Photodechlorination of octachlorodibenzothiophene and octachlorodibenzofuran: comparison of experimental degradation pathways with degradation pathways predicted by DFT

Polychlorodibenzothiophenes (PCDTs) are sulfur analogues of polychlorodibenzofurans (PCDFs) and have been detected in environmental samples. We used density functional theory calculations (Gaussian 98W) to predict the photodechlorination pathways of octachlorodibenzothiophene (OCDT) and octachlorodibenzofuran (OCDF) in hexane, and we compared the predicted pathways with those observed during UV irradiation experiments. OCDT and OCDF were observed to degrade through first-order dechlorination processes, and the rate constant for OCDT was less than one-third that for OCDF. The main experimental photodechlorination pathways of OCDT and OCDF led to hexachlorinated and tetrachlorinated congeners, respectively; that is, the photodechlorination pathway of OCDT differed from that of OCDF. On the assumption that the dechlorination mechanisms involved radical reactions, we used DFT calculations to estimate bond-dissociation energies and single-point energies of OCDT and OCDF and their dechlorinated congeners, and we used the resulting information, along with hypotheses regarding the rate-controlling step of the degradations, to predict theoretical degradation pathways. We propose that reaction of dechlorinated radicals with a hydrogen donor was the rate-controlling step for OCDT and that C-Cl bond dissociation by UV light was the rate-controlling step for OCDF.     

Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory

The objectives of the present research were (i) to report the mass balance of chlorine during pentachlorophenol (PCP) photodegradation and (ii) to reveal the photodegradation pathway experimentally with a theoretical proof based on the density functional theory (DFT). The chlorine of PCP was completely mineralized to produce chloride ions after 24h of UV irradiation. As intermediates, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol were identified. At least 80% of the chlorine balance during PCP photodegradation was accounted by PCP, these intermediates, and chloride ions. A DFT calculation showed differences in the C-Cl bond dissociation energy level and the positions of respective PCP molecular and the PCP intermediates. The dechlorination intermediates predicted using the calculated C-Cl bond dissociation energy were consistent with those experimentally confirmed, indicating the feasibility of this theoretical method in predicting the dechlorination pathway.     

Photodegradation fates of cis-chlordane, trans-chlordane, and heptachlor in ethanol

cis-Chlordane, trans-chlordane, and heptachlor were photodegraded in ethanol, and their degradation fates and degradation products were determined by a computational chemical method. The most degradable material was heptachlor (first-order reaction constant k=0.13 min(-1)). Chlorine balances changed during UV irradiation, and the chlorine atoms in chlordane and heptachlor were eventually mineralized. cis-Chlordane, trans-chlordane and heptachlor each generated two di-dechlorinated products. Reactivities at various positions in these compounds were predicted on the basis of bond dissociation energies calculated by nonempirical molecular orbital calculation (Gaussian 98W).     

Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340–400 °C

Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340–400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8 h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340–400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices.     

Fifteen years of monitoring of POPs in the breast milk, Czech Republic, 1994–2009: trends and factors

Background, aim and scope

The breast milk has been recommended to carry out as a monitoring tool for effectiveness evaluation of the Stockholm Convention on Persistent Organic Pollutants (POPs). Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloro-ethane (DDT) and its metabolites (DDX), hexachlorbenzene (HCB) and isomers of hexachlocyklohexane (HCHs) have been monitored in the breast milk of nursing mothers in the Czech Republic since 1994 as a part of The Environmental Health Monitoring System. Knowledge about long-term POPs distribution and accumulation in the human body is crucial to understanding uptake, degradation and subsequent effects as well as to conduct risk assessments. The main aim of this study is to evaluate 15-years long-term trends of selected POPs in human milk in the Czech Republic and to elucidate the questionnaire information about the age, parity and social habits, to the final concentrations. This effectiveness evaluation of POPs restriction is quite precisely after 15-years monitoring campaigns.

Materials, methods and results

The human milk samples (4,753 samples) were analysed for a number of chlorinated organic chemicals including PCBs and selected chlorinated pesticides (OCPs, HCB, HCHs, DDX). The relative change of concentration per year for all chemicals was analysed. The remaining percentages of POPs in breast milk in comparison to 1994 are also expressed. Czech population half-lives of POPs in breast milk, derived from either linear or exponential models were computed.

Conclusions and perspectives

The long-term data indicates a continuation of a decreasing trend of POPs concentrations on breast milk. Our study did not confirm lactation and parity as an important outflux resulting in the decrease in concentrations in mothers, which is in the antagonism with most of the studies. The higher BMI was associated with higher amounts of HCB and lower amounts of higher chlorinated PCBs. The results confirm the effectiveness of restrictions of POPs usage in the Czech Republic. This ongoing long-term study is very useful tool for parametric effectiveness evaluation of Stockholm Convention.     

Chloroperoxidase-mediated chlorination of aromatic groups in fulvic acid

The aim of the present study is to investigate whether exo-enzymatically mediated chlorination of fulvic acid (FA) results in the formation of chlorinated groups within the macromolecules which correspond to those which were previously detected in soil and surface water samples. The chlorination was carried out by exposing FA to a commercial chloroperoxidase (CPO) in the presence of chloride and hydrogen peroxide. The exposed FA was then chemically degraded using an oxidative technique and finally analysed for four different aromatic groups and their chlorinated analogues. The particular aromatic groups included were the methyl esters of 4-ethoxybenzoic acid, 3-methoxy-4-ethoxybenzoic acid, 3,4-diethoxybenzoic acid, and 3,5-dimethoxy-4-ethoxybenzoic acid, along with their mono- and dichlorinated analogues. Prior to the chemical degradation procedure, the FA was analysed for AOX (adsorbable organic halogens) and chlorinated acetic acids. The original FA contained 1.4 mg Cl(org) g(-1) and detectable amounts of two chlorinated aromatic groups. After exposure to the enzyme, the concentration of AOX increased to 44.3 mg Cl(org) g(-1) and detectable amounts of four chlorinated aromatic groups as well as di- and trichloroacetic acid were found.     

Formation and inhibition of chloroaromatic micropollutants formed in incineration processes

The formation pathways for chlorinated aliphatic and chlorinated aromatic compounds in technical incineration processes are reviewed. It is shown that acetylene is converted to chloroaromatic compounds including PCDD/F in a special flow reactor by catalytic activity of CuCl2 in the temperature regime of a post-combustion zone of technical incinerators. Mechanistic pathways begin with chlorination of acetylene. Dichloroacetylene is further condensed to C-4 and C-6 units. Hexachlorobenzene is the dominant aromatic compound and a likely precursor to chlorinated phenols and PCDD/F. Two specific mechanisms of formation of chlorinated aromatic compounds including PCDD/F have been advanced. Both mechanisms begin with the formation of dichloroacetylene from flame pyrolysis products like acetylene. Condensation of dichloroacetylene is mediated by copper species via metallacyclic intermediates and/or a catalytic cycle involving copper stabilized trichlorovinyl radicals. The final pathways of conversion of chlorinated benzenes to PCDD/F via chlorophenols are under active investigation.     

Uptake and elimination of polychlorinated arokatic ethers by fish: chloroanisoles

Uptake rate constants of 10 chloroanisoles by fish are comparable to those of other hydrophobic chemicals. Since fast elimination is found for all congeners the resulting bioconcentration factors are lower than those predicted from their hydrophobicities. Elimination is mainly due to metabolism at the ether bond and the rate constants are independent of hydrophobicity. The presence of the ether bonds does not influence the octan-1-ol/water partition coefficient of the chlorinated aromatic hydrocarbons significantly.     

Thermal degradation of polychlorinated alkanes

Thermal degradation products of two polychlorinated alkanes (PCA) containing 59 % and 70 % chlorine, respectively, and also a commercial chlorinated paraffin (CP) containing 70 % chlorine were determined by gas chromatography and mass spectrometry. Thermolyses were performed in both inert atmosphere and air at different temperatures and times. Aliphatic and aromatic hydrocarbons and minor amounts of chlorinated substances were identified products of the medium chlorinated PCA. The highly chlorinated PCA and the commercial CP in addition gave products such as polychlorinated benzenes, toluenes, biphenyls and naphthalenes.     

Effects of various ions on the dechlorination kinetics of hexachlorobenzene by nanoscale zero-valent iron

The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.     

六氯苯的O3及UV/O3高级氧化降解试验研究

采用O₃、UV/O₃高级氧化法对水中六氯苯（HCB）的降解效果及机理进行了研究，并对结果进行了比较，结果表明，UV本身对HCB的去除率贡献不大，HCB可被O₃、UV/O₃快速降解，即UV＜O₃＜UV/O₃；O₃、UV/O₃作用时，提高体系的初始pH值不利于HCB的降解，在pH＝3，HCB=0.2 mg/L，反应40 min时，HCB的去除可达50%左右，酸性条件下有利于降解反应的进行；无论是O₃单独作用还是UV/O₃联合作用，HCB的降解基本上满足准一级反应动力学规律，如果体系的pH值基本保持恒定，这种规律就更为明显。根据离子色谱(IC)、GC对六氯苯降解中间产物进行了测定，探讨了O₃、UV/O₃降解六氯苯的途径和机理。     

Variability of enzyme system of Nocardioform bacteria as a basis of their metabolic activity

The present review describes some aspects of organization of biodegradative pathways of Nocardioform microorganisms, first of all, with respect to their ability to degrade aromatic compounds, mostly methylbenzoate, chlorosubstituted phenols, and chlorinated biphenyls and the intermediates of their transformation: 4-chlorobenzoate and para-hydroxybenzoate. Various enzyme systems induced during degradation processes are defined. The ability of microorganisms to induce a few key enzymes under the influence of xenobiotics is described. This ability may increase the biodegradative potential of strains allowing them to survive in the changing environment or demonstrate to some extent the unspecific response of microorganisms to the effect of toxicants. Nocardioform microorganisms responsible for degradation of such persistent compounds as polychlorinated biphenyls, polyaromatic hydrocarbons, chlorinated benzoates and phenols and other xenobiotics are characterized. The possibility of using Nocardioform microorganisms in some aspects of biotechnology due to their ability to produce some compounds important for industry is also estimated.     

Residue levels of chlorinated hydrocarbon compounds in water and sediment samples from Nile branches in the Delta, Egypt.

Water and sediment samples were collected from eight different locations along the River Nile and its branches. Residues of hexachlorocyclohexane (HCH's), hexachlorobenzene (HCB), DDT's, cyclodienes and polychlorinated biphenyls (PCB's) were analyzed by GLC. Data on Grand Total (GT) concentration values pointed out that Rosetta Branch was more polluted with all components than Demietta Branch. Kafr El-Ziate was the most polluted location showing 1355.8 ng/L for water and 7396.9 ng/g for sediments, while Delta Barrage was the least polluted site. The concentrations of gamma-HCH were higher than the other isomers (alpha- and beta-HCH) in all studied sites. The results showed that HCB was the smallest pollutant at all locations on comparison with other chlorinated hydrocarbons. El-Mansoura, Rosetta and Kafr El-Ziate sites contained the highest concentrations of DDT's in both water and sediment samples. P,P'-DDE was dominate in all locations of water samples, but P,P'-DDT was in sediment samples. Also, the results showed the prominent presence of cyclodienes when compared with the other OC's compounds in sediment samples, especially Aldrin. Kafr El-Ziate was the most polluted location by PCB's, particularly the Ar1242. However, there were increasing levels of chlorinated hydrocarbons in the sediment samples parallel to percentage extractable organic matter (% EOM). Sediment/water ratios were calculated for all locations.     

TiO_2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料,采用微波辐射法制备TiO2/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO2/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO2均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO2负载量为18.2%、TiO2/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H2O2、AgNO3、K2S2O8、KIO4和KMnO4均能提高TiO2/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO2/AC光催化效率的强化作用大小顺序为：H2O2〉AgNO3〉K2S2O8〉KMnO4〉KIO4。     

Halogenated compounds in a dated sediment core of the Teltow Canal, Berlin: time related sediment contamination

To study the recent contamination history of DDT (1,1,1-trichloro-2,2-bis(chlorophenyl)ethane) and its metabolites, as well as methoxychlor (1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane), chlorfenson (4-chlorophenyl-p-chlorobenzenesulfonate), and further halogenated aromatics, a sediment core was collected from the Teltow Canal in Berlin (Germany). The sampling site is located nearby a former industrial point source, where recently analyses on pre-samples have indicated high concentrations of halogenated organic compounds. The deposition time of the investigated sediments was determined by gamma-spectrometrical dating. Pollution trends of selected contaminants were attributed to a time period between 5 and 10 years. Concentration profiles reflect not only the recent pollution history of these compounds, but also the time-depending effects of the ban, restriction and termination of DDT-production in the German Democratic Republic (GDR). DDT and other chlorinated aromatic compounds were produced onsite until the late 1980s. Maximum values of 133 mg kg(-1) (dry weight) for p,p'-DDD (1,1-dichloro-2,2-bis(chlorophenyl)ethane) and approximately 100 mg kg(-1) (dry weight) for p,p'-DDMS (1-chloro-2,2-bis(chlorophenyl)ethane), main metabolites of the anaerobic degradation of DDT, were determined. The occurrence of all selected contaminants, most of which have been banned more than 10 years ago, demonstrate recent contamination pathways, and the necessity of a continuous long-term monitoring of the affected environment.     

Chlorophenols and other related derivatives of environmental concern: properties, distribution and microbial degradation processes

Chlorophenols are chlorinated aromatic compound structures and are commonly found in pesticide preparations as well as industrial wastes. They are recalcitrant to biodegradation and consequently persistent in the environment. A variety of chlorophenols derivatives compounds are highly toxic, mutagenic and carcinogenic for living organisms. Biological transformation by microorganisms is one of the key remediation options that can be exploited to solve environmental pollution problems caused by these notorious compounds. The key enzymes in the microbial degradation of chlorophenols are the oxygenases and dioxygenases. These enzymes can be engineered for enhanced degradation of highly chlorinated aromatic compounds through directed evolution methods. This review underscores the mechanisms of chlorophenols biodegradation with the view to understanding how bioremediation processes can be optimized for cleaning up chloroaromatic contaminated environments.     

A multi media load model for the Baltic Sea

The background of this work is the international decision process with regard to the selection of chemicals to be assessed with priority. In order to stress the precautionary principle, mass flows were analysed rather than concentrations, threshold values, etc., as preferred by the chemical legislation (which still excludes the marine area). Lindane, hexachlorobenzene (HCB), trichloroacetic acid and its sodium salt, medium-chained chlorinated paraffins and tributyltin (TBT) were selected due to their great relevance for the marine area. Trichloroacetic acid is an interesting model compound on account of its accidental formation by degradation of volatile chlorinated hydrocarbons and during chlorination processes. In addition, a hypothetical compound was modelled, representing a highly water-soluble substance with low vapour pressure. The balancing area is the Baltic Sea and its catchment area. In order to model the substance flows, the 'Input/Output-load model' has been developed. The model quantifies the shift and the distribution of a yearly load of the substance investigated from the terrestrial-limnic into the marine compartment (Baltic Sea). Water-soluble substances, which are usually considered to be of no concern, may enter the sea in great amounts and, if not degradable, remain there. It turned out to be necessary to take into account remobilisation, unintended formation and point as well as line-sources.     

Formation of polychlorinated diphenyl ethers from condensation of chlorophenols with chlorobenzenes

BACKGROUND AND AIMS: Polychlorinated diphenyl ethers (PCDEs), which are among the members of persistent organic pollutants, and PCDEs have been determined in a number of environmental samples. The main possible sources are the technical production of chlorinated phenols and all processes of incomplete combustion. PCDEs were observed in the fly ash from a municipal waste incinerator (MWI). It was speculated that the condensation of chlorophenols with chlorobenzenes occurred via PCDEs to form polychlorinated dibenzofurans (PCDFs). Nevertheless, PCDEs formation from condensation of chlorophenols with chlorobenzenes has not been confirmed by experimental observation. The objective of this paper is to investigate the formation mechanism of PCDEs from the condensation of chlorophenols with chlorobenzenes. The results are expected to be helpful in understanding the formation of PCDEs and in controlling and abating PCDEs emissions from MWI. METHODS: The pyrolysis of pentachlorophenol (PCP) and/or polychlorobenzenes (PCBz) was carried out in a sealed glass tube. The reaction products were extracted and purified with K2CO3 solution. The samples were concentrated and then cleaned up on an alumina column. GC/MS was used for identification and quantification of reaction products. RESULTS AND DISCUSSION: The results showed that the pyrolysis of hexachlorobenzene (HCB) at 340 degrees C for 6 h led to the formation of decachlorodiphenyl ether (DCDE) (2.41 microg/mg) and octachlorodibenzo-p-dioxins (OCDD) (0.24 micropg/mg), while the pyrolysis of PCP yielded DCDE (13.08 microg/mg) and OCDD (180.13 microg/mg). In addition, the amount of DCDE formation from the pyrolysis of the mixture of PCP and HCB was 4.65 times higher than the total amount of DCDE formation from the pyrolysis of HCB and PCP, respectively. This indicated that PCP and HCB were prone to condensation and formation of DCDE. DCDE was the main congener of PCDEs from condensation of PCP with HCB at 340, 400 and 450 degrees C. A small amount of nonachlorodiphenyl ether (NCDE) was formed by dechlorination reaction at 450 degrees C. The condensation of PCP with 1,2,4,5-tetrachlorobenzene (Cl4Bz) formed 2,2',3,4,4',5,5',6-octachlorodiphenyl ether (OCDE). Small amounts of heptachlorodiphenyl ether (HpCDE) and hexachlorodiphenyl ether (HxCDE) were detected at 450 degrees C. Meanwhile, polychlorinated dibenzo-p-dioxins (PCDDs) and PCDFs were detected from the condensation of PCP and PCBz. CONCLUSIONS: Experimental studies clarified the behavior of the formation of PCDEs from condensation of polychlorophenols and PCBz. The condensation of polychlorophenols with PCBz formed PCDEs through elimination of HCl between polychlorophenols and PCBz molecules. Another pathway of PCDEs formation was elimination of H2O between two polychlorophenol molecules. In addition, dechlorination processes had caused the specific homologous pattern of PCDEs under higher temperatures.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.