OCDD Research Articles

Behavior of PCDD/Fs and PCBs from Wastewater Treatment Plants during Sewage Sludge Composting: Study of Semi-Anaerobic Conditions and Different Stages of the Process

Composting is a common treatment for the high amounts of sewage sludge produced in wastewater treatment plants, and the product is used in agriculture. Composting reduces the levels of biodegradable organic pollutants, although other compounds present in wastewater and not eliminated previously by conventional physical–chemical and chemical treatments, such as polychorodibenzo-p-dioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs), have been found in the final compost at higher levels than those observed in the initial sludge. Their formation was studied during composting under unfavorable aeration conditions and paying attention to different stages of the process. Experiments were carried out in small vessels inside a controlled oven for three types of sewage sludge. Pentachlorophenol was previously added as a dioxin precursor. A clear formation of PCDD/Fs was found, especially during the maturation stage for two experiments. Mainly octachlorodibenzo-p-dioxin (OCDD) and 1234678-heptachlorodibenzo-p-dioxin (1234678-HpCDD) to a lesser extent were formed. OCDD levels in the final samples were around 10 times higher than those of the initial mixture after removing the concentration effect. No clear formation nor degradation of PCBs was observed. The toxicity values due to PCDD/Fs and PCBs found in the initial mixtures were 1.20–2.46 ng WHO-TEQ/kg, and those from the final samples were 2.30–7.86 ng WHO-TEQ/kg. Although the toxicity values are below the most restrictive limits found in Europe in this case, toxicity could increase considerably with the presence and concentration of other precursors. Compost from sewage sludge is an ecological product, but the operating conditions must be controlled to avoid PCDD/F formation and facilitate degradation of persistent organic pollutants.

Investigating the presence of dioxins in drinking water: implications for public health

ABSTRACT The presence of highly toxic dioxins, specifically polychlorinated dibenzo-p-dioxins (PCDDs), in drinking water is a matter of great concern due to their long-lasting nature and harmful effects. In this study, we detected three out of the five dioxin congeners: 2, 3, 7, 8-tetrachlorodibenzodioxin (TCDD), 1, 2, 3, 7, 8-pentachlorodibenzo-p-dioxin (PeCDD), and octachlorodibenzo-p-dioxin (OCDD). The investigation revealed that three dioxins were present in water samples of winter season, while TCDD and OCDD were found in the summer season. The geometric mean concentrations of PCDDs were 229.9 ng/L (winter) and 108.4 ng/L (summer), exceeded the maximum contaminant level of 30 pg/L set by the USEPA in surface water. The estimated daily intake of PCDDs for residents through drinking water was 273.97 ng-WHO2005-TEQ/kg/days during winter and 78.875 ng-WHO2005-TEQ/kg/days during summer. Our study emphasizes the urgent need for further research on persistent organic pollutants in drinking water to safeguard public health and community well-being.

Determination of PCDD/F and DL-PCB pollution levels, source appointment and risk assessment of surface sediments in dam lakes in Istanbul, Türkiye.

The current situation of the water resources of Istanbul, which is one of the important metropolises of Europe, should be known and constantly monitored by the reasons of the rapid increase in the city population, the acceleration of production-related industrial activities, the expansion of the city with construction activities, and the decrease in precipitation. The purpose of this study was to reveal the situations of surface sediments collected from Istanbul water reservoirs in terms of PCDD/Fs and DL-PCBs, to identify possible sources, and to conduct their ecological risk assessment. Total PCDD/Fs and DL-PCBs concentrations varied between 28.13 and 457.4pg/g (average 136.8pg/g) and 12.19-340.1pg/g (average 72.09pg/g). The corresponding TEQ values of PCDD/Fs and DL-PCBs were between 0.53 and 5.37pg TEQ/g (average 2.23pg TEQ/g) and 0.02-0.44pg TEQ/g (average 0.12pg TEQ/g), respectively. Octachlorodibenzo-p-dioxin (OCDD) is the dominant congener by constituting about 75% of the total PCDD/Fs on average, while congener distributions of DL-PCBs showed the dominance of PCB-118 and PCB-105. The sediments taken from Kazandere dam have the lowest pollution levels for both PCDD/Fs and DL-PCBs. The highest PCDD/F and DL-PCB amounts were measured in sediments of Alibey and Elmalı dams (closest to highly populated settlements of Istanbul), which are most affected by the air pollution caused by the traffic, commercial/industrial combustion (like waste incineration facility) and combustion for residential heating. Almost all the sediments have total dioxin-like toxicity levels higher than the safe threshold level (with two exceptions) of 0.85pg TEQ/g dw, proposed for ecological risk. Health risk assessment shows that levels of dioxin-like compounds would result in a total intake of 0.33pg TEQ/kg bw/day even in the worst-case scenario, not exceeding the tolerable daily intake value of 1pg TEQ/kg bw/day. Among exposure pathways, consumption of fish constitutes almost all the total intake, while contributions of other pathways are minimal.

Emission Characteristics of Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans (PCDD/DFs) in Commercial Bio-SRF and SRF Incineration Plants

Incineration plants using solid refused fuel (SRF) should control their air pollution materials to minimize environmental impact. This study evaluated the emission of polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/DFs) congener patterns in seven commercial incineration plants in Korea using SRF and biomass SRF (bio-SRF). We examined the reduction rate differences of PCDD/DFs, depending on the air pollutant control device. All seven incineration plants sufficiently managed their dioxin emissions. However, both SRF and bio-SRF incineration plants showed active chlorination reactions and resulted in a large amount of highly chlorinated dioxins. The average dioxin concentration was 0.02 ng international toxic equivalency quantity (I-TEQ)/Sm3. Ratios of 1,2,3,4,6,7,8-HpCDF and 1,2,3,7,8-PeCDF were high in the waste heat boilers of both SRF and bio-SRF incineration plants. The octachlorinated dibenzofuran (OCDF) ratio was only high in the SRF incineration plants. Octachlorodibenzo-p-dioxin (OCDD) and OCDF exhibited high dioxin ratios. SRF incineration plants had a low ratio of OCDF to 1,2,3,4,6,7,8-HpCDF. In addition, the reduction rate of PCDD/DFs was substantially high after treatment with the air pollutant control device.

Effect of hydrogenation of palm oil products spiked with octachlorodibenzo-p-dioxin on dioxin congener profiles and toxic equivalent levels

Between 1999 and 2020, there were twelve rapid alerts on dioxins in palm fatty acid distillate (PFAD) products, six of which were associated with hydrogenated palm fatty acid distillates (HPFADs). In palm oil refineries for food and feed, refined palm oil and PFADs can be processed into hydrogenated palm oil and HPFADs. This study investigated the effect of hydrogenation of palm oil products which contain OCDD and impact on the profiles of dioxins in palm oil products and on the toxic equivalent (TEQ) level. Palm oil and PFADs were spiked with octachlorodibenzo-p-dioxin (OCDD) and hydrogenated at different pressures, temperatures, and catalyst conditions. Initially, the concentrations of the lower-chlorinated dioxin congeners, some with a higher toxic equivalency factor, increased. Consequently, the TEQ levels increased and exceeded the regulatory limit. However, further hydrogenation extended the dechlorination of dioxins resulting in decreased TEQ levels. Optimisation of the hydrogenation process is required to reduce the risk of exceeding the limits on dioxins. • Hydrogenation of palm oil products affected the toxicity of dioxin congeners. • Octachlorodibenzo-p-dioxin (OCDD) dechlorinated during hydrogenation. • OCDD dechlorination initially formed congeners with higher toxicity. • Further hydrogenation reduced dioxin concentration and toxic equivalence level.

Ionic liquid screening of Octachlorodibenzo-p-dioxin captured from water samples by [formula omitted]-profile analysis for microextraction applications

The extraction of octachlorodibenzo-p-dioxin (OCDD) is very challenging due to its highly non-polar nature, demanding the use of large amounts of toxic solvents. Ionic Liquids (ILs) for OCDD extraction were screened to replace traditional solvents using the Conductor-like Screening MOdel for Real Solvents (COSMO-RS). The analysis was performed by studying the σ-profile of a variety of commercially available cations and anions employed in the literature. The effects of different alkyl chain lengths and configurations were studied in cations. In the case of anions, different reported structures, including fluorine- or oxygen-bearing structures, were assessed. Results indicate that the alkyl chain, symmetry, and nature of the central atom in the cations are critical factors to achieve high affinity to OCDD. The polarity of anions was found to be modified by adding highly electronegative atoms, a steric hindrance to the central atom and the use of planar geometries with symmetrical groups. The performance of ILs for extracting OCDD was compared with that of conventional solvent extractants used for quantifying dioxins in the US EPA-1613 method. Finally, three cations and anions are proposed as candidates for dioxin extraction.

Kaolinitic clays as a potential source of dioxins in the Noosa River catchment, Queensland, Australia

Environmental context Dioxins have been found along the east coast of Australia in agricultural areas where there is no obvious source of dioxins. These dioxins have an unusual signature that does not match common industrial sources, but it has been suggested that they may be associated with pesticide use. This study found a strong correlation between dioxins with this unique signature and the amount of a kaolinitic clay in the sediments sampled. Abstract The presence, concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in sediment were investigated in this study with the aim of determining whether dioxin-like compounds were present and, if found, a likely source could be deduced. The sampled catchment lies within an area of high conservation value. Sediments from seven lake sites were sampled as possible sinks for any contamination from historical pesticide use. PCDD/Fs were measured in all the lake sediments. The 2,3,7,8-substituted congener profile was dominated by octachlorodibenzo-p-dioxin (OCDD) with furans at or below the limit of detection, a profile that has been associated with kaolinitic clays from around the world. A strong and significant correlation was found between the total dioxin concentration and the percentage of kaolinitic clay in the sediments. The lack of furans in the 2,3,7,8-substituted PCDD/F profile indicates pesticides or pentachlorophenol (PCP) are unlikely to be the source in the catchment. Further, the concentration of total dioxins and OCDD tended to be higher than those measured outside the study area, even though, overall, the study area is likely to have had less pesticide use than the other intensive agricultural areas previously studied. The results presented in this paper indicate that caution should taken when attributing the presence of dioxins in soil and sediment to anthropogenic sources.

Exposure and risk assessment of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) for primiparous mothers and breastfed infants in Penang, Malaysia

ABSTRACT An average 50 ml breast milk samples were collected from 21 lactating primiparous mothers (range 25 to 45 years, mean 33 years), 4–8 weeks after delivery in Penang Island, Malaysia. The geometric mean concentration of the most toxic congeners, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.14 pg WHO2005-TEQ g−1 zlipid. The most abundant congeners of PCDD/Fs were octachlorodibenzo-p-dioxin (OCDD) (5.9–75.4%), followed by 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (1,2,3,4,6,7,8-HpCDD) (1.1–30.7%). The geometric mean level of total dioxins and dl-PCBs was 2.2 pg WHO2005-TEQ g−1 lipid, significantly lower than those in developed countries or highly contaminated areas. The total dioxins and dl-PCBs in pg WHO2005-TEQ levels in breast milk were significantly correlated with years of residence at potential contaminated site. The average daily intake of 11.8 pg WHO2005-TEQ kg−1 body weight was estimated for a breastfed infant at 6 months of age. This demonstrates the exposure risk to infants, especially from Penang region, to these pollutants from human milk intake are potentially high during the lactation period.

PCDD/Fs in paired hair and serum of workers from a municipal solid waste incinerator plant in South China: Concentrations, correlations, and source identification

Human hair has been widely used to evaluate the exposure to drugs and organic pollutants. However, reports on the relationship between polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-p-furans (PCDFs) in hair and the body burden of PCDD/Fs are limited. In this study, the association between PCDD/Fs in paired hair and serum samples from workers was examined in a municipal solid waste incinerator (MSWI) plant in South China. Fly ash and flue gas from the MSWI plant were also analyzed to determine the source apportionment of PCDD/Fs in the hair. The median international toxic equivalents (I-TEQs) of ΣPCDD/F in serum and hair were 28.0 pg TEQ/g (lipid weight) and 0.30 pg TEQ/g (dry weight), respectively. The indicator congener of PCDD/Fs for the TEQ levels was 2,3,4,7,8-pentachlorodibenzofuran (PeCDF) in both hair and serum, the concentrations of which both exhibited significant and strong linear dependence on the total TEQ levels (p < 0.01, R2 = 0.966 and R2 = 0.670, respectively). Significant positive correlations were found in the 1,2,3,6,7,8-hexachlorodibenzo-p-dioxin (HxCDD) and octachlorodibenzo-p-dioxin (OCDD) levels between the hair and serum samples (p < 0.05). Flue gas (which is an external source) was identified as the primary source of PCDD/Fs in human hair. Blood and flue gas were accountable for, on average, 37% and 61% of the PCDD/Fs in hair, respectively.

Effect of reducing agent on catalytic hydrodechlorination of aqueous-phase OCDD/F

Removal/destruction of aqueous-phase octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) via hydrodechlorination process (HDC) is experimentally evaluated over palladium/activated carbon (Pd/AC) catalyst. Pd catalyst is mainly used as active component for effectiveness in removing dioxin from wastewater. Studies on the removal of PCDD/Fs accomplished with HDC reaction in aqueous phase are limited and the influencing factors have not been clarified. In this study, high-concentration OCDD/F are selected as targets, and the effects of solvent and operating temperature on dechlorination efficiency are investigated via experimental tests. The results indicate that the highest hydrodechlorination efficiency is achieved with isopropanol as solvent. The OCDD/F removal efficiency achieved with the solution of 80% isopropanol is higher than that of 50% isopropanol, whereas the destruction efficiency of OCDD/F reveals the opposite trend. Generally, the removal and destruction efficiencies of PCDFs are higher than those of PCDDs. In addition, the activation energies of OCDD and OCDF are calculated with the Arrhenius equation as 24.8 and 23.1 kJ/mol, respectively. Stability tests are conducted with three cycles. Overall, the results indicate that a high performance (≥99%) can be achieved by combining hydrodechlorination with Pd/AC at a temperature range of 303–353 K, demonstrating that Pd/AC has good potential for removing PCDD/Fs from wastewater.

PCDD/F determination in sewage sludge composting. Influence of aeration and the presence of PCP

Composting of sewage sludge is a common practice for sludge disposal. Some previous studies found high levels of polychorodibenzo-p-dioxins and polychorodibenzofurans (PCDD/Fs) after composting, especially octachlorodibenzo-p-dioxin (OCDD) but also 1234678-heptachlorodibenzo-p-dioxin (1234678-HpCDD) to a lesser extent. In this work, the concentrations of OCDD, 1234678-HpCDD and the rest of the 17 toxic congeners of PCDD/Fs were determined in compost obtained under different conditions. Although the toxicity of the two compounds mentioned above is small, their generation may reach undesirable levels. The PCDD/F content was analyzed in a composting plant and in a laboratory test. In both cases, the composted material was a mixture of sewage sludge, straw and sawdust. The composting plant was a tunnel with air turbine aeration and with a turner to homogenize and move the mixture upwards. The laboratory tests were carried out with Dewar vessels (with air dispersion at the bottom and controlled temperature) and with small vessels inside a controlled oven with non-forced aeration. The laboratory runs were also carried out with the addition of pentachlorophenol in some runs, as a dioxin precursor. The highest OCDD levels were found in three samples of the composting plant (30000–90000pg/g dry matter or dm), with toxicity values surpassing the limit level for soil amendment (17pgI-TEQ/gdm). Their formation was analyzed considering their concentration vs. that of octachorodibenzofuran (OCDF), which is not formed during composting. In the laboratory, in experiments carried out in a vessel with non-forced aeration conditions and with the addition of pentachlorophenol, the formation of OCDD was significant (e.g. from 80 to 1500pg/gdm). That means that these two factors, non-forced aeration and the presence of pentachlorophenol, can cause the OCDD formation.

Human exposure to PCDDs and their precursors from heron and tern eggs in the Yangtze River Delta indicate PCP origin

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are highly toxic to humans and wildlife. In the present study, PCDD/Fs were analyzed in the eggs of whiskered terns (Chlidonias hybrida), and genetically identified eggs from black-crowned night herons (Nycticorax nycticorax) sampled from two lakes in the Yangtze River Delta area, China. The median toxic equivalent (TEQ) of PCDD/Fs were 280 (range: 95–1500) and 400 (range: 220–1100) pg TEQ g−1 lw (WHO, 1998 for birds) in the eggs of black-crowned night heron and whiskered tern, respectively.Compared to known sources, concentrations of PCDDs relative to the sum of PCDD/Fs in bird eggs, demonstrated high abundance of octachlorodibenzo-p-dioxin (OCDD), 1,2,3,4,6,7,8-heptaCDD and 1,2,3,6,7,8-hexaCDD indicating pentachlorophenol (PCP), and/or sodium pentachlorophenolate (Na-PCP) as significant sources of the PCDD/Fs. The presence of polychlorinated diphenyl ethers (PCDEs), hydroxylated and methoxylated polychlorinated diphenyl ethers (OH- and MeO-PCDEs, known impurities in PCP products), corroborates this hypothesis. Further, significant correlations were found between the predominant congener CDE-206, 3′-OH-CDE-207, 2′-MeO-CDE-206 and OCDD, indicating a common origin.Eggs from the two lakes are sometimes used for human consumption. The WHO health-based tolerable intake of PCDD/Fs is exceeded if eggs from the two lakes are consumed regularly on a weekly basis, particularly for children. The TEQs extensively exceed maximum levels for PCDD/Fs in hen eggs and egg products according to EU legislation (2.5 pg TEQ g−1lw). The results suggest immediate action should be taken to manage the contamination, and further studies evaluating the impacts of egg consumption from wild birds in China. Likewise, studies on dioxins and other POPs in common eggs need to be initiated around China.

Catalytic decomposition of gaseous PCDD/Fs over V2O5/TiO2-CNTs catalyst: Effect of NO and NH3 addition

There is a strong need for a control technology that simultaneously achieving the abatement of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) and nitrogen oxides (NOx) emissions in waste incineration industry. TiO2 and carbon nanotubes (CNTs) were used as composite carriers to support vanadium oxide as an innovative catalyst to simultaneously control PCDD/Fs and NO emissions. The removal efficiencies (RE) of PCDD/Fs by V2O5/TiO2-CNTs catalyst under a space velocity (SV) of 20,000 h−1 reaches 99.9% at 150 °C and adsorption is supposed to be the main mechanism at this temperature. The influence of NONH3 reaction on PCDD/Fs catalytic reaction is investigated. The kinetics analysis exhibits that the addition of NO and NH3 reduces the activation energies for OCDD (octachlorodibenzo-p-dioxin) and OCDF (octachlorodibenzofuran) decomposition to 3.6 kJ/mol and 5.4 kJ/mol respectively.

Isomer-specific investigation of PCDD/F mobility and other fate processes in deep soil cores

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are highly hydrophobic compounds with low migration potential in soil–water. Nevertheless, they have been occasionally reported in subsurface soils hypothesised as the result of facilitated transport processes with colloids or surfactants, or yet unidentified in-situ formation processes. To date, however, the prevalence of deep soil contamination, involved processes and their kinetics remain poorly understood. This study investigated PCDD/F concentrations and isomer profiles through deep soil cores (to 20m) from agricultural, industrial and urban sites in Queensland, Australia. Based on isomer profiles, a unique source common to all core soils (regardless of depth) was identified, dominated by octachlorodibenzo-p-dioxin (OCDD). The source was consistent with contamination resulting from pesticide impurities. Elevated PCDD concentrations (μg/kg range) to depths up to ∼4–17m and a continuous increase of peri-chlorinated (1,4,6,9-substituted) isomers through the cores suggested that vertical transport and lateral dechlorination were key post-depositional processes at these sites. The mobility of PCDDs in the present study is far greater than previously reported in soils in general. High estimated mass transport rates for OCDD in four agricultural cores (3.0–6.2% year−1) likely reflect significant levels of facilitating species, including surfactants, and intensive rainfall at these sites. The implications of such extensive subsurface transport of PCDD/Fs for groundwater contamination and load estimates may be significant. If the cores of the present study are assumed representative of the region, a total PCDD/F load in the order of 800tonnes (1.6tonnes TEQ) could be present in subsurface Queensland coastal soils.

Detection and identification of trace amounts of organochlorine substances by gas chromatography-high-resolution mass spectrometry

A search and identification of organochlorine compounds in soils with abnormally high level of octachlorodibenzo-p-dioxin from the northern province of Vietnam were carried out by gas chromatography-high-resolution mass spectrometry using a magnetic sector mass spectrometer in the scan and multi-ion detection modes at resolution 8000–10000. An algorithm for determining the exact mass, molecular formula, and molecular structure of organochlorine substances at ultratrace concentrations was proposed. Twenty-eight organohalogen compounds were found, 22 of which were derivatives of polychlorinated dibenzo-p-dioxins and polychlorinated diphenyl ethers with from one to three methoxy groups; the concentration range for these compounds is 0.0001–0.5% relative to the level of octachlorodibenzo-p-dioxin (OCDD). The existence of such substances was assumed, as they may be metabolites of polychlorinated dibenzo-p-dioxins (PCDD) or other chlorinated aromatic compounds, but most of these compounds have never been described in the literature. Some of the compounds could be considered as possible biotransformation products of OCDD; the others of different origin and may be byproducts of the formation of OCDD in nature.

Dioxin-like PCBs and PCDD/Fs in surface sediments near the shore of Winam Gulf, Lake Victoria

Winam Gulf of Lake Victoria is considered to be contaminated with toxic chemicals emanating from anthropogenic activities, especially near large industrial towns such as Kisumu. This has recently caused concerns about its water quality and impact on aquatic organisms and human beings. This study was justified by the need to generate baseline concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in surface sediment from selected sites in the lake and determine the influence of activities on their concentrations and potential risks to fish-eating birds living near the lake. Surface sediments (<30cm) from three different fish landing beaches, located 200m from the shore of Winam Gulf of Lake Victoria near Kisumu city, Homa Bay and Mbita (control) towns, were analysed. The total mean concentrations (in pgg−1drywt) were found to range from 17.4–812 (Σdl-PCBs), 36.6–813 (ΣPCDDs) and 1.45–46.4 (ΣPCDFs). The calculated Toxic Equivalents (TEQWHO(2005)) ranged from 0.001–0.43 (Σdl-PCBs) and 0.09–31 (ΣPCDD/Fs). The fish landing beaches at Kisumu city were found to be contaminated with respect to dl-PCBs and dioxins, followed by Homa Bay and Mbita. The relatively high levels of octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) influenced the TEQ and the ΣPCDFs/ΣPCDDs ratios indicated chemical processes as partial sources of the dioxins. The levels of contaminants obtained in this study showed potential exposure to aquatic organisms and fish eating birds through food chain transfer.

Background concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in the global oceanic atmosphere.

The remote oceans are among the most pristine environments in the world, away from sources of anthropogenic persistent organic pollutants (POP), but nevertheless recipients of atmospheric deposition of POPs that have undergone long-range atmospheric transport (LRAT). In this work, the background occurrence of gas and aerosol phase polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin like polychlorinated biphenyls (dl-PCB) is evaluated for the first time in the atmosphere of the tropical and subtropical Atlantic, Pacific, and Indian oceans. Thirty-nine air samples were collected during the eight-month Malaspina circumnavigation cruise onboard the R/V Hespérides. The background levels of dioxins and dl-PCBs remained very low and in many cases very close to or below the limit of detection. Expectedly, the levels of PCBs were higher than dioxins, PCB#118 being the most abundant compound. In the particular case of dioxins, octachlorodibenzo-p-dioxin (OCDD) was the most abundant PCDD/F congener. Distribution of dl-PCB is dominated by the gas phase, while for PCDD/F the aerosol phase concentrations were higher, particularly for the more hydrophobic congeners. The Atlantic Ocean presented on average the highest PCDD/F and dl-PCB concentrations, being lower in the southern hemisphere. The assessment of air mass back trajectories show a clear influence of continental source regions, and lower concentrations when the air mass has an oceanic origin. In addition, the samples affected by an oceanic air mass are characterized by a lower contribution of the less chlorinated dioxins in comparison with the furans, consistent with the reported higher reaction rate constants of dibenzo-p-dioxins with OH radicals than those of dibenzofurans. The total dry atmospheric deposition of aerosol-bound ∑PCDD/F and ∑dl-PCB to the global oceans was estimated to be 354 and 896 kg/year, respectively.

Enhanced anaerobic biodegradation of OCDD-contaminated soils by Pseudomonas mendocina NSYSU: Microcosm, pilot-scale, and gene studies

In this study, microcosm and pilot-scale experiments were performed to investigate the capability and effectiveness of Pseudomonas mendocina NSYSU (P. mendocina NSYSU) on the bioremediation of octachlorodibenzo-p-dioxin (OCDD)-contaminated soils. The objectives were to evaluate the (1) characteristics of P. mendocina NSYSU, (2) feasibility of enhancing OCDD biodegradation with the addition of P. mendocina NSYSU and lecithin, and (3) variation in microbial diversity and genes responsible for the dechlorination of OCDD. P. mendocina NSYSU was inhibited when salinity was higher than 7%, and it could biodegrade OCDD under reductive dechlorinating conditions. Lecithin could serve as the solubilization agent causing the enhanced solubilization and dechlorination of OCDD. Up to 71 and 62% of OCDD could be degraded after 65 days of incubation under anaerobic conditions with and without the addition of lecithin, respectively. Decreased OCDD concentrations caused significant increase in microbial diversity. Results from the pilot-scale study show that up to 75% of OCDD could be degraded after a 2.5-month operational period with lecithin addition. Results from the gene analyses show that two genes encoding the extradiol/intradiol ring-cleavage dioxygenase and five genes encoding the hydrolase in P. mendocina NSYSU were identified and played important roles in OCDD degradation.

Pollution characteristics of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in PM2.5 of Hangzhou City during winter

In order to evaluate the distributions and concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in aerosol, PM2.5 samples were collected concurrently at five sites in January 2014 in Hangzhou. The analytes were analyzed with isotope dilution and high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) based on US EPA 1613B method and US EPA 1668B method. The results showed that the mass concentrations of PM2.5 were in the range of 85-168 μg/m3, which were much higher than the national quality standard. The values suggested that the PM2.5 pollution was relatively serious in Hangzhou City, yet it has been improved when compared with the results of 2004. The toxic equivalent quantities (TEQs) of PCDD/Fs in PM2.5 were in the range of 0.277-0.488 pg I-TEQ/m3, which were much higher than the results in 2004. Octachlorodibenzo-p-dioxin (OCDD) accounted for a large proportion to the total concentrations in PCDD/Fs, while 2,3,4,7,8-pentachlorodibenzofurans (2,3,4,7,8-PeC- DF) contributed the highest to the TEQ. The values of PCBs and dioxin-like PCBs (DL-PCBs) varied from 2.9-8.1 pg/m3 and 2.6-6.1 fg WHO-TEQ/m3, respectively. PCB-28 was the most abundant contributor to the concentrations of PCBs, while PCB-126 contributed the highest to the TEQ of DL-PCBs. Gas-particle distributions of PCDD/Fs and PCBs shows that PCDD/Fs were mainly distributed in the particle phase, but PCBs were preferably adsorbed in the gas phase.

Analytical Method Development for the Screening and Determination of Dioxins in Clay Matrices

Dioxin‐contaminated kaolin receives great attention by workers in the fields of environmental science, soil geology, and mining, due to its impact on the areas of health and business. The concept of “natural dioxin” formation in the clay attracts researchers to look for dioxins quantities in these soils and establish the actual route of their formation, as already proved their presence in large unjustified quantities in a number of kaolinitic soil sources and in a unique profile that denies any anthropogenic sources. On the other hand, other researches revealed the absence of dioxins in other kaolinitic sources. For rapid screening of dioxins presence an analytical method was developed basically for the determination of octachlorodibenzo‐p‐dioxin (the major dioxin congener in dioxin‐contaminated kaolin) and octachlorodibenzofuran (does not exist in dioxin‐contaminated kaolin). The method was considered as a rapid, selective, accurate and sensitive method for screening octachlorodibenzo‐p‐dioxin (OCDD) and octachlorodibenzofuran (OCDF). The method achieved linearity for OCDD/F over the range 126.5–6144.0 ng/kg dry weight (dw) with limit of quantitation of 76 ng/kg dw for OCDD and 111 ng/kg dw for OCDF. The precision (RSD%) ranged between 1.87 and 8.09% for OCDD and between 3.93 and 9.48% for OCDF. Recovery was between 85.5 and 91.1% for OCDD and between 57.9 and 64.1% for OCDF, while the accuracy for OCDD ranged from 93.8 to 97.8% and from 102.9 to 125.1% for OCDF. The developed analytical method in this research is a good alternative for known methods, because it saves time, effort, supplies, and equipments for chemical analysis. It shortens the analysis time to less than a quarter (6 h) and need less chemicals. Also it is suitable for work on a normal resolution GC/MS rather than high resolution one.