Gas phase equilibria for dibenzo‐p‐dioxin,dibenzo‐p‐furan and biphenyl in the C‐H‐O system

The gas phase equilibrium calculation for the C‐H‐O system at atmospheric pressure and temperature from 773 to 1773 K at intervals of 250 K was performed to understand the generation and decomposition behavior of dibenzo‐p‐dioxin (DD), dibenzo‐p‐furan (DF) and biphenyl (BP) in relation to the existing oxygen potential. It is possible to categorize these results into three regions from the viewpoint of this potential: region (A), region (B) and region (C) are that of the higher, modest and lower oxygen potential, respectively. In region (A), the equilibrium amounts of DD, DF and BP are nearly zero. In region (B), they increase once and then decrease with rise in temperature. In the most characteristic region (C), they increase uniformly with rise in temperature.     

Catalytic decomposition of polychlorinated biphenyls (PCBs)

In this study, polychlorinated biphenyls (PCBs) were decomposed by low‐temperature heat treatment with metallic catalyst, and with metallic catalyst and a hydrogen source. Of the catalysts used, iron (Fe) was the most active catalyst for the decomposition of PCBs, and the decomposition was due to dechlorination. The addition of hydrogen sources accelerated the decomposition of PCBs in the presence of catalyst. Surface analysis of the catalyst using X‐ray photoelectron spectroscopy (XPS) suggested that the emitted chlorine was presumed to form metal chloride. The reactions of each homolog can be expressed by a successive first‐order reaction model. This means that a substituted chlorine is successively detached during this reaction. The overall decomposition rate in this reaction system was controlled by that of the lower chlorinated homologs. The decomposition rates with Fe and NaBH₄ for the lower chlorinated homologs were about 10 times as fast as the rates with only Fe.     

Chlorinated dioxins and furans as trace products of combustion: Some theoretical aspects

Recent advances in combustion theories are reviewed, especially the detailed mechanisms of hydrocarbon oxidation, formation of polynuclear aromatic hydrocarbon from aliphatic fuels, and the behavior of halogens in flames. Experimental observations of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) formation in combustion of aliphatic fuels such as acetylene, ethylene and methane in the presence of hydrogen chloride are summarized. Then, from combustion chemistry considerations a reaction mechanism for T₄CDD/F formation in the CH₄/ HCl/O₂ system is developed. This mechanism consists of elementary reactions describing the main oxidation steps, formation of chlorinated C₁‐ to C₄‐species, formation of the first aromatic ring, and T₄CDD/F formation. The mechanism may be extended to other hydrocarbon fuels and higher PCDD/F homologues. Possible relevance of the mechanism to the “trace chemistries of fire hypothesis”; is discussed.     

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/Fs) in dated environmental samples,and their connection to known sources

This article investigates available environmental data from measurements of the everywhere present contaminants polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) in dated trends in sediment, soil and herbage from locales in Europe and North America. The PCDD/F data are examined in relation to potential major PCDD/F sources based on volume: wood and coal, example of natural combustion; pentachlorophenol (PnCP), example of chlorinated aro‐matics; and polyvinyl chloride (PVC) pyrolysis, example of chlorinated aliphatic. Collected PCDD/F data of congener sums and 2, 3, 7, 8‐substituted congener (PCDD/F profiles) have been investigated with multivariate methods: principal component analysis (PCA) and partial least squares projection to latent structures model (PLS). The results show that PCDD/F data from 12 locales can be separated in one to three independent profiles. Normally one profile is related to the PCDD/F found in PnCP and another to combustion. A subtype of the ‘PnCP’ and ‘combustion’ profiles indicates PCDD/F contributions from PVC‐related combustions. The environmental profiles exhibit some differences from the suggested sources. The relatively unprotected PCDD/F related to PnCP is suggested to have passed photolytic and/or thermal dechlorinations. Lower‐chlorinated congeners in environmental profiles related to combustion appear to have been influenced by environmental distribution processes. PCDD/F data before industrial production of chlorinated organics have only limited similarity to PCDD/F in technical PnCP profiles; an average 4.6% of the PCDD/F is related to PnCP. This suggests that PnCP similarity in recent deposition profiles cannot be a result of environmental transformation. The average proportion of PnCP‐related PCDD/F profile in recent depositions is 35% with North America high (average 57%) and Europe low (average 24%).     

Soxhlet extraction parameters’ influence on the recovery of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) from a sediment,and artifact formation of PCDD

Soxhlet extraction of polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/F) from sediment was studied using a designed experimental set‐up. Three variables were studied: three solvent combinations n‐hexane/methanol, dichloromethane/acetone and toluene/methanol; two extraction times, 8 and 16 h, and addition of bulk substances (sodium carbonate). The extraction efficiency was almost identical in all extractions, with the exception of extraction where toluene/ methanol was combined with sodium carbonate. In these samples a major effect was observed, due to formation of Hx‐, Hp‐ and OCDD isomers. Composition of formed PCDD was similar to PCDD isomers found in pentachlorophenol products.     

Hydrogen sulfide removal by iron containing activated carbon

Activated carbon modified by impregnation with iron (III) chloride solution (Fe‐ACs) were studied to try to raise their adsorption capacity for hydrogen sulfide, a malodorous substance.

The surface area and pore volume of activated carbon were decreased by impregnation, but the amount of hydrogen sulfide adsorbed onto Fe‐AC was larger than that onto raw activated carbon (R‐AC). In particular, a large increase of the amount adsorbed onto Fe‐AC was noted at low equilibrium pressure. It was assumed that the increase of amount of hydrogen sulfide adsorbed onto Fe‐AC was due to the chemical interaction between iron (III) chloride on the pores in addition to the physical adsorption onto pores of activated carbon. Fe‐AC shows a high selectivity for hydrogen sulfide.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part IV†: Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations

The pyrolysis and chlorination of petroleum coke in a NaCl‐KCl melt results in the production of CCl₄ and C₆Cl₆. Polychlorinated dibenzo‐p‐dioxins (PCDDs) are produced from the air oxidation and chlorination of coal using HCl or Cl₂. Smoking of tobacco containing ³⁶Cl^e provides CH₃ ³⁶Cl.

At 350°C, the rateof aromatization of 1,3‐cyclohexadiene is negligible as compared to that of 1,4‐cyclohexadiene. The aromatization of the latter diene proceeds through the molecular elimination of hydrogen; while that of 1,3‐cyclohexadiene expecially at higher pressure (10–90 Torr) and at 362–421 °C involves free radical chain mechanism.     

Abstracts to forthcoming papers

Soil and sediments collected at a former chlor‐alkali plant in coastal Georgia (United States), revealed the presence of PCDF concentrations as great as 82.3 ng/g, dry wt. PCDF congener profile in soil was typical of “chlorine pattern”; with elevated proportions of OCDF and HpCDF. Concentrations of PCDFs declined gradually by 44‐fold at a distance of about 500 m along the contamination gradient. Of PCDDs/DFs, 2,3,7,8‐substituted PCDFs accounted for 94–98% of the TCDD‐like activity, which declined by 25‐fold, corresponding with the reduction of total PCDF concentrations. Concentrations of PCDDs in sediments were as great as 17 ng/g, with an elevated contribution from OCDD. The magnitude of decline in PCDD concentrations with distance from the source was less pronounced than that for PCDFs. PBDDs and PBDFs were not detected. Polybrominated biphenyl ether (PBBE) and monobromo‐heptachloro dibenzo‐p‐dioxins and dibenzofurans (PXDDs/DFs) were found, though, at low concentrations. Their spatial distribution was similar to those of PCDDs.     

Comparative study on the efficiency and environmental impact of two methods of utilizing polyvinyl chloride waste based on life cycle assessments

Two processes of utilizing polyvinyl chloride （PVC） waste, an incineration process and a vacuum pyrolysis process, for energy conversion were compared to determine their efficiency and environmental perfor- mance. We carried out a life cycle assessment with each of the two processes to evaluate their environmental impact and defined the goals and limits of our remit. As well, we established an inventory of PVC waste from incineration and vacuum pyrolysis based on process analysis, data collection and calculations. The results show that electrical power output per unit mass of PVC waste in the incineration process was twice as high as that of the vacuum pyrolysis process. Incineration had a larger total environmental impact potential than vacuum pyrolysis. The total environmental impact potential of PVC waste from incineration was three times higher than that from vacuum pyrolysis. Incineration of PVC disposed 300 ng. 100 kgI of dioxins and vacuum pyrolysis 98.19 ng- 100 kgI of dioxins. As well, we analyzed the data for their uncertainty with results quantified in terms of three uncertainties： basic uncertainty, additional uncertainty, and computational uncertainty. The coefficients of variation of the data were less than 25% and the quality of the inventory data was acceptable with low uncertainty. Both PVC waste disposal processes were of similar quality and their results comparable. The results of our life cycle impact assessment （LCIA） showed considerable reliability of our methodology. Overall, the vacuum pyrolysis process has a number advantages and greater potential for development of PVC disposal than the incineration process.     

Dioxins: Sources of environmental load and human exposure

Polychlorinated dibenzo‐p‐dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) represent a class of tricylic, almost planar, aromatic ethers with 1 to 8 chlorine atoms. Congeners with substituents in the positions 2, 3, 7, and 8 are of special concern due to their toxicity, stability, and persistence. These compounds have been identified in almost all environmental compartments and humans.

Dioxins are a potent carcinogen for animals and—at the moment—considered a probable carcinogen for humans. Actual toxicological risk assessment for humans are based on 2,3,7,8‐Cl4DD carcinogenicity studies on rodents. Tumorigenic effects were found for 2 strains of rats and 2 strains of mice. All dioxins and furans elicit common toxic and biological responses, starting with a specific binding to a protein receptor, but existing epidemiologic data do not provide definitive data on human health effects.

Toxicity equivalency factors (TEFs) have been developed by several agencies as a provisional method of risk assessment for complex mixtures of PCDD/PCDF.

Dioxins have never been produced intentionally and have never served any useful purpose. They are formed in trace amounts as by‐products in industrial processes; for instance within the chemical industry, of the pulp and paper industry, metallurgical processes, processes for reactivation of granular carbon, dry cleaning, and the manufacture of flame‐retarded plastics.

The main pathway for dioxins to enter the environment is via combustion processes. Incineration is of special importance since PCDD/PCDF are directly released to the atmosphere from either stationary sources, such as municipal, hazardous and hospital waste incinerators, the combustion of sewage sludge, and scrap metal recycling, or diffuse sources, e.g. automobile exhausts, private home heating with fossil fuels, forest fires, and cigarette smoking. Furthermore, fires with PCB and PVC have additionally contributed to the total dioxin load. The emission gases can undergo long‐range transport, so that dioxins have been found even in remote areas.

Besides the two primary sources (industrial processes and combustion processes) the release of dioxins from contaminated areas and waste dumps via the leachate and the application of sewage sludge for fertilization represents a third source of PCDD/PCDF.

After more than 10 years of dioxin research the most important sources of PCDD/PCDF have been identified and analytical methods have been developed for their quantification in trace levels and in complex matrices.

Various efforts have been undertaken to reduce the emission of dioxins: for example, optimization of combustion processes for municipal waste incineration, use of unleaded gasoline, ban of chemicals, such as polychlorinated biphenyls (PCBs) and pentachlorophenol (PCP). More detail is provided in the pulp and paper section where changes have been initiated to significantly reduce the sources of PCDD/PCDF.

However, relatively little is known about transport and transformation processes, so only rough estimates can be made. Photodegradation has been found to be the primary process for 2,3,7,8‐Cl4DD breakdown. A half‐life of 3–4 days has been estimated for photochemical degradation under oxidative conditions. Field studies on the fate of 2,3,7,8‐Cl4DD in soil gave a half‐life of 9.1 (Seveso) and 12 years (under special conditions: sand, erosion), respectively. Biodegradation seems to be negligible. Transfer factors soil‐plants for PCDD/PCDF have been determined—with a high degree of uncertainty—to be less than 0.1.

Human exposure primarily occurs via ingestion whereas inhalation is a minor pathway. Dermal absorption can be neglected although skin contact to polluted surfaces may occur. Due to the lipophilicity of PCDD/PCDF and their potential for accumulation, foods such as meat and especially dairy products contribute most to the dioxin body burden of humans.

Both national agencies and international organizations have recognized the significance of this problem and as a result have initiated regulations, recommendations and research programmes (1) to understand where and how PCDD/PCDF are formed, (2) to reduce their impact on the environment and to humans, and (3) to start remedial action on contaminated areas.     

Predicting the transportation tendency and potential reservoirs of dioxins by compartment distribution coefficient

We assessed the transportation tendency of dioxins and predict locations at high risk for dioxin pollution. A new parameter, the compartment distribution coefficient D_C, was created to account for the tendency of dioxins to preferentially accumulate in particular compartments. It was obtained by a model using levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in four countries: Japan, the United States, the United Kingdom, and Australia. The comparison with the temporal and spatial variation of D_C indicated whether the location release or long-range transportation caused the changes. This study showed that PCDD/Fs have the greatest tendency to remain in soil among studied media. A higher D_C value in Australia may indicate that this location is a potential future reservoir source of dioxins.     

Instrument tuning for trace analysis of dioxins and furans for the vg 70s/se gas chromatography/mass spectrometry system using electron impact mode

We present the salient characteristics of tuning procedures that have evolved from our 3 years of experience while producing large amounts of data of the highest quality. Our laboratory routinely analyzes 2,3,7,8‐substituted dioxins and furans at parts per quadrillion levels in 50–100 g of human serum samples using the VG 70S/SE stand‐alone gas chromatography/mass spectrometry (GC/MS) system at 10000 resolution (defined by 5% overlap) in the selected ion recording mode. Trace measurement of dioxins and furans in human biological matrices—for example, whole blood, serum, or adipose tissue‐requires reproducible instrument tuning within day as well as among days for quality results. Additionally, instument‐tuning procedures among operators must be reproducible to minimize operator bias because periodically different operators are used. Instrument tuning is highly subjective and argumentive; therefore, to minimize the ambiguity within our laboratory, we have standardized our technique to reproducibly tune the GC/MS system.     

Study on polychlorinated dibenzo‐p‐dioxins and dibenzofurans in rivers and estuaries in Osaka Bay in Japan

In order to search the source of polychlorinated dibenzo‐p‐dioxins (PCDDs) and dibenzofurans (PCDFs) in blue mussel in Osaka bay, sediments from Osaka bay and from rivers running near an urban municipal incinerator were analysed for PCDDs, PCDFs and PCBs. The river and estuary sediments were all found to be contaminated with PCDDs at average levels of 9.8 and 12ppb on the dry basis, PCDFs of 7.8 and 5.1 ppb, and PCBs of 1600 and 1300ppb, respectively. The two sediments contained similar profiles of specific isomers and congeners of PCDDs and PCDFs with each other. In addition, there was observed positive close correlations between PCDD and PCDF levels in the two specimens as well as fly ash from urban municipal incinerators. These allow the conclusion that the main source of the two chemicals in Osaka bay is fly ash from waste incineration.     

PCDD/DFs and coplanar PCBs in fly ash samples from various types of incinerators in Taiwan

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/DFs) and coplanar polychlorinated biphenyls (Co‐PCBs) were determined in fly ash samples from municipal solid waste (MSW), medical waste (MW), and electricity power plant incinerators in Taiwan. The average concentrations of PCDD/DFs and Co‐PCBs are 7.02 ng‐TEQ/g and 1.06 ng‐TEQ/g, respectively. The contributions to total TEQ are 24% from PCDDs, 64% from PCDFs, and 12% from Co‐PCBs, indicating that PCDFs generate the highest environmental impact and MSW and MW incinerators are potential Co‐PCBs contaminating sources. The levels of PCDD/DFs and Co‐PCBs found in ash samples increase from petroleum‐fired, coal‐fired, large municipal solid waste, small medical waste, to small municipal solid waste incinerators, and are generally lower than those from incinerators built earlier. All fly ash samples analyzed in this study were considered hazardous materials. More research is suggested to establish the relationship between the amounts of PCDD/DFs and Co‐PCBs in fly ash and in flue gas.     

Control of hydrogen sulphide in digestor gas using iron salts

Different dosages of ferrous chloride and ferric chloride were added to digestors separately, and the volumes of methane and hydrogen sulphide contained in the digestor gas (biogas) were monitored. It was noted that the effects of adding of 16, 18 and 32 kg ferrous chloride/ tonne volatile solids, and 16 and 18 kg ferric chloride/tonne volatile solids were similarly effective in controlling the hydrogen sulphide levels.

According to an average amount of undigested sludge (primary sludge mixed with surplus activated sludge) of 41 tonne volatile solids produced each day during the sewage treatment process in Shatin sewage treatment works, and the required dosage of 16 kg ferric chloride/ tonne volatile solids, the amount of iron salts required should be 656 kg/day or 3.3 mg/L for the actual application, based on an average sewage flow of 200,000 m³/day.     

Alignment between values of dryland pastoralists and conservation needs for small mammals

Policies for conservation outside protected areas, such as those designed to address the decline in Australian mammals, will not result in net improvements unless they address barriers to proenvironmental behavior. We used a mixed‐methods approach to explore potential value‐action gaps (disconnects between values and subsequent action) for small mammal conservation behaviors among pastoralists in dryland Australia. Using semistructured surveys and open‐ended interviews (n = 43), we explored values toward small mammals; uptake of a range of current and intended actions that may provide benefit to small mammals; and potential perceived barriers to their uptake. Pastoralists assigned great conservation value to small mammals; over 80% (n = 36) agreed to strongly agreed that small mammals on their property were important. These values did not translate into stated willingness to engage in voluntary cessation of wild‐dog control (r² = 0.187, p = 0.142, n = 43). However, assigning great conservation value to small mammals was strongly related to stated voluntary willingness to engage in the proenvironmental behavior most likely to result in benefits to small mammals: cat and fox control (r² = 0.558, p = 0.000, n = 43). There was no significant difference between stated voluntarily and incentivized willingness to engage in cat and fox control (p = 0.862, n = 43). The high levels of willingness to engage in voluntary cat and fox control highlight a potential entry point for addressing Australia's mammal declines because the engagement of pastoralists in conservation programs targeting cat and fox control is unlikely to be prevented by attitudinal constraints. Qualitative data suggest there is likely a subpopulation of pastoralists who value small mammals but do not wish to engage in formal conservation programs due to relational barriers with potential implementers. A long‐term commitment to engagement with pastoralists by implementers will thus be necessary for conservation success. On‐property cat and fox control programs that build and leverage trust, shared goals, collaboration, and shared learning experiences between stakeholders and that explicitly recognize the complexity of small mammal dynamics and the property‐level ecological knowledge of pastoralists are more likely to gain traction.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part V†: Hypotheses and summary

The hypotheses on the de novo syntheses of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo‐p‐dioxins (PCDDs), based on known literature, are presented. Polychlorinated benzenes and polychlorinated phenols are probably key intermediates.

In the present article, hypotheses that may account for the presence of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs) in the effluents from municipal and industrial incinerators are put forward. These hypotheses are based on the previously surveyed literature (Ref. 203–206) and experimental results on laboratory scale and thermodynamic calculations are considered. The interconnections of various reaction steps are speculative and no technological information was added to account for conditions in real incinerators. Conclusion of the discussions on the related subject matter, presented in the Parts I‐IV (Ref. 203–206), are also described in this paper.     

Cosolvency. I. some non‐hydrogen bonding solutes with non‐hydrogen bonding solvents

The solubility data for a series of non‐hydrogen bonding, monosubstituted benzenes in binary mixtures of water and non‐hydrogen bonding cosolvents is presented. Good correlation between log solubility and fraction cosolvent is obtained, therefore the estimation of solubility in mixed solvents by a log‐linear relationship can be attained. Slight positive or negative deviations from predicted solubility values are seen at high volume fractions of cosolvents. These deviations are attributed to the cosolvent‐water interactions.     

Capacity estimation and preliminary strategy for reducing the release of dioxins in China

As a party of the Stockholm Convention on Persistent Organic Pollutants, China must submit its national implementation plan (NIP) for this convention. The strategy and action plan for reducing the release of dioxins in China are the most important components of the NIP. Three problems are key points for developing such strategy and action plan—what are the key sources for applying the best available technology/best environmental practice (BAT/BEP) to reduce the release of dioxins? How about the capacity for reducing the dioxins release from the key sources? Where are the areas of priority for applying BAT/BEP? This paper shows the efforts towards the solution of these problems. The list of key sources covering about half of the total dioxins release was determined considering four criteria. The capacity of key sources were estimated based on the difference between the emission factor corresponding to the actual situation in 2004 and that corresponding to the scenario that all key sources have been applied BAT/BEP to reduce the dioxins release. The priority analysis using the geographical information system (GIS) tool has revealed that castern provinces should be of high priority in the future reduction activities of dioxins release in China.     

氯代多环芳烃的污染现状及毒性研究进展

氯代多环芳烃(chlorinated polycyclic aromatic hydrocarbons,Cl-PAHs)是一种多环芳烃的氯代衍生物,具有与二噁英相似的毒性效应,并且在各种环境介质中广泛存在。Cl-PAHs已成为一种新型有机污染物,对生态环境和人体健康造成潜在的威胁。本文从Cl-PAHs的来源、污染现状、毒性效应与人体健康风险评价等几个方面对国内外有关Cl-PAHs的研究现状和最新进展进行了系统综述。