PCDD/F formation from oxy-PAH precursors in waste incinerator flyash

The yield of PCDD/F in relation to the presence of oxygenated PAH in model waste incinerator flyash has been investigated in a fixed bed laboratory scale reactor. Experiments were undertaken by thermal treatment of the model flyash at 250 and 350 °C under a simulated flue gas stream for 2 h. After reaction, the PCDD/F content of the reacted flyash and the PCDD/F released into the exhaust gas, and subsequently trapped by XAD-II resin in a down-stream condensation system were analyzed. The PAHs investigated were, dibenzofuran and benzo[b]naphtho[2,3-d]furan and were spiked onto the model flyash as reactant precursors for PCDD/F formation. The results showed significant formation of furans from both of the PAH investigated, however except from some highly chlorinated dioxin congeners, the formation of dioxins was not so common. Benzonaphthofuran was significantly more reactive than dibenzofuran in PCDD/F formation, in spite of the fact that dibenzofuran is structurally more similar to that of PCDD/F. Thus, there was no clear attribution between the chemical structure of PAH used and the formation of PCDD/F. There were considerable differences between the yields of PCDD/F congeners in the gaseous species and those in the reacted flyash under the same operational conditions. The concentration of PCDD/Fs was reduced at the higher reaction temperature of 350 °C; however, the higher temperature resulted in the majority of the PCDD/F formed on the flyash being released into the gas phase.     

Evaluation of PCDD/F congener distributions in MWI flue gas treated with SCR catalysts

Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m³, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m³. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.     

Destruction of PCDD/Fs by SCR from flue gases of municipal waste incinerator and metal smelting plant

Partitioning of PCDD/F congeners between vapor/solid phases and removal and destruction efficiencies achieved with selective catalytic reduction (SCR) system for PCDD/Fs at an existing municipal waste incinerator (MWI) and metal smelting plant (MSP) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP, operating temperature: 230 degrees C), wet scrubbers (WS, operating temperature: 70 degrees C) and SCR (operating temperature: 220 degrees C) as major air pollution control devices (APCDs). PCDD/F concentration measured at stack gas of the MWI investigated is 0.728 ng-TEQ/Nm(3). The removal efficiency of WS+SCR system for PCDD/Fs reaches 93% in the MWI investigated. The MSP investigated is equipped with EP (operating temperature: 240 degrees C) and SCR (operating temperature: 290 degrees C) as APCDs. The flue gas sampling results also indicate that PCDD/F concentration treated with SCR is 1.35 ng-TEQ/Nm(3). The SCR system adopted in MSP can remove 52.3% PCDD/Fs from flue gases (SCR operating temperature: 290 degrees C, Gas flow rate: 660 kN m(3)/h). In addition, the distributions of PCDD/F congeners observed in the flue gases of the MWI and MSP investigated are significantly different. This study also indicates that the PCDD/F congeners measured in the flue gases of those two facilities are mostly distributed in vapor phase prior to the SCR system and shift to solid phase (vapor-phase PCDD/Fs are effectively decomposed) after being treated with catalyst. Besides, the results also indicate that with SCR highly chlorinated PCDD/F congeners can be transformed to lowly chlorinated PCDD/F congeners probably by dechlorination, while the removal efficiencies of vapor-phase PCDD/Fs increase with increasing chlorination.     

Analysis of polychlorinated dibenzo-p-dioxins and furans in various aqueous samples in Taiwan

Twenty-one fresh water samples were taken from reservoirs, wells and drinking water treatment plants in Taiwan for measurement of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) concentrations. Due to low concentration of PCDD/Fs, water samples (400-1000 L) were collected by using the on-site large volume pre-concentration system and analyzed by high resolution gas chromatography (HRGC)/high resolution mass spectrometer (HRMS). Different characteristics of dioxin profiles in surface water and groundwater are observed. The PCDD/F concentrations in fresh water samples varied from 0.001 to 0.265 pg WHO₉₈-TEQ/L which are lower than the standard (12 pg WHO₉₈-TEQ/L) set by the Taiwan Environmental Protection Administration (TEPA) for drinking water. Only a small fraction (<5%) of the total PCDD/F concentration in fresh water samples was water-soluble. As a result of their hydrophobicity, PCDD/Fs are effectively removed along with suspended solid via the water treatment process (average 98% removal efficiency).     

Removal of PCDD/Fs from contaminated sediment and released effluent gas by charcoal in a proposed cost-effective thermal treatment process

A novel cost-effective thermal treatment technology has been proposed for the removal of PCDD/Fs from contaminated sediment and released effluent gas using charcoal as both an adsorbent and a thermal source. When a reactor was used for thermal treatment, the PCDD/Fs removal efficiency exceeded 98% from the sediment at the three different air superficial velocities employed in this study. The total PCDD/F international toxic equivalent (I-TEQ) contents, both in the treated sediments and effluent gas, were below the Japanese emission standard limit. Analysis of the PCDD/F contents in different fractions showed that large quantities of PCDDs but not PCDFs were evaporated from the sediment and adsorbed in the moist sediment column. This difference was attributed to the formation of PCDDs from pentachlorophenol (PCP) during the cooling process following the thermal treatment process in the reactor. This proposed thermal process provides a promising alternative to the conventional methods.     

Analysis of PCDD/Fs and dioxin-like PCBs in atmospheric deposition samples from the Flemish measurement network: Optimization and validation of a new CALUX bioassay method

Since the CALUX (Chemically Activated LUciferase gene eXpression) bioassay is a fast, sensitive and inexpensive tool for the analysis of a high number of samples, validation of new methods is urgently needed. In this study, a new method for the analysis of PCDD/Fs and dioxin-like PCBs in atmospheric deposition samples with the CALUX bioassay was developed, optimized and validated. The method consists of 4 steps: filtration, extraction, clean up and bioassay analysis. To avoid the use of large amounts of toxic solvents, new techniques were used for filtration and extraction: a C18 filter was used instead of a liquid/liquid extraction and an Accelerated Solvent Extractor (ASE) was used instead of the traditional soxhlet extraction. After pre-oxidation of the sample extract, clean up was done using a multi-layer silica gel column coupled to a carbon column. The PCDD/F and PCB fractions were finally analyzed with the H1L7.5c1 and/or the H1L6.1c3 mouse hepatoma cell lines. The limit of quantification was 1.4 pg CALUX-BEQ m⁻² d⁻¹ for the PCBs and 5.6 pg CALUX-BEQ m⁻² d⁻¹ for the PCDD/Fs, when using the new sensitive H1L7.5c1 cell line. The GC-HRMS recovery for all PCDD/F congeners was between 55% and 112%, with a mean recovery of 90%. CALUX recoveries of spiked procedural blanks were between the accepted ranges of 80-120%. Repeatability and reproducibility were satisfactory and no interferences from metals were detected. The first results from the Flemish measurement program showed good correlation between CALUX and GC-HRMS.     

Formation of dioxins during exposure of pesticide formulations to sunlight

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n = 2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n = 1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57 000 μg ∑PCDD/F kg⁻¹) as well as the 2,4-D formulation (by 3000%, to 140 μg ∑PCDD/F kg⁻¹). TEQ also increased by up to 980%, to a maximum concentration of 28 μg kg⁻¹ in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum⁻¹, contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.     

Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) from a refinery process for zinc oxide used in feed additives: a source of dioxin contamination in Chilean pork

The Republic of Korea found dioxin at concentrations exceeding the Korean maximum residue limit (MRL) in pork (2 pg TEQ g⁻¹ fat) imported from Chile in June 2008. Korea and Chile collaborated and investigated to find out the sources of contamination. An isotope dilution method and high resolution gas chromatography/mass spectrometry (HR-GC/MS) were used for the analysis of PCDD/Fs. PCDD/Fs were found from 2.17 to 36.7 pg TEQ g⁻¹ fat from Chilean pork. 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF were found as the major congeners in pork samples. 2,3,4,7,8-PeCDF showed the highest concentration and contributed about 30% among the congeners in most of the samples. 2,3,7,8-TCDD, 1,2,3,7,8,9-HxCDD, OCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 1,2,3,7,8,9-HxCDF, and OCDF were not detected or exist at background levels in the less contaminated samples. Remarkably high concentrations of PCDD/Fs were found in samples of zinc oxide (17 147 pg TEQ g⁻¹), zinc oxide based premix (6673 pg TEQ g⁻¹), and the residue crust (800 pg TEQ g⁻¹) in a mixing chamber in the feed mill. From the results of various investigations, this case concluded that zinc oxide in the feed was the major source of the dioxin contamination in pork. The dioxins were formed from a metal refinery process to collect zinc oxide.     

Simultaneous removal of PCDD/Fs and mercury by activated carbon from a full-scale MSW incinerator in southeast China

This study emphasized on the removal performance of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and mercury by different activated carbon injection (ACI) rates from a full-scale (700 t/d) MSW incinerator. The result exhibited that the emission standard of PCDD/Fs and mercury could be met when the ACI rate reached 50 mg/Nm³ and 30 mg/Nm³, respectively. Lower chlorinated PCDD/Fs and PCDFs showed higher removal efficiencies compared with highly chlorinated PCDD/Fs and PCDDs, which could be attributed to the larger competitiveness of highly volatile congeners in AC adsorption than the lower volatile ones. AC turned out to have different adsorption selectivity for CP-routes PCDD/Fs congeners, among which 1379-TCDD was preferred to be absorbed while others exhibited little or poor selectivity for AC adsorption. The removal efficiency of PCDD/Fs was positively correlated with ACI rate at 99% confidence interval with a linear relationship (R²?=?0.98). Also, the outlet concentration of mercury decreased with the increase of ACI rate in a nearly linear function (R²?=?0.96). These results will be meaningful for the rational use of AC for pollutants control.

     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Partitioning and removal of dioxin-like congeners in flue gases treated with activated carbon adsorption

Activated carbon adsorption is commonly used to control dioxin-like congener (PCDD/Fs and PCBs) emissions. Partitioning of PCDD/Fs and PCBs between vapor and solid phases and their removal efficiencies achieved with existing air pollution control devices (APCDs) at a large-scale municipal waste incinerator (MWI) and an industrial waste incinerator (IWI) are evaluated via intensive stack sampling and analysis. Those two facilities investigated are equipped with activated carbon injection (ACI) with bag filter (BF) and fixed activated carbon bed (FACB) as major PCDD/F control devices, respectively. Average PCDD/F and PCB concentrations of stack gas with ACI+BF as APCDs are 0.031 and 0.006ng-TEQ/Nm(3), and that achieved with FACB are 1.74 and 0.19ng-TEQ/Nm(3) in MWI and IWI, respectively. The results show that FACB could reduce vapor-phase PCDD/Fs and PCBs concentrations in flue gas, while the ACI+BF can effectively adsorb the vapor-phase dioxin-like congener and collect the solid-phase PCDD/Fs and PCBs in the meantime. Additionally, the results of the pilot-scale adsorption system (PAS) experimentation indicate that each gram activated carbon adsorbs 105-115ng-PCDD/Fs and each surface area (m(2)) of activated carbon adsorbs 10-25ng-PCDD/Fs. Based on the results of PAS experimentation, this study confirms that the surface area of mesopore+macropore (20-200A) of the activated carbon is a critical factor affecting PCDD/F adsorption capacity.     

Atmospheric bulk deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of an iron and steel making plant

An IRA-743 resin bulk sampler was validated to monitor long-term bulk deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Six consecutive sampling campaigns (2008-2009) were conducted at four sites around steel complexes in Pohang, South Korea to investigate spatial and seasonal variations of PCDD/F bulk deposition. The bulk deposition within the steel complex showed the highest ∑_4-8PCDD/F (Tetra-Octa) fluxes, ranging from 204 to 608 (mean: 352) pg m⁻² d⁻¹, indicating steel complexes were major sources of PCDD/Fs. The homologue profiles were dominated with lower chlorinated PCDFs. Furthermore, the prevailing winds were confirmed to influence the spatial distribution of PCDD/F deposition. There were apparent seasonal variations of the bulk deposition at each site, and seasonal homologue patterns of PCDD/Fs were clearly observed. According to the passive air sampling, however, no significant seasonal change of ambient air concentrations of PCDD/Fs was observed. Therefore, it was concluded that the seasonal variations of deposition fluxes of PCDD/Fs probably resulted from temperature-dependent gas/particle partitioning.     

Evaluation of the emission characteristics of PCDD/Fs from electric arc furnaces

Distribution of PCDD/F (polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran) congeners at two electric arc furnaces (EAFs) in Taiwan is evaluated via intensive stack sampling and analysis. Two kinds of exhaust system in EAFs including stack system and shutter system are selected for measuring dioxin emissions. In addition, dioxin emissions during oxidation and reduction stages at EAF-A were characterized. Results indicate that the PCDD/F concentration of stack gas in EAF-A was 4.39 ng/N m³ while total Toxic Equivalent Quantity (TEQ) concentration was 0.35 ng I-TEQ/N m³. The PCDD/F concentration of stack gas in EAF-B was 2.20 ng/N m³ and the TEQ concentration was 0.14 ng I-TEQ/N m³. 1,2,3,4,6,7,8-H_pCDF, OCDD and OCDF are the major contributors of the dioxin concentrations for two EAFs investigated and the percentage of PCDD/F in particulate phase increases as the chlorination level of the PCDD/F congener increases. The results obtained on gas/particulate partitioning of PCDD/Fs in flue gases prior to the APCD in EAFs indicate that more than 90% exists in particulate phase. In EAF-A, the PCDD/F concentration during oxidation stage is slightly higher than that measured during reduction stage, including the sampling points of CO converter outlet, prior to bag filter and stack. Majority of PCDD/Fs emitted from steel-making processes exists in particulate-phase (about 60–70%) at both EAFs investigated.     

Thermal removal of PCDD/Fs from medical waste incineration fly ash--effect of temperature and nitrogen flow rate

The fly ash used in this study was collected from a bag filter in a medical waste rotary kiln incineration system, using lime and activated carbon injection followed by their collection as mixed fly ash. Experiments were conducted on fly ash in a quartz tube, heated in a laboratory-scale horizontal tube furnace, in order to study the effect of temperature and nitrogen flow rate on the removal of PCDD/Fs. Results indicated that in this study PCDD/Fs in the fly ash mostly were removed and desorbed very little into the flue gas under thermal treatment especially when the heating temperature was higher than 350 °C, and dechlorination and destruction reactions took important part in the removal of PCDD/Fs. However, in terms of flow rate, when flow rate was higher than 4 cm s⁻¹, destruction efficiency of PCDD/Fs decreased dramatically and the main contributors were P₅CDF, H₆CDF and H₇CDF desorbed to flue gas, the PCDD/Fs in the fly ash decreased with enhanced flow rate.     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm³. In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.     

Estimation and characterization of PCDD/Fs and dioxin-like PCBs from Chinese iron foundries

The iron foundry industry is considered to be a potential source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study investigated the emission factors and total emission amounts of PCDD/Fs and dioxin-like polychlorinated biphenyls (DL-PCBs) from iron foundries in China. The concentrations and the World Health Organization toxicity equivalents (WHO-TEQs) are presented and the congener profiles are discussed in this paper.In the present work, 26 fly ash samples were collected and tested to quantify the PCDD/Fs and DL-PCBs generated by 14 plants of different scales, and five stack gas samples were collected from two (named as EFG and LFG) of those plants. The emission levels of PCDD/Fs and DL-PCBs indicated that hot-air cupolas had lower emissions than cold-air cupolas. When iron ore lump and sinter were used as raw material, the emission factors were about 250 ng TEQ t⁻¹ of product. However, if the raw material was scrap, the emission factors varied owing to the different contents of organic materials in the raw materials. It was found that the mean WHO-TEQ values of PCDD/Fs and DL-PCBs were 144 and 34.2 pg Nm⁻³ in stack gas and 20.0 and 1.58 pg g⁻¹ in fly ash. In multiple tests, it was estimated that the mean emission factors of PCDD/Fs and DL-PCBs were 365 and 10.9 ng WHO-TEQ t⁻¹ released to residue and 2719 and 555 ng TEQ t⁻¹ released to air. The total emission amounts of PCDD/Fs and DL-PCBs from Chinese iron foundries with cupola furnaces released to residue and air were 16.8 and 146 g WHO-TEQ in 2008, respectively.     

Emission characterization of unintentionally produced persistent organic pollutants from iron ore sintering process in China

Emission of unintentionally produced persistent organic pollutants (Unintentional POPs), including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychorinated biphenyls (PCBs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz), were investigated in four typical iron ore sintering plants in China. The emission factors and annual mass releases of the Unintentional POPs were calculated. The results indicated that PCDFs contributed more than 60% to the overall toxic equivalent quantity (TEQ) values, while the contribution of the dl-PCBs is relatively low, and only in the range of 8-9%. The dominant congeners of PCDD/Fs and dl-PCBs contributing most to the total TEQ were 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126. With regard to the TEQ contributions, the most abundant homologues were PeCDFs and HxCDD/Fs, followed by PeCDDs and non-ortho dl-PCB, whereas HpCDD/Fs, OCDD/Fs and mono-ortho dl-PCBs almost made no contributions. Due to the massive use of recycled waste in the feeding materials, the average emission factor of PCDD/Fs and dl-PCBs of the four plants was 3.95 μg WHO-TEQ ton⁻¹. Based on the results, the annual release of PCDD/Fs and dl-PCBs in 2007-2009 were estimated to be 2070 g, 2212 g, and 2307 g WHO-TEQ, respectively.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.