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。     

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.     

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.     

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.     

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.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

Solubilization of substituted indole compounds by beta-cyclodextrin in water

The solubilization of four pairs of substituted indole compounds (SICs) by β-cyclodextrin (β-CD) in water was investigated. The results show that 1,2,3,4-tetrahydrocarbazole and N-methyl-1,2,3,4-tetrahydrocarbazole form 1:1 inclusion complexes with β-CD, while the other six SICs form 1:2 inclusion complexes, respectively. To each pair of SICs with similar structures, the differences between their solubilization in β-CD/water solutions has been explained by the difference of their contact area within the β-CD cavity, the difference of their molecule polarity, or the presence of hydrogen bond between SIC molecule and β-CD molecule.     

Spatial gradients and source apportionment of volatile organic compounds near roadways

Concentrations of 55 volatile organic compounds (VOCs) (C₂–C₁₂) are reported near a highway in Raleigh, NC. Thirty-minute samples were collected at eight locations, ranging from approximately 10–100 m perpendicular from the roadway. The highest concentrations of VOCs were generally measured closest to the roadway, and concentrations decreased exponentially with increasing distance from the roadway. The highest mean concentration for individual VOCs were for ethylene (3.10 ppbv) (mean concentration at x = 13 m), propane (2.27 ppbv), ethane (1.91 ppbv), isopentane (1.54 ppbv), toluene (0.95 ppbv), and n-butane (0.89 ppbv). Concentrations at the nearest roadway location (x = 13 m) were generally between 2.0 and 1.5 times those from the farthest roadway location (x = 92 m). The data were apportioned into four source categories using the EPA Chemical Mass Balance Model (CMB8.2): motor vehicle exhaust, compressed natural gas, propane gas, and evaporative gasoline. The majority of the VOCs resulted from motor vehicle exhaust (67 ± 12%) (% of total VOC at x = 13 m ± S.D.). Compressed natural gas, propane gas, and evaporative gasoline accounted for approximately 15%, 7% and 1% of the total VOC emissions, respectively, at x = 13 m.     

Occurrence and behaviour of selected hydrophobic alkylphenolic compounds in the Danube River

Six hydrophobic alkylphenolic compounds were investigated for the first time simultaneously in four different matrices in the Danube River. Maximum sediment concentrations were 2.83, 2.10, 0.28, and 0.035 mg kg⁻¹ for nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and octylphenol. Maximum levels in suspended particulate matter (SPM) were 0.18, 0.12, 0.10, and 0.003 mg kg⁻¹. No correlation between concentrations in SPM and sediments was found. Octylphenol monoethoxylate and octylphenol diethoxylate were recorded only in sediment at one location. In mussels and water only nonylphenol and octylphenol were found. Nonylphenol concentrations in mussels (up to 0.34 mg kg⁻¹) correlate with concentrations found in SPM and indicate a slight bioaccumulation. Concentrations in water were close to the limit of quantification. We assume in situ formation of nonylphenol monoethoxylate and nonylphenol in sediments at some locations. In some cases nonylphenol in sediments exceeded the provisional EU environmental quality standards.     

Comparison of competitive and synergetic adsorption of three phenolic compounds on river sediment

Knowledge of toxic chemical sorption by soil/sediment is critical for environmental risk assessment of toxic chemicals, especially for the multi-sorbate system in river ecosystem. Sorption characteristics of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol on sediment were investigated. Adsorption isotherms in single- and multi-sorbate systems fitted well the Freundlich model. The adsorption effects were different among three selected phenolic compounds in single- and multi-sorbate systems. The synergetic affect that 2, 4-Dinitrophenol and 2, 4-Dimethyphenol bring to 2, 4-Dichlorophenol can be explained by the compression of double electronic layer and the charge neutrality. Adsorption kinetic results showed that pseudo-second-order model can be used to describe the experimental data and the adsorption affinity of phenolic compounds influenced greatly by the adsorption velocity. The present study suggests that the fate and transport of emerging pollutants such as phenolic compounds could be affected in the presence of different hydrophobic pollutants in aquatic systems.     

Antiradical activity of natural honeys and antifungal effect against Penicillium genera

The purpose of the study was to examine the antiradical activity of 11 natural honeys and to evaluate the antifungal properties of honey. Honey samples (10) were collected from different locations of Slovak Republic. Honeys were native to different plant species of Robinia pseudoacaccia, Brassica napus subs. napus, Castanea sativa Mill. Thymus serpyllum vulgaris and the other samples had multifloral origin. The low antiradical activitity in honey samples was determined. The best results were found in thyme honey from Rhodos (11.84 %) and Castanea honey from Nitra (10.61 %). The lowest antiradical activity was found in Acacia honey and determined to be 7.62 %. Statistically significant differences (P< 0.001) were found among thyme/Rhodos and Castanea/Nitra. The antifungal activities of honey samples were tested by 10 %, 25 % and 50 % (by mass per volume) concentration against fungi Penicillium crustosum, P. expansum, P. griseofulvum, P. raistrickii and P. verrucosum and by the agar well diffusion method. The solutions containing 10 % (by mass per volume) of honey did not have any effect on the growth of fungi. The strongest antifungal effect was shown by 50 % honey concentration against P. raistrickii.     

气相色谱法分离和测定合成革用胶粘剂中的挥发性有机物

对合成革用胶粘剂中的发挥有机成份进行了色谱分离,并测定了胶粘剂中的9种挥发性有机物,方法的加标回收率为89.4%～102.8%,变异系数为1.2%～5.0%。     

咪唑类[PF6]^-型离子液体萃取胺类化合物

以眯唑类[PF6]^-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺、对氯苯胺等7种胺类化合物的萃取,考察了溶液初始浓度、相比、盐类、pH及离子液体眯唑基团上取代烷基对萃取平衡的影响,并研究了萃取过程的热效应。实验结果表明：溶液初始浓度对分配系数影响较小;相比10：1是离子液体对胺类化合物的溶解饱和临界点,当相比大于10：1时,分配系数降低;NaCl、K2SO4可以增大萃取分配系数,ZnSO4对分配系数几乎没有影响;pH增加,分配系数增大;离子液体对不同取代基的胺类萃取能力有较大的差异,咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著;萃取过程属于焓增大的吸热过程。     

火电灰渣场自然恢复下灰渣养分及重金属含量研究

对自然恢复下4类不同年代样地的灰渣养分含量及重金属含量进行研究,通过对比分析发现,有机质、全氮、全钾、全磷含量随着自然恢复时间的增加呈现递增的趋势,全磷含量在各恢复阶段与对照样地之间并不存在显著差异(P0.05)。pH随着恢复时间的增加呈现递减的趋势。对灰渣综合质量指数进行研究发现,自然恢复长期、中期、短期与自然恢复初期对比均有显著提高(P0.05),且随着自然恢复时间的增加灰渣综合质量指数逐渐提高。对灰渣场锌、铅、铜3种重金属研究后发现,在自然恢复下随着时间的增加,灰渣中重金属含量均呈现递减的趋势。