PCDD/Fs in ambient air in north-east Italy: The role of a MSWI inside an industrial area

The stack gases of a municipal solid waste incinerator (MSWI), and ambient air were sampled in four locations around the plant for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). The sampling area was close to an industrial area near Trieste, in north-east Italy. The purpose of the study was to estimate the impact of the MSWI emissions and to distinguish the contribution of these emissions from other potential emission sources in the industrial area.PCDD/F atmospheric concentrations were similar to those generally detected in urban–rural areas with one location about 2–3 times more contaminated than the others. Since the most contaminated location was inside the industrial area but upwind of the MSWI, principal component analysis (PCA) was used to establish whether other sources were the cause. This analysis clearly showed that a local steel plant’s emission was the main source of PCDDs/Fs in ambient air. This study highlights the usefulness of multivariate data analysis such as PCA to identify, among different potential emission sources, the one really responsible for the contamination.     

垃圾焚烧过程中二恶英污染控制技术

本文对垃圾焚烧过程中如何控制二恶英的产生及焚烧后的残渣、飞灰的处理技术进行了综合分析,并对适合我国国情的垃圾焚烧技术作了初步探讨。     

Atmospheric deposition of PCDD/Fs measured via automated and traditional samplers in Northern Taiwan

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the atmosphere are bound to particles which are suspended in the atmosphere, and eventually settle on soil, vegetation, water bodies or other receptors in the environment. Monitoring atmospheric deposition fluxes (dry/wet) is important in tracing the environmental fate and behavior of PCDD/Fs. PCDD/F depositions were collected via an automated PCDD/F ambient sampler and traditional cylindrical vessels, respectively, from April 2007 to February 2008. The automated PCDD/F ambient sampler used in this study can prevent both re-suspension and photo degradation of the PCDD/Fs collected and effectively separates the PCDD/F samples into dry and wet contributions. The results indicated that the ambient PCDD/F concentrations collected using the PS-1 sampler ranged from 0.02 pg I-TEQ/m³ to 0.16 pg I-TEQ/m³ in Northern Taiwan. The results also indicated that the PCDD/F deposition flux collected using the automated PCDD/F sampler (17.5 pg I-TEQ/m² d to 25.8 pg I-TEQ/m² d) was significantly higher than that sampled with the cylindrical vessels (2.0 pg I-TEQ/m² d to 9.9 pg I-TEQ/m² d). The difference was attributed to the fact that part of the PCDD/F depositions collected using the traditional cylindrical vessels had undergone photo degradation and evaporation. In addition, the wet deposition flux of PCDD/Fs (39.4 pg I-TEQ/m² rainy day to 228 pg I-TEQ/m² rainy day) observed in this study was significantly higher than the dry deposition flux (12.3 pg I-TEQ/m² sunny day to 16.7 pg I-TEQ/m² sunny day). These results demonstrated that wet deposition is the major PCDD/F removal mechanism in the atmosphere.     

Fish products available in Polish market – Assessment of the nutritive value and human exposure to dioxins and other contaminants

Chemical analyses were performed on one hundred and twenty of the most popular varieties of fish products (smoked fish, salted fish, and marinated fish) of the fish market in Poland. The contents of the nutritive substances of fish products (protein, micro- and macronutrients, vitamins A₁, D₃, E, and fatty acids) and the chosen contaminant (toxic metals – mercury, cadmium, lead, arsenic; dioxin/furans – PCDDFs; dioxin-like PCB – dl-PCBs; seven congeners of polybrominated diphenyl ethers – PBDEs; organochlorine pesticides – ΣDDT, HCB, ΣHCH and marker polychlorinated biphenyls – PCB₇) levels were determined. It was confirmed that fish products are a good source of digestible proteins, iodine, selenium, and vitamin D₃. The fundamental nutritive benefit of processed fish lies in its highly beneficial fatty acid composition, which is what imparts them healthy nutritive qualities. The high content of long-chain polyunsaturated fatty acids (LC-PUFAs), which is not noted in other food products, is particularly important.The majority of contaminants studied were present in low levels. The possible threats, particularly in the case of pregnant/nursing women and young children, can pose the levels of dioxin/furans (PCDD/Fs) and dioxin-like (dl-PCBs) in smoked Baltic salmon and smoked sprat, elevated in a relation to particular requirements concerning the content of sum of PCDD/Fs and dl-PCBs in fish (8 pg WHO-TEQ g⁻¹).The health benefits and risks stemming from consumption of fish products were determined according to the Provisional Tolerable Weekly Intake (PTWI) for chosen contaminants (Cd, Hg, As, PCDD/Fs + dl-PCB) and the quantity of ingredients that render a fish diet healthy based on data from the EFSA Journal [EFSA (European Food Safety Authority), 2005. Opinion of the scientific panel on contaminants in the food chain on a request from the European Parliament related to the safety assessment of wild and farmed fish. EFSA J. 236, 1–118]. In regard of high content of LC-PUFAa and other nutritive ingredients, fish products available in Polish market may be considered as healthy food.However, many authors point at contaminants (methylmercury, PCDD/Fs) occurring in fish and fish products as on potential health problem, and emphasize that the amount of that hazardous substances should be limited in human diet.     

Serum concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans among former New Zealand trichlorophenol workers

This study examined serum levels of 2,3,7,8-substituted chlorinated dioxins and furans, and 15 PCBs for 346 New Zealand employees who worked at a site that manufactured 2,4,5-trichlorophenol (TCP) and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T). Participants with potential TCP or 2,4,5-T exposures had mean lipid-adjusted 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) levels of 9.9 ng kg⁻¹ lipid compared to 4.9 ng kg⁻¹ for workers with no exposure at the site. Among exposed workers, we found evidence of differences in 2,3,7,8-TCDD levels by department and duties. Workers involved in an accidental release had the highest mean 2,3,7,8-TCDD levels, 37.9 ng kg⁻¹, followed by workers in the trichlorophenol plant, 23.4 ng kg⁻¹. Workers with potential intermittent exposures to 2,3,7,8-TCDD in construction, maintenance, mechanics, and transport had 2,3,7,8-TCDD levels above New Zealand background levels of 3.9 ng kg⁻¹, indicating workplace exposures. Among participants with work history indicating no 2,3,7,8-TCDD exposures, we observed some individuals with 2,3,7,8-TCDD levels above background levels. However, in most cases, these workers reported workplace exposures not recorded on their work histories or held other jobs with the potential for 2,3,7,8-TCDD exposures outside the plant. All other dioxin, furan, and PCB levels were similar among the exposed and unexposed workers.     

Evaluation of PCDD/F oxidation catalysts: confronting studies on model molecules with tests on PCDD/F-containing gas stream

Titania supported vanadium oxide is a renowned catalyst for the abatement of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from gas effluents. To develop more active formulations, researchers mainly rely on lab-scale experiments on “PCDD/Fs-mimicking substances”, like (chloro)-benzene. Using such model compounds is convenient whereas handling PCDD/Fs in the laboratory is potentially hazardous and complicated. Recent studies, however, challenged some foremost conclusions of model compound based studies, starting from the observation that different model compounds gave contrasted results. Thus the present work aims at confronting some of these dubious conclusions with direct experimental tests on PCDD/Fs. One reference V₂O₅/TiO₂ catalyst and three modified formulations (V₂O₅/TiO₂-SO₄, V₂O₅-MoO₃/TiO₂, and V₂O₅-WO₃/TiO₂) have been evaluated. A dedicated apparatus was used which allows safe and reliable tests on a mixture of PCDD/Fs congeners. Some of the previously proposed catalyst improvement strategies actually prove to be disadvantageous in the removal of PCDD/Fs. In particular, MoO₃- and WO₃-modified catalysts were significantly less active than the reference catalyst. These observations show that conclusions from model compound based studies must be drawn with care and should ideally be confronted with tests on the actual target pollutants.     

Comprehensive two-dimensional gas chromatography time of flight mass spectrometry (GC×GC-TOFMS) for environmental forensic investigations in developing countries

The disposal and dumping of toxic waste is a matter of growing concern in developing countries, including South Africa. Frequently these countries do not possess access to gas chromatography-high resolution mass spectrometry (GC-HRMS) for the determination of persistent organic pollutants (POPs). This publication describes an alternative approach to the investigation of toxic waste using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS). The technology permits both comprehensive screening of toxic samples for numerous classes of organic pollutants and also quantitative analysis for the individual compounds. This paper describes the use of this technique by analysing samples obtained from a hazardous waste treatment facility in South Africa. After sampling and extraction the samples were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and four dioxin-like non-ortho substituted polychlorinated biphenyls (PCBs). The quantitative values, as well as detection limits, obtained using the GC × GC-TOFMS methodology compares well with those obtained using GC-HRMS; the accepted benchmark technology for this analysis. Although GC × GC-TOFMS is not a target compound analytical technique (as is GC-HRMS), it is possible to obtain information on numerous other classes of organic pollutants present in the samples in one analytical run. This is not possible with GC-HRMS. Several different column combinations have been investigated for handling very complex waste samples and suggestions are presented for the most suitable combination.     

Deposition fluxes of PCDD/Fs in a reservoir system in northern Taiwan

In this study, polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations and depositions in ambient air, water column and sediment were measured at a coupled reservoir-watershed system in northern Taiwan. The atmospheric PCDD/F concentration measured in the vicinity of the reservoir ranged from 4.9 to 39 fg I-TEQ m⁻³ and the Asian dust storm in February accounted for the peak value, which corresponded to a total suspended particle concentration of 128 μg m⁻³. The atmospheric PCDD/F deposition ranged from 1.4 to 19 pg I-TEQ m⁻² d⁻¹, with higher deposition occurring during winter and spring (long-range transport events). During summer, when atmospheric deposition is lower, consecutive tropical cyclones (typhoons) bring heavy rainfall that enhances soil erosion and creates turbidity-driven intermediate flow. This results in significantly higher PCDD/F deposition in water column of the reservoir at 70 m water depth (179 pg I-TEQ m⁻² d⁻¹) than at 20 m (21 pg I-TEQ m⁻² d⁻¹) during typhoon event. The accumulation rate of PCDD/Fs (9.1 ng I-TEQ m⁻² y⁻¹) in the reservoir sediments (depth: 0-2 cm) was consistent with PCDD/F deposition obtained from water column (6.1 and 8.3 ng I-TEQ m⁻² y⁻¹); however, it is significantly higher when compared to the atmospheric deposition (2.0 ng I-TEQ m⁻² y⁻¹). Based on the mass balance between the measurements of atmospheric deposition and sinking particles in water column, around 54-74% of PCDD/F inputs into the reservoir were contributed by the catchment erosion during normal period. However, the PCDD/F input contributed by the enhanced catchment erosion significantly increased to 90% during intensive typhoon events.     

大体积进样与分流/不分流进样气相色谱/质谱测定二噁英的对比

选取传统分流／不分流进样技术与大体积进样技术,结合气相色谱／质谱测定条件,对二者的测定效果和不同进样量的色谱图进行了分析对比。结果表明,使用大体积的进样测定二噁英,在不影响色谱分离度的同时可以大幅度提高仪器分析的灵敏度,可以代替传统分流／不分流进样。     

Verification results of jet resonance-enhanced multiphoton ionization as a real-time PCDD/F emission monitor

A jet resonance-enhanced multiphoton ionization (REMPI) monitor was tested on a hazardous-waste-fired boiler for its ability to determine concentrations of polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs). Jet REMPI is a real-time instrument capable of highly selective and sensitive (from parts per billion to parts per trillion) detection of a broad range of aromatic compounds, including a number of air toxic compounds. The PCDD/F toxic equivalency (TEQ) value was derived from a predetermined correlation (R ² = 0.74) with monochlorobenzene (MClBz). This relationship was applied to nine subsequent jet REMPI on-line measurements of MClBz and parallel, standard extractive sampling for PCDD/F TEQ. For high waste-firing rates, with a range of PCDD/F TEQ values between 3.9 and 6.0 ng TEQ/m³, the TEQ values predicted by jet REMPI had a relative difference of 26% with the standard EPA Method 23 results. At low waste-firing rates (0.9–1.6 ng TEQ/m³), the relative difference increased to 219%. This limited testing shows that jet REMPI has promise as an on-line diagnostic monitor, providing feedback on the effects on PCDD/F emissions of operating parameter changes such as fuel feed interruptions or air pollution control failures.