Discrimination and thermal degradation of toxaphene compounds in capillary gas chromatography when using split/splitless and on-column injection

Technical toxaphene and a 22-component Reference Mixture were analyzed using capillary gas chromatography with split/splitless injection (SSL) and on-column injection (OC). In both techniques, electron-capture, negative ionization mass spectrometry (ECNI-MS) was used for detection of chlorobornanes, chlorocamphenes and related compounds. Significant discrimination of highly chlorinated congeners was observed as a result of incomplete transfer of these compounds from the vaporizer to the analytical column when using SSL. This resulted in a much lower response for nona- and decachloro congeners than when using OC. In addition, several toxaphene components, especially the chlorobornanes with gem dichloro substitution on the six-member carbon ring, undergo thermal degradation when using SSL. Some of these congeners are major components of technical toxaphene, but generally are not present, except at low concentrations, in environmental and biological samples. Therefore, technical toxaphene may be discriminated and/or degraded differently than toxaphene compounds in environmental samples when using SSL. This results in significant bias of the quantitative data when using the technical material as a reference. OC suffers much less from these deficiencies and, therefore, is a preferable technique for toxaphene analysis.     

Degradation of toxaphene in water during anaerobic and aerobic conditions

The degradation of technical toxaphene in water with two kinds of bioreactors operating in sequence was studied. One packed bed reactor was filled with Poraver (foam glass particles) running at anaerobic conditions and one suspended carrier biofilm reactor working aerobically. Chemical oxygen demand (COD), chloride, sulphate, pH, dissolved oxygen, total toxaphene and specific toxaphene isomers were measured. After 6 weeks approx. 87% of the total toxaphene was degraded reaching 98% by week 39. The majority of the conversion took place in the anaerobic reactor. The concentrations of toxaphene isomers with more chlorine substituents decreased more rapidly than for isomers with less chlorine substituents.     

Degradation of toxaphene in aged and freshly contaminated soil

Degradation of toxaphene in soil from both newly contaminated (from Sweden) and aged spills (from Nicaragua) were studied. The newly contaminated soil contained approximately 11 mg kg(-1) toxaphene while the aged Nicaraguan soil contained approximately 100 mg kg(-1). Degradation was studied in anaerobic bioreactors, some of which were supplied with lactic acid and others with Triton X-114. In this study we found that the lower isomers Parlar 11, 12 were degraded while the concentration of isomer Parlar 15 increased. This supported an earlier evaluation which indicated that less chlorinated isomers are formed from more heavily isomers. Lactic acid when added to the soil, interfere with the degradation of toxaphene. Lactic acid was added; several isomers appeared to degrade rather slowly in newly contaminated Swedish soil. The Swedish soil, without any external carbon source, showed the slowest degradation rate of all the compounds studied. When Triton X-114 at 0.4 mM was added, the degradation rate of the compounds increased. This study illustrates that biodegradation of toxaphene is a complex process and several parameters have to be taken into consideration. Degradation of persistent pollutants in the environment using biotechnology is dependent on bioavailability, carbon sources and formation of metabolites.     

Persistence of two neonicotinoid insecticides in wastewater, and in aqueous solutions of surfactants and dissolved organic matter

Wastewater treatment plants receive organic contaminants, such as pesticides, which reach the sewage system from domestic, industrial or agricultural activities. In wastewater, which is a complex mixture of organic and inorganic compounds, biotic or abiotic degradation of contaminants can be affected by the presence of co-solutes. The photodecomposition in natural sunlight of two neonicotinoid insecticides, thiamethoxam and thiacloprid, was investigated in wastewater, aqueous extracts of sewage sludge and in aqueous surfactant solutions, which are abundant in wastewater. Dissipation in the dark was also studied in wastewater, due to reduction of transmitted sunlight in wastewater ponds. With regard to photolysis, thiamethoxam degraded rapidly in all the aqueous solutions. Among them sewage sludge extracts slightly modified (average half-life 17.6 h), wastewater increased (13.7 h) and non-ionic surfactants led, as a family, to the highest dissipation rates (average 6.2 h), with respect to control water (18.7 h). Additionally this pesticide also underwent a slower biodegradation process in wastewater in the dark under anaerobic conditions (around 25 d). A metabolite of thiamethoxam from the biological decomposition in wastewater was identified by HPLC/MS. On the other hand thiacloprid was found to be resistant to photo- and biodecomposition and remained almost unchanged during the experimental periods in all the tested media.     

Studies of toxaphene in technical standard and extracts of background air samples (Point Petre, Ontario) using multidimensional gas chromatography-electron capture detection (MDGC-ECD)

MDGC-ECD procedures have been used to provide insight into the compositional complexity of some of the specific peaks or clusters observed in the gas chromatographic analysis of a technical toxaphene standard, with reference to individual toxaphene congeners (Parlar # components) that are flow commercially available. These investigations have focussed initially upon those peaks and clusters recently identified (Shoeib. M., Brice, K.A., Hoff, R., 1999. Chemosphere 39, 849-871) as dominant constituents of background ambient air. Multiple electron-capturing components have been found to be present in all the species studied: the available individual toxaphene congeners have been matched against these components where possible. In similar fashion, the responses obtained in equivalent gas chromatographic elution windows from the analysis of typical processed air sample extracts have been investigated, with the results showing clear differences relative to the patterns found in the technical toxaphene standard. In most cases, the air sample shows reduced complexity with fewer components present in the cluster. Also, the presence of interfering responses (due to PCBs and other organochlorines) is quite apparent and significant, showing that major problems and errors could arise when using single-column GC-ECD procedures for quantitation of toxaphene in environmental samples. The presence of certain of the Parlar species in the air samples has been confirmed and in most cases these represent the dominant toxaphene component found in the targeted cluster. Furthermore, the persistence of certain congeners in the atmospheric samples appears to be strongly dependent upon chemical structure, since the congeners in question possess an alternating exo-endo chlorine substitution pattern around the six-membered ring in the bornane skeleton. Such persistence is probably the result of lower metabolization of toxaphene residues in soils, water and sediments leading to a similar pattern in the atmosphere following volatilization.     

Toxaphene and other chlorinated compounds in human milk from northern and southern Canada: a comparison.

Human milk from residents of northern Canada (Keewatin) was compared to that in national surveys of southern Canada with respect to residues of toxaphene, PCBs, PCDD/PCDFs, chlordane, and several other persistent organic compounds. Concentrations of toxaphene were approximately ten-fold higher in specimens from Keewatin than from the south. Toxaphene concentrations in samples from the Great Lakes Basin collected in 1992 were not significantly (p < 0.05) different from those of the rest of Canada; however they were significantly (p < 0.05) lower than concentrations reported in a 1986 survey. Hexachlorobenzene, trans nonachlor and oxychlordane were three to five times higher in concentration in the Keewtin samples than in samples reported in the 1992 national survey. Total PCB congeners, DDTs, PCDD/PCDFs, and other chlorinated compounds were not significantly higher in northern samples.     

Study of evolution of PCDD/F in sewage sludge-amended soils for land restoration purposes

The evolution of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in sewage sludge-amended soils used in the restoration of degraded lands, like quarries, has been studied. Two experiments were performed: one in the lab, under controlled conditions, and another in a quarry. Two different doses of sewage sludge were applied in both experiments (with two types of application in the quarry experiment) and the evolution of the amended soils were compared with that of the respective control soils (without addition of sewage sludge). The samples were analyzed with a previously validated method by HRGC HRMS after the extraction and the necessary clean-up steps. The results reveal that polluted sewage sludge increases PCDD/F concentration in soils and that these compounds are persistent in the matrix after long periods of time.     

Biodegradation of phthalate esters during the mesophilic anaerobic digestion of sludge

Phthalic acid esters (PAE) are commonly found in the sludge generated in the wastewater treatment plants. Anaerobic digestion followed by land application is a common treatment and disposal practice of sludge. To date, many studies exist on the anaerobic biodegradation rates of PAE, especially of the easily biodegradable ones, whereas the higher molecular weight PAE have reported to be non-biodegradable under methanogenic conditions. Furthermore, there is no information on the effect of the PAE on the performance of the anaerobic digesters treating sludge. In this study, the anaerobic biodegradation of di-n-butyl phthalate (DBP), di-ethyl phthalate (DEP) and di-ethylhexyl phthalate (DEHP) was investigated and their relative rates of anaerobic degradation were calculated. Also, the biological removal of PAE during the anaerobic digestion of sludge in bench-scale digesters was investigated using DBP and DEHP as model compounds of one biodegradable and one recalcitrant PAE respectively. The degradation of all the PAE tested in this study (DEP, DBP and DEHP) is adequately described by first-order kinetics. Batch and continuous experiments showed that DEP and DBP present in sludge are rapidly degraded under mesophilic anaerobic conditions (a first-order kinetic constant of 8.04 x 10(-2) and 13.69 x 10(-2)-4.35 day(-1) respectively) while DEHP is degraded at a rate between one to two orders of magnitude lower (0.35 x 10(-2)-3.59 x 10(-2) day(-1)). It is of high significance that experiments with anaerobic sludge of different origin (US and Europe) showed that degradation of DEHP occurs under methanogenic conditions. Accumulation of high levels of DEHP (more than 60 mg/l) in the anaerobic digester has a negative effect on DBP and DEHP removal rates as well as on the biogas production.     

Anaerobic degradation of hexachlorocyclohexane isomers in liquid and soil slurry systems

Gamma-hexachlorocyclohexane (gamma-HCH or lindane), one of the most commonly used insecticides, has been mainly used in agriculture. Organochloride compounds are known to be highly toxic and persistent, causing serious water and soil pollution. The objective of the present study is the evaluation of the anaerobic degradation of alpha-, beta-, gamma-, delta-HCH in liquid and slurry cultures. The slurry system with anaerobic sludge appears as an effective alternative in the detoxification of polluted soils with HCH, as total degradation of the four isomers was attained. While alpha- and gamma-HCH disappeared after 20-40d, the most recalcitrant isomers: beta- and delta-HCH were only degraded after 102d. Intermediate metabolites of HCH degradation as pentachlorocyclohexane (PCCH), tetrachlorocyclohexene (TCCH), tri-, di- and mono-chlorobenzenes were observed during degradation time.     

Teil II: Analytik von Toxaphenrückst?nden (UWSF 2/1998)

Zusammenfassung  Die Rückstandsanalytik des Insektizides Toxaphen galt früher als problematisch wegen der gro?en Anzahl an Komponenten mit ?hnlicher Struktur und unterschiedlichem Chlorgehalt. Erschwerend kam hinzu, da? die Zusamensetzung von Toxaphenrückst?nden in Umweltproben sich von der des technischen Standards signifikant unterscheidet. Deshalb war die Quantifizierung einzelner Komponenten früher nicht m?glich. Seit jedoch eine ganze Reihe von Toxaphenkomponenten in ausreichenden Mengen isoliert wurden, von denen einige für Umweltproben repr?sentativ sind, besteht die M?glichkeit, Toxaphenrückst?nde in Umweltkompartimenten zuverl?ssig zu bestimmen. In der letzten Zeit konzentriert sich die Entwicklung vor allem auf die Trennung der chiralen Bestandteile des Gemisches, um anhand der Zusammensetzung der Rückst?nde Verteilungswege und Abbaumechanismen besser identifizieren zu k?nnen.

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Residue analysis of toxaphene has been difficult because of the complexicity of the technical mixture consisting of a high number of compounds with very similar structure and differing chloro content. Furthermore, the composition of toxaphene in environmental samples varies widely and is normally not like that of the technical mixture. Therefore, quantification of single components in environmental samples was impossible. After the isolation and identification of a great number of components during the last decade, enough standards are available for reliable quantification of toxaphene in all environmental compartments. Recently, most research has been done on the separation of chiral components of toxaphene with a view to identify degradation mechanisms and distribution pathways.

     

用于四氯乙烯降解的厌氧污泥的培养与驯化研究

由于四氯乙烯 (PCE)的大量使用和不合理的处置使其成为常见的污染物之一。PCE在好氧条件下不发生生物降解 ,只在厌氧条件下通过还原脱氯发生生物降解。本研究主要是对从不同处理厂获得的厌氧污泥进行培养 ,选出合适的厌氧污泥 ,进行降解PCE的厌氧污泥的驯化 ,为以后进行降解PCE的动力学研究和优势菌种的筛选做准备。同时 ,在实验中检测到了三氯乙烯 (TCE) ,表明PCE是通过还原脱氯发生生物降解的。     

金属铁铝对混凝强化初沉污泥中温厌氧消化的影响简

选取FeCl₃和AlCl₃·6H₂O作为混凝剂对城市污水进行一级强化混凝处理，降低二级生物处理的进水负荷，减少污水生物处理系统的能量消耗。主要研究混凝过程投加的金属盐对一级强化混凝产生的初沉污泥中温厌氧消化的影响。和剩余污泥相比，初沉污泥更适合厌氧消化处理，污泥降解性能和产气性能更高。当采用城市污水一级强化混凝处理时，污泥中的金属和金属盐水解引起的pH降低，使混凝强化初沉污泥的厌氧消化受到一定抑制。随着污泥中铝含量的降低和铁含量的增加，厌氧消化的COD降解率和挥发性固体（VS）降解率逐渐升高，生物气产量逐渐增大，产气速率加快。当混凝强化初沉污泥只含有铁时（铁含量为10.16 mg/L），混凝强化初沉污泥厌氧消化效果最好，产气稳定，而且产气速率高，生物气产量为237 mL，生物气甲烷含量为55.5%，降解单位VS产气量为0.80 L/g，均高于其他含铝的混凝强化初沉污泥。污泥中的铁对初沉污泥厌氧消化的抑制作用远远小于铝的作用，说明铁盐适合用于城市污水的一级强化混凝处理。     

污泥水解酸化过程中污染物的释出及其影响因素研究

为了回收利用污泥中的有机物、氮和磷，研究了将厌氧污泥接种到吸附了污染物质的剩余污泥中，对污泥水解酸化的促进以及污泥中微生物所摄取污染物质的释出规律；揭示了厌氧条件下发酵时间、污泥量、pH和热处理对污染物释出的影响。结果表明，接种24 h后污染物被大量释放出来；在发酵时间为24 h条件下，污染物释出量与污泥质量成正比；吸附了污染物的剩余污泥相对含量越高，释磷量越大；污泥厌氧发酵时，碱性条件下有机物和正磷酸盐的释出量大于酸性条件，加碱调高pH可有效促进氨氮的释出；对吸附了污染物的剩余污泥进行短时热处理可有效缩短其厌氧发酵时污染物的释出时间。结果表明，控制污泥厌氧水解发酵条件可以促进污染物的释出，有利于下一步的回收。     

Total toxaphene and specific congeners in fish from the Yukon, Canada

Toxaphene is one of the major persistent organic pollutants with global environmental impacts. We have measured total toxaphene and specific congeners concentrations in 19 fish samples collected from the Yukon, Canada using gas chromatography coupled to ion trap MS/MS. The total toxaphene concentrations ranged from 42 to 242 ng/g (mean = 107+/-61 ng/g). The sum of the three specific congeners (Parlar 26, 50 and 62) was within 10-55 ng/g. The ratio of the sum of the three congeners to the total toxaphene varied between 8% and 25% in the fish samples but the ratio may be species specific. Our results suggest that consumption of these Yukon fish should have minimal risk of toxaphene exposure.     

Analysis of some polyhalogenated organic pollutants in sediment and sewage sludge

A laminated sediment core collected in the southern part of the Baltic Proper was analysed for DDT compounds, polychlorinated biphenyls (PCB) including the coplanar congeners, polybrominated diphenyl ethers (PBDE) and polychlorinated naphthalenes (PCN). Two sewage sludge samples were also analysed for the same compounds.

The results of the sediment analyses indicate the presence of PCB, DDT and PBDE compounds in sediment layers dating from the 1950s and later. Neither coplanar PCB nor PCN were detected at any level of the sediment core. The PCB concentrations indicate a slight increase in levels during the last decades, while there were no changes in the levels of DDT compounds. In contrast, TeBDE levels increase 4- to 8-fold and one PeBDE congeners levels increase 10- to 20-fold. The results of sewage sludge analyses showed the concentration of the individual PBDE to be at about the same level as for the individual PCB congeners. The congener pattern in sludge samples indicates low-chlorinated products to be the main PCN source.     

Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax)

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.     

Degradations of urobilin and stercobilin during activated sludge treatment of night soil

This paper deals with the degradation of urobilin and stercobilin in the sewage treatment plant or domestic septic tank and elucidates the factors contributing to their decomposition. The quantities of urobolin or stercobilin in the effluents from the sewage treatment plants were low and these substances were degraded by treatment with activated sludge. The efficacies of aeration, bacterial decomposition and free chlorine treatment in degrading urobilin or stercobilin were examined. Urobilin and stercobilin were decomposed by aeration and the decomposition rate was accelerated under alkaline conditions. Both compounds were decomposed by activated sludge, isolated bacteria and free chlorine treatments. These results show the decomposition of urobilin and stercobilin at sewage treatment plants.     

Anaerobic inhibition and biodegradation of antibiotics in ISO test schemes

Municipal sewage is the main exposure route for antibiotics that are used in human medical care. Antibiotics that adsorb to the primary sludge and/or sur-plus activated sludge will enter the anaerobic digesters of municipal sewage treatment plants. Here anaerobic biodegradation or inhibition of anaerobic bacteria resulting in a disturbance of the process might occur. ISO standards 13641 (2003) and 11734 (1999) were used for assessing the anaerobic inhibition of 16 and the anaerobic biodegradability of 9 antibiotics respectively. Digestion sludge from a municipal sewage treatment plant (1g/l d.s.) was used as inoculum in both tests. In ISO 13641 (2003) most antibiotics showed only moderate inhibition effects after a 7 day incubation period, with EC50 values between 24 mg/l and more than 1000 mg/l (equal to mg/g d.s.). In contrast, metronidazol was decisively toxic to anaerobic bacteria with an EC50 of 0.7 mg/l. In the anaerobic degradation tests according to ISO standard 11734 (1995), only benzylpenicillin showed certain ultimate biodegradation after 60 days and most antibiotics inhibited the digesting sludge in the respective parallel tested inhibition controls. Thus the inhibition of anaerobic bacteria by antibiotics observed in the degradation tests was higher than expected from the results of the inhibition tests. The possible explanations are that distinct substrates are used (yeast extract versus sodium benzoate), that the digestion sludge loses activity during the washing steps performed for the degradation tests and that the exposure time in the degradation tests was 8 times longer than in the inhibition test.     

Degradation of organic pollutants in Mediterranean forest soils amended with sewage sludge

The degradation of two groups of organic pollutants in three different Mediterranean forest soils amended with sewage sludge was studied for nine months. The sewage sludge produced by a domestic water treatment plant was applied to soils developed from limestone, marl and sandstone, showing contrasting alkalinity and texture. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10–13 carbon alkylic chain, and nonylphenolic compounds, including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO + NP2EO). These compounds were studied because they frequently exceed the limits proposed for sludge application to land in Europe. After nine months, LAS decomposition was 86–96%, and NP + NP1EO + NP2EO decomposition was 61–84%, which can be considered high. Temporal trends in LAS and NP + NP1EO + NP2EO decomposition were similar, and the concentrations of both types of compounds were highly correlated. The decomposition rates were higher in the period of 6–9 months (summer period) than in the period 0–6 months (winter + spring period) for total LAS and NP + NP1EO + NP2EO. Differences in decay rates with regard to soil type were not significant. The average values of decay rates found are similar to those observed in agricultural soils.