[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.

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.

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.

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.

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.

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.

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.

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).

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.

Maternally transferred dioxin-like compounds can affect the reproductive success of European eel.

Reported concentrations of dioxin-like compounds accumulated in the European eel (Anguilla anguilla) were used to perform a risk assessment for eel larval survival, taking into account a modeled amplification of tissue concentrations with a factor of 1.33 during spawning migration. The calculated concentrations of dioxin-like compounds finally deposited in the eggs were compared with the internal effect concentrations for survival of early life stages of the European eel; these concentrations, by lack of experimental data, were estimated from a sensitivity distribution based on literature data by assuming that eel larvae are among the 10% most sensitive teleost fish species. Given concentrations of dioxin-like contaminants and assuming a relatively high sensitivity, it can be expected that larvae from eggs produced by eel from highly contaminated locations in Europe will experience increased mortality as a result of maternally transferred dioxin-like contaminants. As historical persistent organic pollutant concentrations in eel tissue were higher, this impact must have been stronger in the past. Potential effects of other compounds or effects on the migration, condition, and fertility of the parental animals were not taken into account. It is important to further study the overall impact of contaminants on the reproductive success of the European eel as this may have been underestimated until now.

Serum concentrations of chlorinated dibenzo-p-dioxins, furans and PCBs, among former phenoxy herbicide production workers and firefighters in New Zealand.

PURPOSE: To quantify serum concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and dioxin-like compounds in former phenoxy herbicide production plant workers and firefighters, 20 years after 2,4,5-T production ceased. METHODS: Of 1025 workers employed any time during 1969-1984, 430 were randomly selected and invited to take part in a morbidity survey and provide a blood sample; 244 (57%) participated. Firefighters stationed in close proximity of the plant and/or engaged in call-outs to the plant between 1962 and 1987 also participated (39 of 70 invited). Reported here are the serum concentrations of TCDD and other chlorinated dibenzo-dioxins, dibenzofurans, and polychlorinated biphenyls (PCBs). Determinants of the serum concentrations were assessed using linear regression. RESULTS: The 60 men who had worked in the phenoxy/TCP production area had a mean TCDD serum concentration of 19.1 pg/g lipid, three times the mean concentration of the 141 men and 43 women employed in other parts of the plant (6.3 and 6.0 pg/g respectively), and more than 10 times the mean for the firefighters (1.6 pg/g). Duration of employment in phenoxy herbicide synthesis, maintenance work, and work as a boilerman, chemist, and packer were associated with increased serum concentrations of TCDD and 1,2,3,4,7-pentachlorodibenzo-p-dioxin (PeCDD). Employment as a boilerman was also associated with elevated serum concentrations of PCBs. CONCLUSIONS: Occupations in the plant associated with phenoxy herbicide synthesis had elevated levels of TCDD and PeCDD. Most other people working within the plant, and the local firefighters, had serum concentrations of dioxin-like compounds comparable to those of the general population.

Adsorption of polychlorinated dibenzo-p-dioxins/dibenzofurans on activated carbon from hexane.

Activated carbon is widely used to abate dioxins and dioxin-like compounds from flue gas. Comparing commercial samples regarding their potential to adsorb dioxins may proceed by using test columns, yet it takes many measurements to characterise the retention and breakthrough of dioxins. In this study, commercial activated carbon samples are evaluated during tests to remove trace amounts of dioxins dissolved in n-hexane. The solution was prepared from fly ash collected from a municipal solid waste incinerator. The key variables selected were the concentration of dioxins in n-hexane and the dosage of activated carbon. Both polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) showed very high removal efficiencies (94.7%-98.0% for PCDDs and 99.7%-99.8% for PCDFs). The presence of a large excess of n-hexane solvent had little effect on the removal efficiency of PCDD/Fs. The adsorbed PCDD/Fs showed a linear correlation (R(2) > 0.98) with the initial concentrations. Comparative analysis of adsorption isotherms showed that a linear Henry isotherm fitted better the experimental data (R(2) = 0.99 both for PCDDs and PCDFs) than the more usual Freundlich isotherm (R(2) = 0.88 for PCDDs and 0.77 for PCDFs). Finally, the results of fingerprint analysis indicated that dioxin fingerprint (weight proportion of different congeners) on activated carbon after adsorption did not change from that in hexane.

PBDEs, PCBs and PCDD/Fs in the sediments from seven major river basins in China: Occurrence, congener profile and spatial tendency.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were extensively investigated in the sediment samples collected from seven major river basins around China. The concentrations were in the range of 0.05-6.15 × 10(4) ng g(-1) dry weight (dw), 0.29-21.7 ng g(-1) dw and 0.01-6.49 ng g(-1) dw for PBDEs, PCBs and PCDD/Fs, respectively. The concentrations showed wide variations among different river basins, while the congener profiles in all the sediments were generally characterized by only a few compounds, such as BDE-209, -99 and -47, CB-11 and -28, OCDD and OCDF, etc. The spatial analysis identified a decreasing trend of these persistent organic pollutants (POPs) from south to north China, consistent with regional industrialization. However, relatively higher level of POPs was also observed in the upstream of Yellow River Basin. The present study gives insight into the spatial occurrence of the three POPs in the major river basins in China.

PCDDs, PCDFs, and PCBs co-occurrence in TiO2 nanoparticles.

In the present study, we report on the co-occurrence of persistent organic pollutants (POPs) adsorbed on nanoparticular titanium dioxide (TiO2). We report on the finding of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) on the surface of commercially available TiO2 nanoparticles, being formed during the fabrication process of the TiO2. Thereby, the samples comprise PCBs with higher congener numbers or, in the absence of PCBs, a high concentration of PCDDs and PCDFs. This new class of POPs on an active catalytic surface and the great range of applications of nanoparticular TiO2, such as in color pigments, cosmetics, and inks, give rise to great concern due to their potential toxicity.

Iron and copper catalysis of PCDD/F formation.

The formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) was explored during de novo tests designed to compare the catalytic activity of copper (II) chloride (CuCl2) with that of iron (III) oxide (Fe2O3) and to test some synergistic effect between these two catalytic compounds. Both copper chloride (CuCl2) and iron oxide (Fe2O3) were earlier proposed as catalysts to explain the PCDD/F emissions from, e.g. municipal solid waste incineration (MSWI). In addition, haematite (Fe2O3) is the main iron ore and could be responsible for the typical iron ore sintering plant fingerprint. A total of nine model fly ash (MFA) samples were prepared by mixing and grinding of sodium chloride (NaCl), activated carbon and a powder matrix of silica (SiO2) with the selected metal compound(s). The conditions of these de novo tests were 1 h in duration, 350 °C in a flow of synthetic combustion gas (10 vol.% oxygen in nitrogen). The effect of Fe-Cu catalyst concentration on yield and distribution pattern of PCDD/F was systematically explored; three strongly differing ratios of [Fe]:[Cu] were considered (1:1, 10:1 and 100:1) to study the potential interactions of Fe2O3 and CuCl2 suggested earlier. The results show some slight rise of PCDD/F formed with raising iron concentration from 0 to 10.1 wt% (no Cu added; 0.1 wt% Cu), as well as strong surging of both amount and average chlorination level of PCDD/F when rising amounts of copper (0 to 1.1 wt%) are introduced. The resulting fingerprints are compared with those from sintering and from MSWI.

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.

Catalytic decomposition of gaseous 1,2-dichlorobenzene over CuOx/TiO2 and CuOx/TiO2-CNTs catalysts: Mechanism and PCDD/Fs formation.

Gaseous 1,2-dichlorobenzene (1,2-DCBz) was catalytically decomposed in a fixed-bed catalytic reactor using composite copper-based titanium oxide (CuOx/TiO2) catalysts with different copper ratios. Carbon nanotubes (CNTs) were introduced to produce novel CuOx/TiO2-CNTs catalysts by the sol-gel method. The catalytic performances of CuOx/TiO2 and CuOx/TiO2-CNTs on 1,2-DCBz oxidative destruction under different temperatures (150-350 °C) were experimentally examined and the correlation between catalyst structure and catalytic activity was characterized and the role of oxygen in catalytic reaction was discussed. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generation during 1,2-DCBz catalytic oxidation by CuOx/TiO2-CNTs composite catalyst was also examined. Results indicate that the 1,2-DCBz destruction/removal efficiencies of CuOx (4 wt%)/TiO2 catalyst at 150 °C and 350 °C with a GHSV of 3400 h(-1) are 59% and 94% respectively and low-temperature (150 °C) catalytic activity of CuOx/TiO2 on 1,2-DCBz oxidation can be improved from 59 to 77% when CNTs are introduced. Furthermore, oxygen either in catalyst or from reaction atmosphere is indispensible in reaction. The former is offered to activate and oxidize the 1,2-DCBz adsorbed on catalyst, thus can be generally consumed during reaction and the oxygen content in catalyst is observed lost from 39.9 to 35.0 wt% after reacting under inert atmosphere; the latter may replenish the vacancy in catalyst created by the consumed oxygen thus extends the catalyst life and raises the destruction/removal efficiency. The introduction of CNTs also increases the Cu(2+)/Cu(+) ratio, chemisorbed oxygen concentration and surface lattice oxygen binding energy which are closely related with catalytic activity. PCDD/Fs is confirmed to be formed when 1,2-DCBz catalytically oxidized by CuOx/TiO2-CNTs composite catalyst with sufficient oxygen (21%), proper temperature (350 °C) and high concentration of 1,2-DCBz feed (120 ppm).