[Correlation of Persistent Free Radicals, PCDD/Fs and Metals in Waste Incineration Fly Ash].

Environmentally persistent free radicals (EPFRs) are relatively highly stable and found in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Recent studies have concentrated on model dioxin formation reactions and there are few studies on actual waste incineration fly ash. In order to study EPFRs and the correlation with dioxins and heavy metals in waste incineration fly ash, the spins of EPFRs, concentration of PCDD/Fs and metals in samples from 6 different waste incinerators were detected. The medical waste incineration fly ash from Tianjin, municipal solid waste incineration fly ash from Jiangxi Province, black carbon and slag from municipal solid waste incinerator in Lanxi, Zhejiang Province, all contained EPFRs. Above all the signal in Tianjin sample was the strongest. Hydroxyl radicals, carbon-center radicals and semiquinone radicals were detected. Compared with other samples, Jiangxi fly ash had the highest toxic equivalent quantity (TEQ) of dioxins, up to 7.229 4 ng · g⁻¹. However, the dioxin concentration in the Tianjin sample containing the strongest EPFR signals was only 0.092 8 ng · g⁻¹. There was perhaps little direct numeric link between EPFRs and PCDD/Fs. But the spins of EPFRs in samples presented an increasing trend as the metal contents increased, especially with Al, Fe, Zn. The signal strength of radicals was purposed to be related to the metal contents. The concentration of Zn (0.813 7% ) in the Tianjin sample was the highest and this sample contained much more spins of oxygen-center radicals. We could presume the metal Zn had a greater effect on the formation of EPFRs, and was easier to induce the formation of radicals with a longer half-life period.

Maternal body burdens of PCDD/Fs and PBDEs are associated with maternal serum levels of thyroid hormones in early pregnancy: a cross-sectional study.

BACKGROUND: Thyroid hormones (THs) regulate many biological functions in the human body and are essential for normal brain development. Epidemiological studies have observed diverging associations between halogenated persistent organic pollutant (POP) exposure and concentrations of THs in pregnant women and their infants. We investigated whether background exposure to polybrominated diphenyl ethers (PBDEs) is related to TH status in a Swedish population of pregnant women and their infants. Furthermore, we examined associations between polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) and TH status in early pregnancy as an extension of an earlier study focusing on late pregnancy TH status. METHODS: Free thyroxine (T4), total triiodo-thyronine (T3) and thyroid stimulating hormone (TSH) were analysed in serum from first-time mothers (N = 220-281) in the first and third trimester, and in infants (N = 115-150) 3 weeks and 3 months after delivery. Antibodies to thyroid peroxidase (anti-TPO) (N = 260) were measured in maternal third trimester serum. Maternal body burdens of PCBs (N = 281) were estimated from serum lipid PCB concentrations in late pregnancy, and PCDD/F (N = 97) and PBDE (N = 186) body burdens were estimated from concentrations in mother's milk lipids 3 weeks after delivery. Linear regression models allowed for covariate adjustment of the associations between ln-transformed POP body burdens and concentrations of TH and anti-TPO. RESULTS: Maternal body burden of BDE-153 was inversely associated with first trimester total T3, otherwise no associations between PBDEs and first and second trimester THs were observed. No associations were found between maternal PBDE body burdens and infant THs. Maternal body burden of PCDD/Fs were inversely associated with first trimester total T3. No associations were observed between PCBs and first trimester THs. Third trimester anti-TPO was not associated with maternal PCBs, PCDD/Fs and PBDEs. CONCLUSIONS: Our results suggest that maternal PCDD/F and BDE-153 body burdens influence maternal TH status in early pregnancy, which is a critical period when maternal TH status influences fetal development.

Effects of Stormwater and Snowmelt Runoff on ELISA-EQ Concentrations of PCDD/PCDF and Triclosan in an Urban River.

The aim of the study was to determine the effects of stormwater and snowmelt runoff on the ELISA EQ PCDD/PCDF and triclosan concentrations in the small urban Sokolówka River (Central Poland). The obtained results demonstrate the decisive influence of hydrological conditions occurring in the river itself and its catchment on the quoted PCDD/PCDF ELISA EQ concentrations. The lowest PCDD/PCDF values of 87, 60 and 67 ng EQ L-1 in stormwater, the river and its reservoirs, respectively, were associated with the highest river flow of 0.02 m3 s-1 and high precipitation (11.2 mm) occurred five days before sampling. In turn, the highest values of 353, 567 and 343 ng EQ L-1 in stormwater, the river and its reservoirs, respectively, were observed during periods of intensive snow melting (stormwater samples) and spring rainfall preceded by a rainless phase (river and reservoir samples) followed by low and moderate river flows of 0.01 and 0.005 m3 s-1. An analogous situation was observed for triclosan, with higher ELISA EQ concentrations (444 to 499 ng EQ L-1) noted during moderate river flow and precipitation, and the lowest (232 to 288 ng EQ L-1) observed during high river flow and high precipitation preceded by violent storms. Stormwater was also found to influence PCDD/PCDF EQ concentrations of the river and reservoirs, however only during high and moderate flow, and no such effect was observed for triclosan. The study clearly demonstrates that to mitigate the high peaks of the studied pollutants associated with river hydrology, the increased in-site stormwater infiltration and purification, the development of buffering zones along river course and the systematic maintenance of reservoirs to avoid the accumulation of the studied micropollutants and their subsequent release after heavy rainfall are required.

A primary estimate of global PCDD/F release based on the quantity and quality of national economic and social activities.

The correlations between polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) releases and factors relevant to human social-economic activities (HSEAs) were analyzed. The multiple linear regression model was successfully developed to estimate the total global PCDD/F release. The PCDD/F releases significantly correlated with population, area, GDP and GNI, suggesting that "quantity" of HSEAs have significantly contributed to the PCDD/F releases. On another aspect, advanced technologies are usually adopted in developed countries/regions, and hence reduce the PCDD/F release. The significant correlation between PCDD/F release and CO2 emission implies the potential of simultaneous reduction of CO2 emission and PCDD/F release. The total global PCDD/F release from 196 countries/regions was estimated to be 100.4 kg-TEQ yr(-1). The estimated annual PCDD/F release per unit area ranged from 0.007 to 28 mg-TEQ km(-2). Asia is estimated to have the highest PCDD/F release of 47.1 kg-TEQ yr(-1), almost half of the total world release. Oceania is estimated to have the smallest total release but the largest per-capita release. For the developed areas, such as Europe and North America, the PCDD/F release per unit GDP is lower, while for Africa, it is much higher.

Solubility enhancement of dioxins and PCBs by surfactant monomers and micelles quantified with polymer depletion techniques.

Partitioning of super-hydrophobic organic contaminants (SHOCs) to dissolved or colloidal materials such as surfactants can alter their behaviour by enhancing apparent aqueous solubility. Relevant partition constants are, however, challenging to quantify with reasonable accuracy. Partition constants to colloidal surfactants can be measured by introducing a polymer (PDMS) as third phase with known PDMS-water partition constant in combination with the mass balance approach. We quantified partition constants of PCBs and PCDDs (log KOW 5.8-8.3) between water and sodium dodecyl sulphate monomers (KMO) and micelles (KMI). A refined, recently introduced swelling-based polymer loading technique allowed highly precise (4.5-10% RSD) and fast (<24 h) loading of SHOCs into PDMS, and due to the miniaturisation of batch systems equilibrium was reached in <5 days for KMI and <3 weeks for KMO. SHOC losses to experimental surfaces were substantial (8-26%) in monomer solutions, but had a low impact on KMO (0.10-0.16 log units). Log KMO for PCDDs (4.0-5.2) were approximately 2.6 log units lower than respective log KMI, which ranged from 5.2 to 7.0 for PCDDs and 6.6-7.5 for PCBs. The linear relationship between log KMI and log KOW was consistent with more polar and moderately hydrophobic compounds. Apparent solubility increased with increasing hydrophobicity and was highest in micelle solutions. However, this solubility enhancement was also considerable in monomer solutions, up to 200 times for OCDD. Given the pervasive presence of surfactant monomers in typical field scenarios, these data suggest that low surfactant concentrations may be effective long-term facilitators for subsurface transport of SHOCs.

The influence of electrodialytic remediation on dioxin (PCDD/PCDF) levels in fly ash and air pollution control residues.

Fly ash and Air Pollution Control (APC) residues collected from three municipal solid waste incinerators in Denmark and Greenland were treated by electrodialytic remediation at pilot scale for 8-10 h. This work presents for the first time the effect of electrodialytic treatment on polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF), and how these levels impact on the valorization options for fly ash and APC residue. PCDD/PCDF levels in the original residues ranged between 4.85 and 197 ng g(-1), being higher for the electrostatic precipitator fly ash. The toxic equivalent (TEQ) varied ten fold, ranging 0.18-2.0 ng g(-1) I-TEQ, with penta and hexa-homologs being most significant for toxicity. After the electrodialytic treatment PCDD/PCDF levels increased in the residues (between 1.4 and 2.0 times). This does not mean PCDD/PCDF were synthesized, but else that soluble materials dissolve, leaving behind the non-water soluble compounds, such as PCDD/PCDF. According to the Basel Convention, PCDD/PCDF levels in these materials is low (<15 µg WHO-TEQ kg(-1)) and the fly ash and APC residue could eventually be valorized, for instance as construction material, provided end-of-waste criteria are set and that a risk assessment of individual options is carried out, including the end-of-life stage when the materials become waste again.

Tracking the Spatial Fate of PCDD/F Emissions from a Cement Plant by Using Lichens as Environmental Biomonitors.

In an area with multiple sources of air pollution, it is difficult to evaluate the spatial impact of a minor source. Here, we describe the use of lichens to track minor sources of air pollution. The method was tested by transplanting lichens from a background area to the vicinity of a cement manufacturing plant that uses alternative fuel and is located in a Natural Park in an area surrounded by other important sources of pollution. After 7 months of exposure, the lichens were collected and analyzed for 17 PCDD/F congeners. The PCDD/F profiles of the exposed lichens were dominated by TCDF (50%) and OCDD (38%), which matched the profile of the emissions from the cement plant. The similarity in the profiles was greatest for lichens located northeast of the plant (i.e., in the direction of the prevailing winds during the study period), allowing us to evaluate the spatial impact of this source. The best match was found for sites located on the tops of mountains whose slopes faced the cement plant. Some of the sites with highest influence of the cement plant were the ones with the highest concentrations, whereas others were not. Thus, our newly developed lichen-based method provides a tool for tracking the spatial fate of industrially emitted PCDD/Fs regardless of their concentrations. The results showed that the method can be used to validate deposition models for PCDD/F industrial emissions in sites with several sources and characterized by complex orography.

Experimental Solubility Approach to Determine PDMS-Water Partition Constants and PDMS Activity Coefficients.

Freely dissolved aqueous concentration and chemical activity are important determinants of contaminant transport, fate, and toxic potential. Both parameters are commonly quantified using Solid Phase Micro-Extraction (SPME) based on a sorptive polymer such as polydimethylsiloxane (PDMS). This method requires the PDMS-water partition constants, KPDMSw, or activity coefficient to be known. For superhydrophobic contaminants (log KOW >6), application of existing methods to measure these parameters is challenging, and independent measures to validate KPDMSw values would be beneficial. We developed a simple, rapid method to directly measure PDMS solubilities of solid contaminants, SPDMS(S), which together with literature thermodynamic properties was then used to estimate KPDMSw and activity coefficients in PDMS. PDMS solubility for the test compounds (log KOW 7.2-8.3) ranged over 3 orders of magnitude (4.1-5700 µM), and was dependent on compound class. For polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs), solubility-derived KPDMSw increased linearly with hydrophobicity, consistent with trends previously reported for less chlorinated congeners. In contrast, subcooled liquid PDMS solubilities, SPDMS(L), were approximately constant within a compound class. SPDMS(S) and KPDMSw can therefore be predicted for a compound class with reasonable robustness based solely on the class-specific SPDMS(L) and a particular congener's entropy of fusion, melting point, and aqueous solubility.

Dioxins and PCBs in game animals: Interspecies comparison and related consumer exposure.

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (DL-PCB) and non-dioxin-like polychlorinated biphenyls (NDL-PCB) are ubiquitous, persistent toxic compounds that are highly bioaccumulative in nature. Wild-living animals are vulnerable to the negative impacts of human activity. Dioxins and PCBs enter the animal organisms through foraging. Due to the toxicological threat, much attention is paid to these compounds worldwide. The aim of this study was to determine the dioxin contamination status of three game animal species (red deer, roe deer, and wild boar) and compare the PCDD/F and PCB congener bioaccumulation in the muscles, abdominal fat and liver. The chemical analysis was performed by the isotope dilution technique (IDMS) with high-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC/HRMS). Dioxins and PCBs were found in specimens collected from all studied species, suggesting the presence of the test compounds in the environment of the animals. The highest concentrations were found in the livers of all animals. The toxic equivalent (TEQ) levels in the muscles, adipose tissue and liver were in the order red deer > roe deer > wild boar. PCDD/Fs were the dominant congeners in TEQ value. For all tested species, the dominant contributors to the total WHO-TEQ were PCB-126, 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD. Among the PCDD/F congeners in the deer tissues, OCDD, OCDF and 2,3,4,7,8-PeCDF were dominant, while in wild boar, OCDD, 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCF occurred in the highest amounts. Among PCBs, PCB-105, 118, 156, 138, 153 and 180 were dominant in all species, but with different levels. The regular consumption of muscle meat from game animals should not cause unacceptable dioxin intake above the Tolerable Weekly Intake (TWI) value for children and adults. However, liver consumption should be avoided, especially by children and pregnant or lactating women. High consumption of contaminated liver may cause dioxin intake at levels up to 300% of TWI for adults and up to 700% TWI for children.

PCDDs, PCDFs and PCBs in farmed fish produced in Greece: Levels and human population exposure assessment.

Fish is among the essential components of Mediterranean diet and has beneficial effects on human health. Farmed fish is an affordable alternative to wild fish and a significant food export product for Greece. Published studies worldwide have reported significant levels of environmental pollutants in fish tissues. Especially for PCDDs/Fs and PCBs, the studies suggest that the most important contribution to human dietary intake is from fish and seafood. In the present study, we investigate the levels of PCDDs/Fs, dioxin-like and non dioxin-like PCBs in the most common farmed fish species produced in Greece i.e. sea bass, sea bream and rainbow trout. These species are widely consumed in Greece and are also exported to many countries worldwide. The mean levels found were WHO-PCDD/F-TEQ: 0.22 pg g(-1) wet weight (w.w.), WHO-PCDD/F-PCB-TEQ: 0.88 pg g(-1) w.w. for sea bream, WHO-PCDD/F-TEQ: 0.13 pg g(-1) w.w., WHO-PCDD/F-PCB-TEQ: 0.68 pg g(-1) w.w. for sea bass and WHO-PCDD/F-TEQ: 0.10 pg g(-1) w.w., WHO-PCDD/F-PCB-TEQ: 0.43 pg g(-1) w.w. for rainbow trout. For non dioxin-like PCBs, mean sum values found were 8.02 ng g(-1) w.w. for sea bream, 5.24 ng g(-1) w.w. for sea bass and 2.90 ng g(-1) w.w. for rainbow trout. All concentrations found were far below maximum levels set by the European Union and in the same range as wild-caught fish also presented for comparison. Daily intake from the consumption of farmed fish species examined is calculated at 1.3 pg WHO-TEQ kg(-1) b.w., which is at the lowest end of TDI values proposed by the WHO.

Estimated dietary intake and risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls from fish consumption in the Korean general population.

We analyzed 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) in samples from various fish species available at food markets in nine Korean cities. The estimated dietary intake of these chemicals was calculated from the raw concentrations of PCDD/Fs and DL-PCBs in each sample and from the food consumption of the Korean general population, and a comparison was made with the provisional tolerable monthly intake (PTMI). The average daily dietary exposure and the 95th percentile of intake of PCDD/Fs and DL-PCBs were 0.21 and 0.49 pg WHO05-toxic equivalents (TEQ) kg(-1) body weight d(-1) representing 5.27% and 12.26%, respectively, of the Korean tolerable daily intake (TDI). We applied the monthly fish consumption limits to the evaluation of improved risk assessment and concluded that unlimited consumption of most fish species does not contribute to the elevated cancer risk. This investigation was the first such large-scale study in Korea, and incorporated 37 species, including a species of whale, and 480 samples. The major aims of this study were to demonstrate the health risks associated with fish intake and to ensure food safety through total analysis of PCDD/Fs and DL-PCBs using gas chromatography/high-resolution mass spectrometry (GC-HRMS).

Abdominal Obesity and Insulin Resistance in People Exposed to Moderate-to-High Levels of Dioxin.

Obesity, a risk factor for developing metabolic complications, is a major public health problem. Abdominal obesity is strongly accompanied by a cluster of metabolic abnormalities characterized by insulin resistance. The link between persistent organic pollutants (POPs) and insulin resistance has been investigated in animal and epidemiological studies. We aimed to examine whether insulin resistance is greater in people with abdominal obesity (AO) and concomitant exposure to serum dioxins (PCDD/Fs). We conducted a cross-sectional descriptive study of 2876 participants living near a PCDD/Fs contaminated area. Seventeen 2,3,7,8-substituted PCDD/Fs congeners were measured, and then the associations between the main predictor variable, serum TEQDF-1998, abdominal obesity (AO), dependent variables, and insulin resistance were examined. Twelve of the 17 congeners, widely distributed among PCDDs, and PCDFs, had trends for associations with abdominal adiposity. In men, the highest quintiles of 1,2,3,7,8-PeCDF; 1,2,3,7,8-PeCDD; 2,3,7,8-TCDD; 2,3,7,8-TCDF; and 2,3,4,7,8-PeCDF had the top five adjusted odds ratios (AORs) + 95% confidence intervals (CIs):[4.2; 2.7-6.4], [3.6; 2.3-5.7], [3.2; 2.1-5.0], [3.0; 2.0-4.5], and [2.9; 1.9-4.7], respectively. In women, the highest quintiles of 1,2,3,4,7,8,9-HpCDF; 1,2,3,6,7,8-HxCDF; and 1,2,3,4,6,7,8-HpCDF had the top three AORs + 95% CIs:[3.0; 1.9-4.7], [2.0; 1.3-3.1], and [1.9; 1.3-2.9], respectively. After confounding factors had been adjusted for, men, but not women, with higher serum TEQDF-1998 levels or abdominal obesity had a significantly (Ptrend < 0.001) greater risk for abnormal insulin resistance. The groups with the highest joint serum TEQDF-1998 and abdominal obesity levels were associated with elevated insulin resistance at 5.0 times the odds of the groups with the lowest joint levels (AOR 5.23; 95% CI: 3.53-7.77). We hypothesize that serum TEQDF-1998 and abdominal obesity affect the association with insulin resistance in general populations.

PCDD/Fs, DL-PCBs and NDL-PCBs in European catfish from a northern Italian lake: the contribution of an alien species to human exposure.

PCDDs/Fs, DL-PCBs and NDL-PCBs are environmentally persistent substances that have been associated with adverse effects on human health. Humans are mainly exposed to these pollutants through ingestion of contaminated fish and fishery products; the consumption of fatty fish such as European catfish can contribute considerably to the intake of dioxins and PCBs. Samples of fish muscle of the top-of-the-food-chain predator Silurus glanis from the northern Italian Lake Varese were analyzed to detect the levels of 17 PCDD/F and 18 PCB congeners. All samples presented detectable levels of PCDD/Fs and PCBs, with concentrations ranging from 0.001 to 1.310pgg(-1) wet weight (w.w.) for Σ PCDD/Fs, 0.031 to 21.000pgg(-1) w. w. for Σ DL-PCBs, and 0.397 to 117.910ngg(-1) w. w. for Σ NDL-PCBs. One sample exceeded the maximum levels of 6.5pgg(-1) w. w. for the sum of PCDD/Fs and DL-PCBs set by European regulations for fish (1259/2011 EU), while other samples exceeded the action levels of 0.75pgg(-1) w. w. for the sum of PCDD/Fs, and 2pgg(-1) w. w. for the sum of DL-PCBs (277/2012 EU). Consuming contaminated catfish may pose a risk for human health, especially for the subpopulation traditionally accustomed to eating this fish, as well as sensitive individuals, such as children and pregnant women.

High temperature suppression of dioxins.

Combined Sulphur-Nitrogen inhibitors, such as sewage sludge decomposition gases (SDG), thiourea and amidosulphonic acid have been observed to suppress the de novo synthesis of dioxins effectively. In this study, the inhibition of PCDD/Fs formation from model fly ash was investigated at unusually high temperatures (650 °C and 850 °C), well above the usual range of de novo tests (250-400 °C). At 650 °C it was found that SDG evolving from dried sewage sludge could suppress the formation of 2,3,7,8-substituted PCDD/Fs with high efficiency (90%), both in weight units and in I-TEQ units. Additionally, at 850 °C, three kinds of sulphur-amine or sulphur-ammonium compounds were tested to inhibit dioxins formation during laboratory-scale tests, simulating municipal solid waste incineration. The suppression efficiencies of PCDD/Fs formed through homogeneous gas phase reactions were all above 85% when 3 wt. % of thiourea (98.7%), aminosulphonic acid (96.0%) or ammonium thiosulphate (87.3%) was added. Differences in the ratio of PCDFs/PCDDs, in weight average chlorination level and in the congener distribution of the 17 toxic PCDD/Fs indicated that the three inhibitors tested followed distinct suppression pathways, possibly in relation to their different functional groups of nitrogen. Furthermore, thiourea reduced the (weight) average chlorinated level. In addition, the thermal decomposition of TUA was studied by means of thermogravimetry-fourier transform infrared spectroscopy (TG-FTIR) and the presence of SO2, SO3, NH3 and nitriles (N≡C bonds) was shown in the decomposition gases; these gaseous inhibitors might be the primary dioxins suppressants.

Bioaccumulation of mercury and polychlorinated dibenzo-p-dioxins and dibenzofurans in salty water organisms.

Mercury and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) accumulate in organisms through food webs and exert potentially toxic effects on aquatic organisms and humans. This study examined the levels of mercury and PCDD/Fs in organisms and sediment samples collected from a saltwater pond at the An-Shun site, a chloralkali factory that shut down in Tainan City, Taiwan. It was also a pentachlorophenol production plant. After the factories were shut down in the 1980s, mercury and PCDD/Fs contamination remained, posing severe health hazards. The correlation between PCDD/Fs congener accumulation patterns in distinct fish organs and the sediment was evaluated. Mercury and PCDD/Fs levels in all the fish samples exceeded food safety limits, and the concentrations of mercury and PCDD/Fs in each species were closely correlated (n = 12, Spearman's rank correlation [R] = 0.811, p < 0.01). The mercury concentrations were positively but non-significantly correlated with the weight (n = 11, R = 0.741, p < 0.01) and length (n = 11, R = 0.618, p < 0.05) of the species. The fish likely accumulated the contaminants through ingestion of other organisms or the sediment. However, after the pollutants entered a fish, they exhibited distinct accumulation patterns because of their differing chemical properties. Specifically, the mercury concentration was correlated with organism weight and length, whereas the PCDD/Fs concentration was associated with organ lipid content. The study results are valuable for assessing the health risks associated with ingesting mercury- and PCFF/F-contaminated seafood from the study site.

Optimized efficiency of mapping a site contaminated with dioxins by immunoassay compared to gas chromatography-high resolution mass spectrometry.

The use of an enzyme-linked immunosorbent assay (ELISA) to screen for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) has shown promise as a complementary tool to gas chromatography-high resolution mass spectrometry (GC-HRMS). This is especially true due to its low cost, ease of sample preparation and fast sample turnaround time. One problem that was unaddressed by other research is how to increase the efficiency of ELISA to a point that makes it practical for the analysis of large groups of samples that can have a wide range of unknown PCDD/F concentrations; one ELISA test is unable to screen for PCDD/F concentrations that can range anywhere from background levels to upwards of 10,000 picograms toxic equivalents per gram of soil (pgTEQ g(-1)). This paper resolves this problem by introducing a sample algorithm which enables the correct amount of dioxin to enter an ELISA tube from a sample (whose unknown PCDD/F concentration can range between 30 and 10,500 pgTEQ g(-1)) in only two ELISA runs. In doing so, the time and cost benefits of ELISA are preserved. ELISA results for soils and sediment samples processed using the algorithm were then plotted on two site maps alongside their GC-HRMS counterparts. A comparison of both analytical methods showed that areas of high and low PCDD/F concentrations were equally identifiable with either analytical tool; 29 of 32 sample locations on the site maps were placed into the same of three possible screening levels. Therefore, processing ELISA samples through the sample algorithm achieves the necessary level of efficiency while producing virtually equal screening results in comparison to GC-HRMS but at a fraction of the cost. The agreement between GC-HRMS and ELISA was 94% (R (2) = 0.99, n = 53). GC-HRMS and ELISA results were significantly correlated (Wilcoxon signed rank test p < 0.001).

Continuous sampling of MSWI dioxins.

Municipal solid waste incineration (MSWI) is generally considered as a well-controlled source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in brief dioxins. Start-up conditions continue, however, to be problematic. A self-developed continuous sampler was specially designed and built to fulfill the various sampling criteria of U.S. EPA Method 23 and monitor the trends of dioxins emissions during diverse operating conditions. In the MSWI plant investigated, a 98.1% TEQ PCDD/F removal efficiency was achieved in normal operation using activated carbon injection + bag filtration (ACI + BF) and the corresponding PCDD/F emission remains well below the standard set by Taiwan EPA (0.1 ng I-TEQ/Nm(3) @ 11% O2). During start-up, however, continuous sampling indicates that this limit value is reached only after 12 and 9 days, respectively for the 1st (2011) and 2nd test campaign (2012). Only 15 days after start-up the PCDD/F emissions shrunk to the levels typically measured during normal operation. The PCDD/F emissions from the 1st and 2nd continuous sampling campaigns were 5.4 and 5.5 mg I-TEQ, respectively. Short-term PCDD/F sampling such as the U.S. EPA Method 23 is less adapted to monitor these transient PCDD/F emissions representatively and accurately, due to a steady decrease of PCDD/F emissions after start-up. This self-developed continuous sampler effectively enhances the ease and reliability of emission data collecting during transient conditions of MSWI.

PCDDs, PCDFs and PCNs in products of microwave-assisted pyrolysis of woody biomass--Distribution among solid, liquid and gaseous phases and effects of material composition.

Microwave-assisted pyrolysis (MAP) of lignocellulosic biomass is a technique that could potentially be used to produce and upgrade renewable energy carriers. However, there is no available information about the formation of dioxins and other organic pollutants in MAP treatment of woody biomass. In this study, MAP experiments were conducted in lab-scale using virgin softwood, bark, and impregnated wood as feedstocks. The non-condensable gas, liquid (fractionated into aqueous and oil phases), and char fractions generated during pyrolysis were collected and analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs). The concentrations of PCDDs, PCDFs and PCNs in the pyrolysis products ranged from 0.52 to 43.7 ng kg(-1). All investigated compound groups were most abundant in the oil fraction, accounting for up to 68% (w/w) of the total concentrations. The highest PCDD, PCDF and PCN concentrations were found from the pyrolysis of bark, which has relatively high contents of chlorine and mineral matter, followed by impregnated wood, which contains organic and metal-based preservatives. The homologue profiles of all three compound groups were dominated by the less chlorinated homologues. The homologue abundance decreased as the degree of chlorination increased. This trend was observed for all three feedstocks.

The role of CuCl on the mechanism of dibenzo-p-dioxin formation from poly-chlorophenol precursors: A computational study.

A computational study is performed for the elucidation of the role played by CuCl in the condensation of two polychlorophenol molecules to yield PCDDs. The mechanism found consists of six sequential steps, which allow the final recuperation of the CuCl molecule, and applies for phenol molecules with an ortho chlorine. In the temperature range of 453-473 K (previously reported as adequate to diminish PCDDs formation in the post-combustion area), CuCl is able to softly retain chlorophenol molecules, mainly those less chlorinated. After a first HCl release, Cu(I) remains bonded to phenol oxygen atom, thus avoiding the formation of phenoxy radicals and the subsequent radical processes. A temperature raise up to 1200 K destabilizes the initial CuCl-chlorophenol complexes and causes that the rate limiting step change from the formation of the first oxygen bridge to HCl elimination. It has been checked that tetra and penta-chlorophenols undergo essentially the same reaction process of 2-chlorophenol. In view of our results and trying to arrive at a practical way to diminish the rate of formation of PCDDs, we propose that an extra addition of powdered CuCl to the post-combustion zone, cooled down to temperatures lower than 473 K, could act as an inhibitor in the formation of these pollutants.

Changing sources of polychlorinated dibenzo-p-dioxins and furans in sediments and ecological risk for nekton in the lower Passaic River and Newark Bay, New Jersey, USA.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were measured in sediments (surface and deeper sediments) and porewater of the lower Passaic River and Newark Bay (New Jersey, USA) to apportion their sources and conduct an ecological risk assessment. Positive matrix factorization was applied to identify sources of PCDD/Fs. Five source profiles were extracted from the positive matrix factorization model applied to the sediment samples including chloranil, combustion, polychlorinated biphenyl impurities, mixed urban sources, and the historical contamination from the former Diamond Alkali plant. The ecological risk assessment was estimated using several lines of evidence depending on site-specific data (blue crab and fish samples representing different feeding habits and positions in the trophic wood web of the river). Porewater concentrations gave the best estimates of lipid concentrations especially in the blue crab samples (with an average factor difference of 3.8). Calculated hazard quotients (HQs) for the fish samples and blue crab were >1 based on the no-effect concentration and tissue screening concentration approaches. At the same time, calculated porewater toxic units were >1. Sediment concentrations exceeded the published sediment quality guidelines for the protection of fish and benthic species, indicating the existence of significant risk to the aquatic life in the Passaic River. Accordingly, further actions and control measures are needed to reduce the emission of PCDD/Fs from ongoing sources.