after 30 days exposure taking Notopterus notopterus as a test fish. Generally/ RBC, WBC and PCV were found to be increased while CT, ESR, Hb, MCH, MCHC and MCV were decreased. However, PCP showed dual ‐ effects in many cases. CT and MCV were decreased in PCP alone and in (DNP+P)/PCP combination, while increased in (P+DNP)/PCP combination. Hb increased both in (DNP+P)/PCP and (P+DNP)/PCP combinations while decreased in PCP alone. Again RBC and MCV were decreased/increased in DNP alone. Significance of findings is that these haematological parameters can be used as scientifically most accurate and reliable laboratory diagonistic indices by fish breeders, administrators and scientists as to know the state of health of fish population and to make warning about deleterious effects of phenolic compounds so that appropriate measure may be taken by all concerned to protect a valuable source of human food.     

单环硝基芳香化合物好氧生物降解及其遗传学研究进展

硝基芳香化合物是环境中难降解的有机污染物之一 ,对环境的污染日益严重 ,利用生物技术对这类有机物进行降解是行之有效的新途径。针对几种单环硝基芳香化合物好氧降解的微生物、降解途径以及降解过程中的主要酶、降解性质粒、基因定位等分子遗传学的研究进展进行了综述