Effect of a base-catalyzed dechlorination process on the genotoxicity of PCB-contaminated soil

We evaluated the genotoxicity of dichloromethane (DCM) extracts of PCB-contaminated soil before and after the soil had been treated by a base-catalyzed dechlorination process. The treatment process involves heating a mixture of the soil, polyethylene glycol (or hydrocarbons with boiling points of 310–387°C), and sodium hydroxide to 250–350°C. Dechlorination reduced by >99% the PCB concentration of the soil, which was initially 2,200 ppm. The DCM extracts of both control and treated soils were not mutagenic in strain TA100 of Salmonella, but they were mutagenic in strain TA98. Based on results in strain TA98, the base-catalyzed dechlorination process reduced the mutagenic potency of the soil by approximately one-half. The DCM extracts of the soils before and after treatment were equally genotoxic in a prophage-induction assay in . , which detects some chlorinated organic carcinogens that are not detected by the Salmonella mutagenicity assay. These results suggest that treatment of PCB-contaminated soil by base-catalyzed dechlorination reduced the mutagenicity of the soil slightly.     

Emission of organic compounds by combustion of waste plastics involving vinyl chloride polymer

Organic compounds emitted from combustion of waste plastics involving vinyl chloride polymer were investigated in an actual waste incinerator. The amounts of volatile aliphatic hydrocarbons and volatile chlorinated organic compounds decreased when the secondary combustion temperature was controlled over 900°C. On the other hand, the amounts of some aromatic hydrocarbons increased with a rise of the secondary combustion temperature.     

Effects of copper chloride on formation of polychlorinated dibenzo-p-dioxins in model waste incineration

Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl₂ · 2H₂O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.     

Development of a new hydrocarbon index for oil-in-water

A new robust method for determination of hydrocarbons in water without use of Freon^™ or other halogenated solvents has been validated and subjected to an interlaboratory exercise. The method is based on extraction with a light hydrocarbon (boiling point in the 39–69°C range), followed by cleanup for removal of polar components and detection by gas chromatography (GC) with flame ionisation (FID) detection. The performance characteristics of the method are comparable with that of the previous Freon-IR method with recoveries in the 60–80% range and reproducibility (between laboratory variations) of about 30%.

A screening method for hydrocarbons in the range 5 ppm and above based on infrared spectroscopy (IR), and a promising method for detection of low levels based on solid phase extraction (SPE) has been tested and validated.     

Experimental study on the thermal oxidation of 2-chlorophenol in air over the temperature range 450-900 degrees C

The thermal oxidation of 2-chlorophenol (2-CP) in air was investigated using a perfectly stirred reactor at 1 atm over the temperature range 450–900 °C. The relative concentration of 2-CP was 1000 ppmV (equivalence ratio Φ = 0.03). About fifty organic products were identified as trace species. The concentration profiles of 2-CP, carbon oxides as well as those of seventeen major organic intermediates and six non-to-lower chlorinated dioxins and furans were presented as a function of temperature for a residence time of 2 s. The most abundant intermediate products were carbon monoxide, 2 H-pyran-2-one, chlorobenzene, 4-cyclopenten-1,3-dione, phenol, benzofuran, 2-chlorohydroquinone and 2-indanone. These concentration profiles have revealed that temperatures of at least 900 °C were needed to completely oxidize 2-CP, CO and all other organic byproducts to carbon dioxide. Reaction pathways accounting for the formation of most observed products are proposed.     

Formation of chloroarenes upon gas-phase pyrolysis and slow combustion of benzene-HCl mixtures

Pyrolysis (800–900°C, ca. 5 s) of benzene/HC1 mixtures leads to chlorobenzene (1) even in a reducing environment of H₂ and/or CH₄. With added oxygen, 1 is formed even at 550°C; such slow combustions also yield chlorinated phenols and dibenzofurans.     

Concentrations and fluxes of organic compounds in the atmosphere of the Swedish west coast

Measurements of organic compounds in air and deposition have been carried out in parallel on the Swedish west coast. In this investigation the importance of long-range transport for the occurrence of organic compounds in deposition has been studied. Air samples were collected using a high volume sampler (HVS) and the deposition was sampled on a 1 m² Teflon-coated horizontal surface with runoff for the precipitation to an adsorbent. The samples were analyzed in order to identify and quantify different semivolatile compounds such as PAH and petrogenic hydrocarbons and chlorinated compounds such as PCB, HCH and HCB. Qualitative differences between the content of organic compounds in air and deposition during periods with varying levels of air pollution and different meteorological conditions have been studied and a comparison with other air pollutants, such as soot, has been carried out. The results of the measurements show that deposition of PAH and other hydrocarbons takes place continuously but the greatest amounts are measured in the deposition in connection with episodes together with heavy precipitation. The highest concentrations of PCB and HCH in the air were obtained during a warm dry period in May and the greatest amounts were deposited in a period in May with heavy precipitation.     

PCBs and chlorinated hydrocarbon pesticides in Antarctic atmosphere and hydrosphere

PCBs and chlorinated hydrocarbon pesticides such as DDTs and HCHs (BHCs) were measured in air, water, ice and snow samples collected around the Japanese research stations in Antarctica and adjacent oceans during December 1980 to March 1982. The atmospheric concentrations of chlorinated hydrocarbons decreased in the transport process from northern lands to Antarctica, but the compositions of PCBs, DDT compounds and HCH isomers were relatively uniform throughout this process. Regional and seasonal variations were found in aerial concentrations of these pollutants at Syowa Station and adjacent seas in Antarctica. Chlorinated hydrocarbons were also detected in snow, ice, lake water and sea water samples, in which rather high concentrations were found in snow and ice samples. This suggests that snow and ice serve as media of supply of these pollutants into Antarctic marine environment. Most interestingly, the concentrations of DDTs and higher chlorinated biphenyls were much lower in sea water under fast ice than in that from outer margin of pack ice. This indicates that the active removal of these pollutants is occurred in the sea under fast ice, and that is strongly associated with high primary productivity. It is, therefore, presumed that the concentrations of PCBs and DDTs in marine organisms living under fast ice in Antarctica could be lower than those in other oceans.     

Decomposition of chlorinated dioxins, odourous compounds and NOx from MSW incineraton plant by oxidizing catalyst

An experiment was carried out to decompose chlorinated dioxins (PCDDs, PCDFs) Chlorobenzenes, NOx and odourous compounds (H₂S, CH₄S, C₂H₆S₂, C₈H₈, C₂H₆S, C₂H₄O, NH₃) simultaneously using a catalyst in the MSW incineration plant. The experiments were conducted at temperatures from 200°C to 400°C and from 3000h⁻¹ to 6000h⁻¹ at space velocity. A catalyst containing V₂O₅ and WO₃ on the basis of TiO₂ is used, an oxidizing catalyst of the honeycomb type. The average decomposition efficiencis were 95%, 98%, 92% for PCDDs(48CDDs), PCDFs(48CDFs) and Chlorobenzenes(36CLBs) at a reaction temperature of 350°C and a space velocity of 3000h⁻¹, more than 90% for NOx at a reactiont temperature of 300°C and more than 80% for odourous compounds at the reaction temperature of 300°C and a space velocity of 6000h⁻¹. All those compounds were decomposed successfully with increasing contact time and surface. The rate-determing step was the chemical reaction of catalyst surface.     

Dechlorination of chlorinated hydrocarbons by bimetallic Ni/Fe immobilized on polyethylene glycol-grafted microfiltration membranes under anoxic conditions

In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE > PCE > CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol⁻¹, showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.     

Formation characteristics of PCDD and PCDF during pyrolysis processes

In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions – industrial light shredder (ILS) and refrigerators (REF) – both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430°C and 470°C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T₄CDF and P₅CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.     

污染土壤及地下水修复的PRB技术及展望

PRB技术是一类就地修复污染土壤及地下水的新型技术 ,主要由注入井、浸提井和监测井3部分所组成。污染地区的水文地质学研究 ,是实施该技术的关键 ;化学活性物质的筛选、注入的部位、浓度、速率以及是否均匀分布 ,是该技术是否有效的关键要素。胶态零价铁PRB技术 ,被证明是一项修复由卤代烃、卤代芳烃和有机氯农药以及一些有毒金属 (如铬、硒、铀、砷和锝等 )引起的土壤及地下水污染的有效技术。尽管这些技术存在一定的弊病 ,但与传统的处理方法相比 ,其技术上的优势是十分明显的。可以预料 ,这一技术在我国有良好的应用前景     

Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

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.     

Thermal behavior of PCDD/PCDF in fly ash from municipal incinerators

The effect of thermal treatment of fly ash on the behaviour of PCDD/PCDF was studied in the range between 120 and 600° C. Annealing at 300° C (2 hrs) resulted in an increase of PCDD/PCDF concentration by a factor of 10 to 15. At 600° C degradation to concentrations below 0.1 ng/g is observed.     

The leachability of carbon-14-labelled 3,4-benzopyrene from coal ash into aqueous systems

The leachability of polycyclic aromatic hydrocarbons from coal ash into aqueous systems was studied. Carbon-14-labeled 3,4-Benzopyrene (BaP) was deposited on coal fly ash by adsorption from the liquid phase in quantities of about 10 μg/g ash. After a thermal treatment in air at 120 °C for 2 hours the desorption of BaP was measured using aqueous solutions of acetone and methanol as extractants and liquid scintillation counting as detection method. In all cases the ¹⁴C-recovery was incomplete. Using water as extractant, ¹⁴C-recoveries of about 1 % were found. In the presence of a non-ionic surface active agent (Tween 80) the ¹⁴C-recovery was enhanced significantly. For these reasons further experiments under realistic waste disposal conditions are necessary.     

Henry's law constants of chlorinated solvents at elevated temperatures

Henry’s law constants for 12 chlorinated volatile organic compounds (CVOCs) were measured as a function of temperature ranging from 8 to 93 °C, using the modified equilibrium partitioning in closed system (EPICS) method. The chlorinated compounds include tetrachloroethylene, trichloroethylene, cis-1,2-dichloroethylene, vinyl chloride, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, chloroethane, carbon tetrachloride, chloroform, dichloromethane, and chloromethane. The variation in Henry’s constants for these compounds as a function of temperature ranged from around 3-fold (chloroethane) to 30-fold (1,2-dichloroethane). Aqueous solubilities of the pure compounds were measured over the temperature range of 8-75 °C. The temperature dependence of Henry’s constant was predicted using the ratio of pure vapor pressure to aqueous solubility, both of which are functions of temperature. The calculated Henry’s constants are in a reasonable agreement with the measured results. With the improved data on Henry’s law constants at high temperatures measured in this study, it will be possible to more accurately model subsurface remediation processes that operate near the boiling point of water.     

Polychlorinated biphenyls (PCBs) in indoor air and in serum among older residents of upper Hudson River communities

A study was conducted to evaluate the association between PCBs in residential indoor air and in the serum of older, long time residents of three upper Hudson River communities. Samples of indoor air and of serum were collected from 170 persons 55 to 74 years of age, and analyzed for PCBs using glass capillary gas chromatography. After adjusting for age, BMI, cigarette smoking, and Hudson River fish consumption with multiple linear regression analysis, the results indicated statistically significant associations between concentrations in indoor air and serum for PCB-28, a lightly chlorinated congener common in air that accumulates in serum, and PCB-105. Duration of exposure was an important factor, since among persons who had lived in their home for 39 years or more, 11 of the 12 most commonly detected congeners were significantly correlated, as was their sum (∑ PCB). Significant associations between indoor air and serum PCB concentrations also were more likely when collected in cooler months and if the two samples were collected within 20 d of each other. The study is among the first to indicate that PCB concentrations characteristic of residential indoor air are associated with a detectable increase in body burden.     

Reduced breeding success of Cormorants (Phalacrocorax carbo sinensis) in relation to persistent organochlorine pollution of aquatic habitats in The Netherlands

Cormorants (Phalacrocorax carbo sinensis) breeding in the heavily contaminated sedimentation area of the rivers Rhine and Meuse have a severely reduced breeding success as compared to several other Dutch colonies. A detailed analysis of reproductive performance in combination with chemical analysis of eggs and food from colonies in differently contaminated aquatic habitats is presented. The differences in breeding success between colonies are caused mainly in the egg-stage of breeding. Eggshell thinning and increased embryonic mortality cause the differences in hatching success. The observed effects seem to be related to chlorinated hydrocarbons. Significant correlations are found for concentrations of DDE with eggshell thinning and for concentrations of PCBs with hatching and breeding success. The correlations between concentrations of chlorinated hydrocarbons in eggs and biological effects measured in the field are established both on colony and individual clutch level.