Polychlorinated Dibenzo-p-dioxins And Dibenzofurans Research Articles

Inhibition of PCDD/Fs in a full-scale hazardous waste incinerator by the quench tower coupled with inhibitors injection

The control of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from the flue gas in hazardous waste incinerators (HWIs) is an intractable problem. To figure out the formation mechanism of PCDD/Fs and reduce the emission, a field study was carried out in a full-scale HWI. Ca(OH)2 & (NH4)H2PO4 or CH4N2S & (NH4)H2PO4 were injected into the quench tower, and the detailed inhibition effect on PCDD/Fs formation by the inhibitors coupled with quench tower was studied. Gas and ash samples were collected to analyze PCDD/Fs. XPS, EDS characterization and Principal component analysis were adopted to further analyze the de novo and precursors synthesis. The PCDD/Fs emissions reduced from 0.135 ng I-TEQ/Nm3 to 0.062 or 0.025 ng I-TEQ/Nm3 after the injection of Ca(OH)2 & (NH4)H2PO4 or CH4N2S & (NH4)H2PO4, respectively. The quench tower was found mainly hindering de novo synthesis by reducing reaction time. CP-route was the dominant formation pathway of PCDD/Fs in quench tower ash. Ca(OH)2 & (NH4)H2PO4 effectively inhibit precursors synthesis and reduce proportions of organic chlorine from 4.11% to 2.86%. CH4N2S & (NH4)H2PO4 show good control effects on both de novo and precursors synthesis by reducing chlorine content and inhibiting metal-catalysts. Sulfur-containing inhibitors can cooperate well with the quench tower to inhibit PCDD/Fs formation and will be effective to reduce dioxins formation in high chlorine flue gas. The results pave the way for further industrial application of inhibition to reduce PCDD/Fs emissions in the HWIs flue gas.

Concentrations, congener patterns, and correlations of unintentional persistent organic pollutants in cement kilns co-processing hazardous waste

Emissions from two typical cement kilns co-processing different kind of hazardous waste were analyzed for 143 congeners of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls, polychlorinated naphthalenes, polybrominated dibenzo-p-dioxins and dibenzofurans, and polybrominated diphenyl ethers. The congener distributions in different process stages were investigated. One of the plants co-processed waste chemical reagents from laboratories. The emission factor (TEQ basis) for the plant was 2.09 ng WHO2005 TEQ/t, with the kiln head and the kiln back end contributing 1.18, 0.91 ng WHO2005 TEQ/t, respectively. The other plant co-processed municipal waste incineration fly ash. The emission factor for the plant was 0.12 ng WHO2005 TEQ/t, with the kiln head and the kiln back end contributing 0.022, and 0.10 ng WHO2005 TEQ/t. These results indicate that co-processing of waste containing reagents from laboratories may lead to higher emission levels than co-processing of other types of waste. The congener patterns of persistent organic pollutants (POPs) in ash samples from the humidifier tower were similar to those in samples from the bag filter at the kiln back end. The correlation coefficients of five pollutants between the humidifier and bag filters samples were generally high, which indicated that conditions in those two stages similarly favored the formation of these POPs. Comparison of the concentrations for different process stages suggested that the main stage for formation of unintentional POPs was the humidifier tower. These results improve our understanding of emission characteristics and could be used for simultaneous control of multiple POPs.

Transfer of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) from oral exposure into cow's milk - Part I: state of knowledge and uncertainties.

Polychlorinated dibenzo-para-dioxins (PCDDs) and dibenzofurans (PCDFs) (collectively and colloquially referred to as 'dioxins') as well as polychlorinated biphenyls (PCBs) are persistent and ubiquitous environmental contaminants that may unintentionally enter and accumulate along the food chain. Owing to their chronic toxic effects in humans and bioaccumulative properties, their presence in feed and food requires particular attention. One important exposure pathway for consumers is consumption of milk and dairy products. Their transfer from feed to milk has been studied for the past 50 years to quantify the uptake and elimination kinetics. We extracted transfer parameters (transfer rate, transfer factor, biotransfer factor and elimination half-lives) in a machine-readable format from seventy-six primary and twenty-nine secondary literature items. Kinetic data for some toxicologically relevant dioxin congeners and the elimination half-lives of dioxin-like PCBs are still not available. A well-defined selection of transfer parameters from literature was statistically analysed and shown to display high variability. To understand this variability, we discuss the data with an emphasis on influencing factors, such as experimental conditions, cow performance parameters and metabolic state. While no universal interpretation could be derived, a tendency for increased transfer into milk is apparently connected to an increase in milk yield and milk fat yield as well as during times of body fat mobilisation, for example during the negative energy balance after calving. Over the past decades, milk yield has increased to over 40 kg/d during high lactation, so more research is needed on how this impacts feed to food transfer for PCDD/Fs and PCBs.

Exploring PCDD/Fs and potentially toxic elements in sewage sludge during smouldering treatment.

Potentially toxic elements (PTEs), persistent organic pollutants, and emerging contaminants make sewage sludge management challenging. There is significant interest in thermal treatment technologies that can destroy these compounds. The most common thermal treatment, incineration, poses risks due to formation and/or release of hazardous substances in process emissions such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and PTEs. Smouldering has been introduced recently as a potential treatment for managing sewage sludge. Smouldering systems present several advantages over traditional incinerators; however, there are still uncertainties regarding process by-products. This key question was investigated in three laboratory-scale tests (0.08m radius) and five oil drum-scale tests (0.3m radius) that were evaluated for PCDD/Fs and PTEs in the mixture before and after treatment as well as in process emissions. Volatile organic compounds (VOCs) were also measured. These experiments represent a broad spectrum of conditions to evaluate process emissions, from robust self-sustaining to extinction of smouldering. Robust smouldering had negligible PCDD/Fs in process emissions. Weak smouldering had low levels of PCDD/Fs (emissions factor: 3.3±0.3μg TEQ/Mg dried sludge destroyed), levels less than uncontrolled emissions from commercial incinerators. Overall, smouldering acted as a sink for PCDD/Fs, as only 0-3% of the PCDD/Fs originally present in the sludge were released in the emissions, and >99% of the remainder were destroyed with <1% remaining in post-treatment ash. No evidence was found to support de novo synthesis or precursor reactions forming new PCDD/Fs. In addition, 94-100% of all the PTEs analyzed were retained in the post-smouldered material. These results indicate that only minimal emissions treatment for PTEs, PCDD/Fs, and VOCs may be necessary for future sewage sludge smouldering systems. These low emissions risks combined with its unique ability to handle high moisture content waste, indicate that smouldering has significant potential as a valuable waste management technique.

PCDD/Fs and DL-PCBs in Chinese Mitten Crab (Eriocheir sinensis) and Its Farming Environment in Shanghai, China.

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in the human body are acquired from dietary intake. The chronic exposure of humans to PCDD/Fs and DL-PCBs is a major health concern, and these compounds are strictly controlled in many areas. This study measured the levels of PCDD/Fs and DL-PCBs in Chinese mitten crab (Eriocheir sinensis) farms in Shanghai and determined potential sources. The mean concentrations of PCDD/Fs and DL-PCBs in the studied crab samples were 264.20 ± 260.14 and 506.25 ± 226.80 pg/g ww (wet weight), respectively. The range of the toxic equivalent (TEQ) for the total PCDD/Fs and DL-PCBs in the crab samples was 1.20–29.04 pg TEQ/g ww. Further analysis revealed that the TEQ input to crabs in aquacultural water was 1.6 times higher than the TEQ in edible crab parts. Aquatic plants, shore plants, and feed contributed about 0.05% of the total TEQ input to crabs. The TEQ contribution from sediment was 317 times that found in edible crab parts, and sediment may be the most prevalent source of PCDD/Fs and DL-PCBs in farm crabs. The evaluation of the Shanghai market crab revealed different levels of PCDD/Fs and DL-PCBs. The TEQs for the mean PCDD/F and DL-PCB levels were 1.55 ± 1.96 and 1.05 ± 0.55 pg TEQ/g ww, respectively. The tolerable daily intake (TDI) levels of adults and children were lower than the prescribed range (1–4 pg TEQ/kg (weight)·d), indicating no significant chronic or acute ingestion risk for adults and children.

Presence and risks of polycyclic aromatic hydrocarbons, dioxins and dioxin-like PCBs in dietary plant supplements as elucidated by a combined DR CALUX® bioassay and GC-HRMS based approach

Plant-based dietary supplements may contain undesirable contaminants such as polycyclic aromatic hydrocarbons, dioxins and dioxin-like polychlorinated biphenyls (dl-PCBs) due to the sources of raw materials or processing methods used. The presence of these contaminants in a series of herbal supplements sold on the Ghanaian market for improving sexual performance was examined using the DR CALUX® bioassay in combination with GC-HRMS analysis. Overall, cell responses at 4 and 48 h exposure to extracts prepared without an acid-silica clean-up were relatively higher than the responses obtained from extracts prepared with an acid-silica clean-up. This indicated that the 40 supplements contained only low levels of stable aryl hydrocarbon receptor (AhR) agonists like polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dl-PCBs, while some contained substantial amounts of less stable AhR-agonists. Ten supplements selected for confirmation with GC-HRMS analysis contained PCDD/Fs and dl-PCBs at levels ranging from 0.01 to 0.19 pg toxic equivalent (TEQ)/g only, while the level of the sum of 4 polycyclic aromatic hydrocarbons (Σ4PAHs) representing less stable AhR agonists, ranged from not detected (ND) to 25.5 ng/g. These concentrations were in line with the responses observed in the DR CALUX® bioassay. The concentration of PCDD/Fs and dl-PCBs corresponded to estimated daily intakes (EDIs) ranging from 0.01 to 1.20 pg TEQ/day, or 0.001 to 0.12 pg TEQ/kg bw/week for a 70 kg bw consumer, which was below the established tolerable weekly intake (TWI) of 2 pg TEQ/kg bw/week, thus indicating low concern for consumers’ health. Similarly, the EDIs based on the detected Σ4PAHs in supplements ranged from 7.2 to 111 ng/day, or 0.1 to 1.6 ng/kg bw/day, which corresponded to MOE values above 10,000, indicating a low health concern.

The Association between Blood Concentrations of PCDD/DFs, DL-PCBs and the Risk of Type 2 Diabetes Mellitus and Thyroid Cancer in South Korea.

Background and Objectives: Epidemiological studies have inconsistently shown an association between dioxin and risk of type 2 diabetes mellitus (T2DM) and cancer. This study aims to examine the effects of blood concentration of dioxin-like polychlorinated biphenyls (DL-PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) on T2DM and thyroid cancer. Methods: We conducted a nested case–control study within the Korean cancer prevention study-II (KCPS-II) consisting of 15 thyroid cancer cases, 30 T2DM cases, and 55 controls. A total of 500 samples were used in 100 pooling samples. An average value of a pooled sample was calculated weighted by the blood volume of each sample. Results: The study population included 100 participants from the KCPS-II (median (IQR) baseline age, 54.06 [21.04] years; 48 women). The toxic equivalents of PCDD/DFs showed a significant positive association with T2DM and thyroid cancer, after adjustments for potential confounders (T2DM ORs = 1.23; 95% CI = 1.05–1.43; thyroid cancer ORs = 1.34; 95% CI = 1.12–1.61). Conclusion: In this study, both T2DM and thyroid cancer were associated with the blood concentrations of PCDD/DFs. The association between PCDD/DFs and T2D was found among women but not among men. Our findings suggest that further biochemical in vivo research and epidemiologic studies are needed to clarify the association between dioxins concentrations and diseases.

Dioxin Congener Patterns in Breast Milk Samples from Areas Sprayed with Herbicide during the Vietnam War 40 Years after the War Ended.

Large amounts of herbicides containing polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) were sprayed in South Vietnam during the Vietnam War. Levels of PCDD/Fs in the environment of South Vietnam remained high even 40 years later. A total of 861 breast milk samples (597 from three areas sprayed with herbicides, Quang Tri, Da Nang, and Bien Hoa, and 264 from three unsprayed areas in North Vietnam) were collected between 2007 and 2015 and the PCDD/F concentrations in the samples were determined. Levels of TEQ-PCDD/Fs and 17 PCDD/F congeners were higher in the sprayed area samples than the unsprayed area samples. We found particular PCDD/F congener patterns for different areas. High tetrachlorodibenzo-p-dioxin (TCDD) concentrations were found in Bien Hoa, high TCDD and 1,2,3,6,7,8-hexadibenzo-p-dioxin concentrations were found in Da Nang, and high 1,2,3,4,6,7,8-heptadibenzo-p-dioxin concentrations were found in Quan Tri. High 1,2,3,4,7,8-hexadibenzofuran and 1,2,3,4,6,7,8-heptadibenzofuran concentrations were also found in Da Nang and Quang Tri. However, breast feeding may have caused associations between the TCDD and polychlorinated dibenzofuran congener concentrations. Advanced statistical analysis will need to be performed in future to assess the characteristic PCDD/F congener profiles in breast milk samples from areas of Vietnam previously sprayed with herbicides.

Dioxins and polychlorinated biphenyls in insect processed animal proteins used as a feed – is there a health risk?

Insects have all the characteristics necessary to become an alternative source of protein in feed. However, as with feed materials of animal origin, insect processed animal proteins (IPAPs) can also accumulate persistent organic pollutants such as dioxins and polychlorinated biphenyls (PCBs). Therefore, the aim of the present study is to complete the information on dioxin and PCB concentrations in feeds and compound feeds containing insect protein from mealworms (Tenebrio molitor) and the black soldier flies (Hermetia illucens). For the IPAPs samples of both mealworms and the black soldier flies, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) results ranged from 0.05 to 0.10 ng WHO-TEQ/kg feed at 12% moisture, for the total PCDDs/PCDFs/dl-PCBs ranged from 0.07 to 0.12 ng WHO-TEQ/kg feed at 12% moisture, and for non-dioxin-like polychlorinated biphenyls (ndl-PCBs) from 0.04 to 0.43 μg/kg feed at 12% moisture. Additionally, an experiment was conducted in which broilers were fed feeds containing IPAPs in an attempt to assess the risk to food consumers regarding dioxins and PCBs. Our studies showed that IPAPs from mealworms (T. molitor) and black soldier flies (H. illucens) will not pose a risk in terms of dioxins and PCBs.

Integration of steam gasification and catalytic reforming of lignocellulosic biomass as a strategy to improve syngas quality and pollutants removal

Residual biomass gasification is a promising route for the production of H2-rich syngas. However, the simultaneous formation of pollutants such as light hydrocarbons (HCs), benzene, toluene and xylenes (BTEX), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during gasification must be controlled. As a result, this study evaluated the effect of temperature and catalytic reforming over a Rh-Pt/CeO2-SiO2 catalyst during steam gasification of sugarcane residual biomass on syngas composition and pollutant removal. The above was carried out in a horizontal moving reactor, an Amberlite XAD-2 polyaromatic resin was used to collect the contaminants and characterization of the catalyst was performed. In this study, a concentration of up to 37 mol% of H2, a yield of 23.1 g H2 kg−1biomass, and a H2/CO ratio ≥2 were achieved when gasification and reforming were integrated. In addition, the catalyst characterization showed that Rh-Pt/CeO2-SiO2 was not susceptible to sintering and favored the formation of hydroxyl groups that promoted CO oxidation, thereby increasing the H2/CO ratio, as confirmed by in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). At 800 °C, where a high H2 yield was obtained, 209 g Nm−3 of light HCs and BTEX, 10.9 g Nm−3 of PAHs, and 32.5 ng WHO-TEQ Nm−3 of PCDD/Fs were formed after gasification. Interestingly, after catalytic reforming, 62% of light HCs and BTEX, 60% of PAHs, and 94% of PCDD/Fs were removed, leading to cleaner syngas with properties that allow it to be used in a wide range of energy applications.

Formation and control of dioxins during thermal desorption remediation of chlorine and non-chlorine organic contaminated soil

Formation and emission of dioxins is a great concern during thermal desorption remediation of organic contaminated soil. The differential formation of dioxins from chlorine organic contaminated soil (COCS) and non-chlorine organic contaminated soil (NCOCS) is still unclear and the control technique for the dioxins generated is an urgent need. In this study, the formation and distribution characteristics of dioxins were investigated in the thermal desorption unit combined with flue gas purification system during COCS and NCOCS treatments. Although organic contaminates were well desorbed, de-novo formation of dioxins was observed for both COCS and NCOCS, as well as synthesis from precursors for NCOCS. The gas-phase dioxin in the flue gas purification system continuously decreased during NCOCS thermal desorption, while the dioxin concentration in the quench tower sharply increased from 0.46 to 2.13 ng/Nm3 through de-novo synthesis during COCS treatment. Furthermore, the emission of dioxins only slightly reduced (for COCS) or even increased (for NCOCS) at 70% operating load. The catalytic adsorption tower within modified activated carbon and V5-Mo5-Ti catalyst after bag filter can reduce the emission of dioxins up to 91.4% at the condition of secondary combustion chamber closure, demonstrating that the catalytic adsorption tower can replace the secondary combustion chamber for controlling dioxin emission. More importantly, the highly toxic low-chlorinated polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/PCDFs) were selectively removed from flue gas by the catalytic adsorption tower. These results reveal the differential formation characteristics of dioxins during COCS and NCOCS thermal treatments and highlight V5-Mo5-Ti/ modified activated carbon as a promising catalytic adsorption material to control the emission of dioxins from the thermal desorption of organic contaminated soil.

PCDD/Fs from a large-scale municipal solid waste incinerator under transient operations: Insight formation pathways and optimal reduction strategies

Polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) emissions from the transient operation of municipal solid waste incinerators can reach up to 690 ng/Nm3, as measured in this study. To control the extreme emissions to meet the national standard, the formation pathways of PCDD/F were investigated under transient operations (cold start-up, hot start-up, and after start-up) and normal operations. Compared with normal operations, transient operations facilitate the formation of low-chlorinated congeners rather than highly chlorinated congeners. Statistically, for transient operations, strong correlations were found among tetrachlorodibenzo-p-dioxin or tetrachlorodibenzofuran isomers. An abundant carbon matrix is an important carbon source for PCDD formation. Moreover, the comprehensive study revealed that the oxidation of deposited soot is the main source of PCDD/F emissions, relative to de novo synthesis, chlorobenzene-route synthesis, chlorophenol-route synthesis, and chlorination of dibenzo-p-dioxin/dibenzofuran. In addition, the optimal start-up procedure was constructed by analyzing main formation pathways and operating conditions. The relationship between the international toxic quantity (I-TEQ) values (CI-TEQ) and the reaction time can be assigned as CI-TEQ = 11.72t−0.65 (R2 = 0.97) for the circulating fluidized bed. The relationship of CI-TEQ = 4.61t−0.59 (R2 = 0.85) was also proven on the dataset with a grate furnace. Then, the optimal feeding rate of activated carbon was further proposed by the relationship between the reaction time and I-TEQ, and the semi-empirical equation for PCDD/Fs adsorption. Finally, the PCDD/Fs emissions can be reduced to 0.1 ng I-TEQ/Nm3 under transient operations according to the time since start-up.

Photochemical degradation of persistent organic pollutants (PCDD/FS, PCBS, PBDES, DDTS and HCB) in hexane and fish oil

This study has investigated the photochemical degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and some organochlorine pesticides, such as hexachlorobenzene (HCB) or dichloro-diphenyl-trichloroethane (DDT) in hexane under UV irradiation at 254 nm. All pollutants were completely degraded after 3.5 h of exposition to the UV light. Moreover, this technique was applied to remove persistent organic pollutants from fish oil, with eliminations of a 34% for PCDD/Fs, 53% for PCBs, 59% for HCB, 67% for PBDEs and 73% for DDTs after 12 h of exposition to the UV light (254 nm). Dioxin-like PCBs increased their concentration after the treatment, probably due to the dehalogenation of other more chlorinated congeners. The fatty acids analysis of the fish oil revealed that the most important ω-3 fatty acids –EPA and DHA-were degraded to 67 and 70% of their initial content respectively. For these reasons elimination of persistent organic pollutants with photochemical treatment has limited applications for oils with food-purposes. However, it still can be a useful technique for decontamination of industrial oils.

Body burden and influencing factors of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) in male workers from a municipal waste incineration plant in China

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) from municipal solid waste incinerators (MSWIs) have aroused public concern around the world. However, biomonitoring evidence regarding the influence of MSWIs on the human body burden of PCDD/Fs is scarce. The aim of this study is to investigate the human body burden levels of PCDD/Fs in MSWI workers and to further explore the potential influencing factors, including duration of occupation and dietary habits, on the PCDD/F levels. A total of 98 paired serum samples from MSWI workers and non-MSWI workers were collected. Seventeen 2,3,7,8-chlorine substituted PCDD/Fs in the serums were analyzed using an isotope dilution high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS). The results showed that the mean levels of toxic equivalent (TEQ)-PCDD/Fs for the MSWI workers and the control group were 18.28 pg TEQ g−1 lipid and 5.81 pg TEQ g−1 lipid, respectively. Significantly higher concentrations of PCDD/Fs existed in the incinerator workers compared with the control subjects after adjustment of the confounding factors. OCDD was the most abundant congener in both the MSWI workers and the control subjects, accounting for 82.2% and 89.4% of the ∑17PCDD/Fs, respectively. The serum levels of PCDFs in the MSWI workers increased with the duration of occupation (β = 0.498, P = 0.031), and a higher total concentration of PCDD/Fs were present in senior workers classified as production supervisors than routine operation staff (β = 8.809, P = 0.008). No significant relationship was found between the PCDD/F concentrations and dietary habits. This study was the first to explore the associations between the body burden of PCDD/Fs and occupational exposure as well as dietary intake of MSWI workers in China. The findings provide scientific information for health risk assessments of human exposure to PCDD/Fs.

Spatial-temporal distribution, cancer risk, and disease burden attributed to the dietary dioxins exposure of Chinese residents

This study analyzed the characteristics of dioxins represented by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as dioxin-like polychlorinated biphenyls (dl-PCBs) in food from China. The spatial-temporal distribution characteristics of dioxins dietary intake, cancer risk, and disease burden were evaluated among the Chinese population. In the temporal dimension, descending trends in animal-origin-food were found both in dietary intake PCDD/Fs and dl-PCBs, with the reverse for plant-origin-food. The probability assessments of dietary intakes showed that after 2007, the exposure level of PCDD/Fs through diets of urban and rural residents in China was significantly lower than that before 2007 (p < 0.05). The spatial distribution results showed that the southern coastal regions were high exposure regions of dietary intakes of PCDD/Fs and dl-PCBs. Cancer risk and disease burden of dietary dioxins showed downward trends after 2007 both under an average exposure scenario and an extreme exposure scenario. After 2007, the disease burden resulting from exposure to dl-PCBs became higher and approached the median of values reported by the WHO, while the disease burden resulting from exposure to PCDD/Fs approached the lower level of 95% CI reported by the WHO. The results indicate that accompanying the National Implementation Plan and a series of subsequent scientific guidance documents launched for reducing dioxins pollution in 2007, the health benefits and the health risks caused by dl-PCBs should be given further attention and evaluation in future studies.

Abatement of chlorobenzene by plasma catalysis: Parameters optimization through response surface methodology (RSM), degradation mechanism and PCDD/Fs formation

Dielectric barrier discharge coupled with 10 wt% Co/γ-Al2O3 catalyst was developed to degrade chlorobenzene in this study. The effects of experimental parameters including applied voltage, flow rate, initial chlorobenzene concentration, and their interactions on the chlorobenzene degradation performance were investigated by the response surface methodology integrated with a central composite design. Results indicated that applied voltage was the most significant parameter affecting the mineralization rate and the concentration of ozone generated, while energy yield was mainly determined by initial chlorobenzene concentration. As a key precursor of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorophenols were found during the identification of the intermediates produced during chlorobenzene degradation through GC-MS. Furthermore, HRGC-HRMS was used to detect the remaining byproducts on the catalyst surface after 3 and 10 h discharge time, and three types of PCDD/Fs (2,3,7,8-TCDF, 1,2,3,4,6,7,8-HCDF and OCDD) were detected after 10 h of discharge. The degradation mechanism of chlorobenzene was analyzed based on these detected intermediates, and the possible formation mechanisms of the three PCDD/Fs were proposed for the first time in plasma catalytic degradation of chlorobenzene.

Burden levels of polychlorinated dibenzo-p-dioxins, dibenzofurans, and polychlorinated biphenyls in typical edible meat animals

The concentrations and distributions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in the whole blood and meat of eight typical edible animals (chicken, donkey, horse, cattle, rabbit, sheep, duck, and pig) were illustrated. Total concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and PCBs (on a basis of liquid volume) in animal bloods were 142-484 pg/L and 46-62 ng/L, respectively. Total concentrations of PCDD/Fs and PCBs (on a basis of dry weight (dw) and lipid weight (lw)) in animal meat samples were 0.47-1090 pg/g dw (0.47-4513 pg/g lw) and 7.2-23 ng/g dw (10-776 ng/g lw), respectively. TEQs for both PCDD/Fs and PCBs in animal blood and meat samples were (67 ± 27) pg/L and (5.3 ± 14) pg/g dw (24 ± 56 pg/g lw), respectively. Besides, the dietary intakes of PCDD/Fs and PCBs were also estimated. Chicken and pig contributed more TEQs than other animals. Chicken contributed the most (95%) with high toxicity, followed by pig (3.4%) with high consumption. The dietary intake of chicken might pose risks to consumers who prefer to eat chicken products, who should comprehensively consider the essential nutrients and contaminants in food during dietary intake.

Instrumental and bioanalytical characterization of dioxin-like activity in sediments from the Yeongsan River and the Nakdong River estuaries, South Korea

In the present study, we investigated the contamination status of dioxin-like chemicals (DLCs) and potential toxic effects associated with river and coastal sediments from two large estuaries of South Korea. Sediments collected from the Yeongsan River and the Nakdong River estuaries were analyzed for several DLCs, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), and polycyclic aromatic hydrocarbons (PAHs). Greater concentrations of target DLCs (except for PCDDs in Nakdong River) were found in the inland creeks with decreasing trends towards estuarine and coastal areas in both regions. The result indicated that the elevated DLCs were attributable to the surrounding land use activities, such as point sources of industrial and municipal areas from the inland regions. Principal component analysis and positive matrix factorization model revealed that major sources of PCDD/Fs and PAHs in sediments were fly ash and dust, and petroleum and diesel emission, respectively. The dioxin-like activities of the sediments ranged from 0.98 to 88% of the maximal induction elicited by 2,3,7,8-tetrachlorodibenzo-p-dioxin, which generally explained the sedimentary contamination by the target DLCs. Dioxin-like activity in sediments from the artificial lake and inland creek of the Nakdong River Estuary was mostly explained by the targeted DLCs (~75%). However, the contribution of known DLCs from the sediments of the Yeongsan River Estuary was relatively low (~35%) compared to that of the Nakdong River Estuary, suggesting the presence of unknown DLCs in sediments. Overall, the distribution of DLCs quite varied by region, generally reflecting the difference in the surrounding land use activity. In the future, it is needed to study the distribution, sources, and potential ecological effects of unknown toxic substances in coastal sediments.

Study on Correlation Characteristics of PCDD/Fs Isomers Generation during the Coal-Combustion Process with Sludge Mixing

The 17 toxic polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) isomers as a persistent and refractory organic pollutant are one of the pollutants produced in solid fuel (including pulverized coal and mixed fuel) combustion, and regulating their distribution characteristics is an important aspect of effectively reducing their toxic equivalent. In this study, a correlation model of PCDD/Fs toxic equivalent was proposed to quantitatively analyze the correlation between HCl and SO2 concentrations in the reaction atmosphere, meanwhile, a pathway-diagnosis method of PCDD/Fs isomers transformation was adopted to analyze the PCDD/Fs distribution characteristics of coal combustion and that mixed with 10% sludge. The results show that the inflection point for the derivative of the relationship between HCl concentration and SO2 concentration moves towards the direction of lower SO2 concentration and higher HCl concentration with the increase of PCDD/Fs toxic equivalent. Besides, the functional pathways of mixing sludge on PCDD/Fs generation in coal combustion were obtained by calculating chlorine substitution probability. It has been deduced that five transformation pathways were improved by mixing sludge. Next, the critical pathways of the influence from mixing sludge on the distribution characteristics of PCDD/Fs isomers in coal combustion were analyzed by drawing the percentage content migration diagram of PCDD/Fs isomers and the average toxic equivalent migration diagram that combined with the toxic equivalent of PCDD/Fs isomers. The results showed that the main reasons for mixing sludge to further reduce the average toxic equivalent of PCDD/Fs isomers in coal combustion were the increased chlorine substitution probability at the 4-position of 12378 Pentachlorodibenzo-p-dioxin (12378-PeCDD), the decreased chlorine substitution probability at the 4-position of 2378 Tetrachlorodibenzo-p-furan (2378-TeCDF), and the increased total chlorine substitution probability of 23478 Pentachlorodibenzo-p-furan (23478-PeCDF), 123478-Hexachlorodibenzofuran (123478-HxCDF) and 123678-HxCDF respectively. Finally, the functional pathway diagram of PCDD/Fs isomers generated from coal combustion with sludge mixing was drawn.

Phase distribution, migration and relationship of polychlorinated dibenzo-p-dioxins and dibenzofurans and heavy metals in a large-scale hazardous waste incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and heavy metals emitted from hazardous waste incinerators have aroused public concern due to the risks to the environment and human health. In the study, phase distribution, migration, and relationship of PCDD/F and heavy metals (arsenic, cadmium, chromium, copper, mercury, nickel, plumbum, zinc) are investigated in a typical hazardous waste incinerator. The PCDD/F mass concentrations and toxic equivalent quantity are reduced to 3.26 ng/Nm3 and 0.0484 ng/Nm3 by air control pollution devices, with 93.1% remove efficiency. High sulfur content in hazardous waste results in low PCDD/F and heavy metals emissions. Moreover, migration analysis of PCDD/F mass concentrations indicates that vast PCDD/F migrates to the mixtures with sodium bicarbonate and activated carbon (52.4%), followed by fly ash (21.8%), sodium hydroxide solution (19.3%), and atmosphere (6.49%). Furthermore, TCDF isomers (37%) dominate among the PCDD/F congeners, while 1,2,3,4,6,7,8-HpCDF (20%) dominates among 2,3,7,8-substituted congeners. Deduced by the ratio of PCDF/PCDD, the dominant mechanism of PCDD/F is de novo synthesis and chlorobenzene route synthesis. Based on the relative enrichment index, heavy metals are classified into three types: volatile heavy metals (plumbum, zinc, cadmium, mercury), medium volatile heavy metals (copper, chromium, arsenic), involatile heavy metals (nickel). Additionally, copper is inclined to deposit into the bottom slag as CuSO4 rather than the volatile substance due to high levels of sulfur dioxide (3000 parts per million). The migration behavior of heavy metals is dependent on the volatility properties of these metals. Statistically, PCDD/F emissions have the highest correlation coefficient with plumbum (r = 0.815), followed by nickel (r = −0.798). Besides, the PCDD/F formation is promoted by the volatile heavy metal, prevented by medium volatile heavy metals. The study not only provides a comprehensive understanding of PCDD/F and heavy metals characteristics but also effective and feasible strategies to reduce the toxic pollutants emissions in large-scale hazardous waste incinerators.