Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

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.     

Application of QSARS to predict potential aquatic toxicities of organochlorine pesticides∗

On the basis of physico‐chemical data, such as water solubility and vapour pressure as well as acute toxicity tests we developed an ecotoxicological model for preliminary hazard assessment. By use of the reciprocal product from log H and LC₅₀ we developed a suitable ranking system that allows us to predict potential damage to aquatic organisms through pesticides.     

Potential sources of unintentionally produced PCB,HCB, and PeCBz in China: A preliminary overview

Under the Stockholm Convention on Persistent Organic Pollutants (POPs), China is required not only to reduce polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) but also unintentionally produced polychlorinated biphenyls (PCB), hexachlorobenzene (HCB) and pentachlorobenzene (PeCBz). A baseline of the sources in China that generate these unintentional POPs is needed for both research and regulation purposes. In this paper, we have compiled production data of potential sources in China and assessed them in five-year intervals from 2000 to 2015. Most of these activities experienced changes from rapid growth to slow growth. Measured data for PCB, HCB and PeCBz in samples collected from potential sources in China were reviewed. Most information was associated to thermal processes with high potential of emission, including waste incineration and ferrous and non-ferrous metal production. In addition, high levels of PCB, HCB and PeCBz were found as impurities in a few chlorinated products or as by-products in solvent production, which suggested organochlorine industry might be important sources. Finally, based on the studies reviewed, recommendations for future actions in research and policy as well as a few regulatory issues in China are discussed.

Open image in new window

     

Insight of chemical environmental risk and its management from the vinyl chloride accident

The combustion of vinyl chloride (VC) after the train derailment accident in Ohio, USA in February, 2023 has caused widespread concern around the world. This paper tried to analyze several issues concerning the accident, including the appropriateness of the VC combustion in the emergency response in this accident, the meanings of so-called “controlled combustion”, the potential environmental risks caused by VC and combustion by-products, and follow-up work. In our view, this accident had surely caused environmental and health risks to some extent. Hence, a comprehensive environmental risk assessment is necessary, and then the site with risk should be comprehensively remediated, hazardous waste should be harmlessly treated as soon as possible. Finally, this accident suggests that further efforts should be taken to bridge the gap between chemical safety management and their environmental risk management.