Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Guangzhou,China

Atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was investigated at four locations, namely at Yuancun, Wushan, Haizhu and Changban in Guangzhou City, Guangdong Province. The annual deposition fluxes of tetra- to octa-CDD/Fs (total PCDD/Fs) were found to range from 170 to 3000 (mean 1500) pg m⁻² day⁻¹, and the fluxes of total 2, 3, 7, 8-substituted PCDD/F congeners ranged from 2.1 to 41 (mean 20) pg WHO-TEQ m⁻² day⁻¹ at Wushan. The average deposition fluxes of total 2, 3, 7, 8-substituted PCDD/F congeners in rainy season were found to be 37, 27 and 28 pg WHO-TEQ m⁻² day⁻¹ at Yuancun, Haizhu and Changban, respectively, and the PCDD/F deposition fluxes behaved obviously higher in rainy season than in dry season. Results from regression analysis showed that number of rainy days, the amount of wet precipitation, PCDD/F concentrations in particles and organic carbon content played important roles in the variation of PCDD/F deposition fluxes. Monthly average temperatures change little over the year. Therefore, it only played a minor role in monthly variation of PCDD/F deposition fluxes. Particle deposition fluxes were generally not considered as the factor that could cause the differences in PCDD/F deposition fluxes between rainy and dry season, but were found to be related with PCDD/F deposition fluxes in rainy season or dry season. It was found that the profiles of PCDD/F homologs or congeners in the samples were the same either spatially or temporally, indicating that the PCDD/F emission sources were similar to one another. The similarities in PCDD/F homolog patterns and the differences in deposition fluxes between samples collected from heavy-traffic roadside and nearby residence house roof indicated that vehicle exhaust might be an important source for PCDD/F in Guangzhou. PCDD/F concentrations and profiles of PCDD/F homologs in atmospheric deposition were compared with those in both total suspended particles in air and soils, and conclusions indicated that atmospheric deposition possibly tended to remove lower-chlorinated DD/Fs from air and was one of sources for PCDD/Fs in soils.     

Identifying source regions for the atmospheric input of PCDD/Fs to the Baltic Sea

PCDD/F contamination of the Baltic Sea has resulted in the European Union imposing restrictions on the marketing of several fish species. Atmospheric deposition is the major source of PCDD/Fs to the Baltic Sea, and hence there is a need to identify the source regions of the PCDD/Fs in ambient air over the Baltic Sea. A novel monitoring strategy was employed to address this question. During the winter of 2006–2007 air samples were collected in Aspvreten (southern Sweden) and Pallas (northern Finland). Short sampling times (24 h) were employed and only samples with stable air mass back trajectories were selected for analysis of the 2,3,7,8-substituted PCDD/F congeners. The range in the PCDD/F concentrations from 40 samples collected at Aspvreten was a factor of almost 50 (range 0.6–29 fg TEQ/m³). When the samples were grouped according to air mass origin into seven compass sectors, the variability was much lower (typically less than a factor of 3). This indicates that air mass origin was the primary source of the variability. The contribution of each sector to the PCDD/F contamination over the Baltic Sea during the winter half year of 2006/2007 was calculated from the average PCDD/F concentration for each sector and the frequency with which the air over the Baltic Sea came from that sector. Air masses originating from the south–southwest, south–southeast and east segments contributed 65% of the PCDDs and 75% of the PCDFs. Strong correlations were obtained between the concentrations of most of the PCDD/F congeners and the concentration of soot. These correlations can be used to predict the PCDD/F concentrations during the winter half year from inexpensive soot measurements.     

Baseline soil levels of PCDD/Fs established prior to the construction of municipal solid waste incinerators in China

In order to determine the baseline contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in different areas in China, prior to the construction of municipal solid waste incinerators (MSWIs), a total of 32 representative soil samples was collected near 16 incinerators and analyzed for their PCDD/F concentrations. The PCDD/F baseline concentrations in the soil samples ranged from 0.32 to 11.4 ng I-TEQ kg⁻¹ (dry matter), with average and median value of 2.73 and 2.24 ng I-TEQ kg⁻¹ (dry matter), respectively, and a span between maximum and minimum recorded value of 36. The PCDD homologues predominated in 26 out of 32 soil samples, with the ratio (PCDDs)/(PCDFs) ranging from 1.1 to 164; however in the other 6 samples, PCDF homologues were larger, with the same ratio varying from 0.04 to 0.8. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used to examine PCDD/F amount and profile in these soil samples, and their possible associations with known emission sources: in this process 6 really distinct isomer fingerprints were identified. Background PCDD/F levels and profiles were comparable to those found in soils from China and other countries and indicate a rather low baseline PCDD/F contamination of soils. The present data provide the tools for future assessment of a possible impact of these MSWIs.     

Dioxins,furans and polycyclic aromatic hydrocarbons emissions from a hospital and cemetery waste incinerator

An experimental campaign was carried out on a hospital and cemetery waste incineration plant in order to assess the emissions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polycyclic aromatic hydrocarbons (PAHs). Raw gases were sampled in the afterburning chamber, using a specifically designed device, after the heat recovery section and at the stack. Samples of slags from the combustion chamber and fly ashes from the bag filter were also collected and analyzed. PCDD/Fs and PAHs concentrations in exhaust gas after the heat exchanger (200–350 °C) decreased in comparison with the values detected in the afterburning chamber. Pollutant mass balance regarding the heat exchanger did not confirm literature findings about the de novo synthesis of PCDD/Fs in the heat exchange process. In spite of a consistent reduction of PCDD/Fs in the flue gas treatment system (from 77% up to 98%), the limit of 0.1 ng ITEQ Nm⁻³ at the stack was not accomplished. PCDD/Fs emission factors for air spanned from 2.3 up to 44 μg ITEQ t⁻¹ of burned waste, whereas those through solid residues (mainly fly ashes) were in the range 41–3700 μg ITEQ t⁻¹. Tests run with cemetery wastes generally showed lower PCDD/F emission factors than those with hospital wastes. PAH total emission factors (91–414 μg kg⁻¹ of burned waste) were in the range of values reported for incineration of municipal and industrial wastes. In spite of the observed release from the scrubber, carcinogenic PAHs concentrations at the stack (0.018–0.5 μg Nm⁻³) were below the Italian limit of 10 μg Nm⁻³.     

Polycyclic aromatic hydrocarbons in Costa Rican air and soil: A tropical/temperate comparison

Surface soil and passive air samples from a network of 23 sampling sites across Costa Rica were analyzed for polycyclic aromatic hydrocarbons (PAHs), allowing for an evaluation of absolute levels, spatial distribution patterns, air/soil concentration (A/S) ratios and relative composition. Annual mean concentrations of four-ring PAHs in air were low (median of approximately 40 pg m⁻³), except in Costa Rica's densely populated central valley (approximately 650 pg m⁻³). PAH concentrations in soil were also low (median of 5 ng g⁻¹ dry weight) and comparable to those reported for other tropical regions. These low soil concentrations result in A/S ratios of four-ring PAHs in Costa Rica that are higher than the equilibrium air–soil partitioning coefficients and also higher than A/S ratios reported for temperate locations. A series of model calculations of increasing complexity were used to seek an explanation for variable A/S ratios of PAHs under tropical and temperate conditions. Temperature-driven changes in air–soil partitioning and differences in PAH degradability under temperate and tropical conditions are insufficient to explain the higher soil concentrations and lower A/S ratios in temperate regions. However, these can be explained by atmospheric deposition of PAHs during historical periods of much higher emissions and air concentrations and by persistence of PAHs in soils on the order of decades. Low PAH concentrations in tropical soils were found to be consistent with constant or increasing emissions, and in particular, do not require that degradation rates in soil are much faster than in temperate areas. In comparison to temperate soils, soils from Costa Rica and other tropical regions have a higher relative abundance of the lighter PAHs. This likely reflects a higher source contribution from biomass burning in the tropics, as well as the preferential loss of lighter PAHs from temperate soils that experienced high PAH deposition in the past.     

Arsenic Background Concentrations in Florida,U.S.A. Surface Soils: Determination and Interpretation

Background concentrations of soil arsenic have been used as an alternative soil cleanup criterion in many states in the U.S. This research addresses issues related to the interpretation of background concentrations of arsenic in near pristine soils in Florida. Total arsenic was measured in 448 taxonomic and geographic representative surface soil samples using USEPA Method 3052 (HCl-HNO₃-HF, microwave digestion) and graphite furnace atomic absorption spectrophotometry analysis procedure. Values were log-normally distributed, with geometric mean and baseline concentration (defined as 95% of the expected range of background concentrations) providing the most satisfactory statistical results. An upper baseline concentration of 6.21 mg As/kg was estimated for undisturbed soils (n = 267) compared to 7.63 mg As/kg for disturbed soils (n = 181). Temporal trend of total soil arsenic concentrations from 1967 to 1989 paralleled decreased usage of arsenic in U.S. agriculture. Soil arsenic background concentrations were generally higher in south Florida than in north and central Florida, and associated with wet soils. Individual high arsenic sites were scattered throughout the state, but the most highly concentrated of these occurred in the Leon-Lee belt along the Ocala uplift district extending to the southwestern flatwoods district. Extrapolation of the data using a single arsenic value regardless of the taxonomic and geographical differences in soil arsenic distribution would underestimate potential arsenic contamination in upland soils.     

Assessment of variations in atmospheric PCDD/Fs by Asian dust in Southeastern Korea

Atmospheric concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were measured in southeastern Korea during the spring of 2002. During this period, severe Asian dust events (ADs) occurred throughout Korea. Total suspended particulates (TSP) of ADs (456.8 μg m⁻³) increased approximately 3.6-fold compared with non-Asian dust events (NADs; 128.5 μg m⁻³). However, the concentrations of PCDD/Fs (average concentration, 3.34 pg m⁻³) did not increase as much as TSP; there was not a significant difference in the concentrations of particle-bound PCDD/Fs collected between ADs (2.45 pg m⁻³) and NADs (2.05 pg m⁻³). Meanwhile, according to TSP levels, the concentrations during NADs were 2.8-fold higher than ADs (16.73 and 5.98 ng g⁻¹-TSP, respectively). High TSP levels during sand storms without an increase in PCDD/Fs reflected an increase in coarse and accumulation mode particles. Gas/particle partitioning studies revealed the additional inputs of particulate matters to the air during ADs which did not relate with the increase of PCDD/Fs. Furthermore, emissions from ADs may consist of relatively complex atmospheric particles; back trajectories showed air masses moving at low altitudes over Korea, but there were no differences in PCDD/Fs or atmospheric pollutants regardless of air movements. The study area, which is located in southeastern Korea, might be affected by both marine and regional anthropogenic sources, which do not appear to cause clear differences in PCDD/F concentrations or congener profiles between different air trajectories.     

Levels of PCDD/FS in ambient air and soil in the vicinity of a municipal solid waste incinerator in Hsinchu

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in twenty-one ambient air samples, eight soil samples and two stack gas samples, collected near or in a municipal solid waste incinerator (MSWI) in Hsinchu, Taiwan. A systematic decrease of PCDD/Fs in the ambient air from the northeastern area was observed. PCDD/Fs levels measured in the ambient air range from 0.058 to 0.127 pg-TEQ/m3. Higher PCDD/Fs levels in the ambient air were found during winter. In addition, PCDD/Fs levels measured in the soil range from 0.524 to 5.02 pg-TEQ/g d.m. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) did not provide sufficient evidence that the environmental PCDD/Fs contamination was caused by emissions from the Hsinchu MSWI. An unknown PCDD/Fs source was proposed using congener profile analysis and supported by both PCA and HCA.     

Biotransformation of atrazine and metolachlor within soil profile and changes in microbial communities

Biotransformation studies of atrazine, metolachlor and evolution of their metabolites were carried out in soils and subsoils of Northern Greece. Trace atrazine, its metabolites and metolachlor residues were detected in field soil samples 1 year after their application. The biotransformation rates of atrazine were higher in soils and subsoils of field previously exposed to atrazine (maize field sites) than in respective layers of the field margin. The DT₅₀ values of atrazine ranged from 5 to 18 d in the surface layers of the adapted soils. DT₅₀ values of atrazine increased as the soil depth increased reaching the value of 43 d in the 80–110 cm depth layer of adapted soils. Metolachlor degraded at slower rates than atrazine in surface soils, subsoils of field and field margins with the respective DT₅₀ values ranging from 56 to 72 d in surface soils and from 165 to 186 d in subsoils. Hydroxyatrazine was the most frequently detected metabolite of atrazine. The maximum concentrations of metolachlor-OXA and metolachlor-ESA were detected in the soil layers of 20–40 cm depth after 90 d of incubation. Principal Component Analysis (PCA) of soil Phospholipid Fatty Acids (PLFAs), fungal/bacterial and Gram-negative/Gram-positive ratios of the PLFA profiles revealed that the higher biotransformation rates of atrazine were simultaneously observed with the abundance of Gram-negative bacteria while the respective rates of metolachlor were observed in soil samples with abundance of fungi.     

Atmospheric bulk deposition of dioxin and furans to Danish background areas

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were measured in bulk deposition at three Danish rural forest sites with a mutual maximum distance of 450 km. At one of the forest sites concentrations in the ambient atmosphere were sampled from a 12 m high tower. Sampling was carried out within a period of 3 years with sampling intervals of 1–2 months. Mean bulk deposition fluxes were 1 ng m⁻² yr⁻¹ I-TEQ and deviated less than 30% between the sites. Yearly average PCDD/F concentrations in the atmosphere were 24 fg m⁻³ I-TEQ with maximum values in the winter period. During winter months atmospheric concentrations of PCDD/F and oxidized sulphur compounds showed a positive correlation, furthermore seasonal bulk deposition showed correlation between PCDD/F and sulphate.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in soils and sediments from Daliao River Basin, China

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) were analyzed in surface sediments and top soils collected from 30 sites in Daliao River Basin. The concentrations of PCDD/F ranged from 0.28 to 29.01 ng TEQ kg(-1) dw (mean value, 7.45 ng TEQ kg(-1)dw) in sediments, and from 0.31 to 53.05 ng TEQ kg(-1)dw (mean value, 7.00 ng TEQ kg(-1)dw) in soils. PCDD/F pollution in sediments from the mid- and downstream sections of Hun River was found to be relatively heavy, and the levels of PCDD/F contamination in paddy soils were generally higher than those of upland soils. Using multivariate statistical analysis, the PCDD/F homologue and congener profiles of all soil and sediment samples were compared with those of suspected PCDD/F sources. The results showed that, PCDD/F contamination in most sediments of Hun River should mainly originated from the production of organochlorine chemicals, while metal smelting was the important potential source of PCDD/F in the drainage area of Taizi River. PCDD/F contamination in paddy soils should be simultaneously attributed to the polluted water irrigation and the organochlorine pesticide application.     

Emissions of PCDD/Fs,PCBs, and PAHs from legacy on-road heavy-duty diesel engines

Exhaust emissions of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin/furan (PCDD/F) congeners, tetra–octa PCDD/F homologues, 12 WHO 2005 polychlorinated biphenyl (PCB) congeners, mono–nona chlorinated biphenyl homologues, and 19 polycyclic aromatic hydrocarbons (PAHs) from three legacy diesel engines were investigated. The three engines tested were a 1985 model year GM 6.2 J-series engine, a 1987 model year Detroit Diesel Corporation 6V92 engine, and a 1993 model year Cummins L10 engine. Results were compared to United States’ mobile source inventory for on-road diesel engines, as well as historic and modern diesel engine emission values. The test fuel contained chlorine at 9.8 ppm which is 1.5 orders of magnitude above what is found in current diesel fuel and 3900 ppm sulfur to simulate fuels that would have been available when these engines were produced. Results indicate PCDD/F emissions of 13.1, 7.1, and 13.6 pg International Toxic Equivalency (I-TEQ) L⁻¹ fuel consumed for the three engines respectively, where non-detects are equal to zero. This compares with a United States’ mobile source on-road diesel engine inventory value of 946 pg I-TEQ L⁻¹ fuel consumed and 1.28 pg I-TEQ L⁻¹ fuel consumed for modern engines equipped with a catalyzed diesel particle filter and urea selective catalytic reduction. PCB emissions are 2 orders of magnitude greater than modern diesel engines. PAH results are representative of engines from this era based on historical values and are 3–4 orders of magnitude greater than modern diesel engines.     

Congener profiles of PCDD/Fs in soil and vegetation samples collected near to a municipal waste incinerator

Recently, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in soil and herbage samples collected in the vicinity of a municipal solid waste incinerator (MSWI) from Tarragona (Catalonia, Spain). Since these concentrations could be increased by the presence of other emission sources of PCDD/Fs in the same area in which the MSWI is placed, the main goal of the present study was to determine the PCDD/F congener profiles in the soil and vegetation samples collected in 1996 and again in 1997 near to the facility and to compare with those from samples collected in a close area outside of direct emissions of the plant. From an accurate inspection of the PCDD/F congener profiles, it was concluded that PCDD/F emissions from the MSWI here examined are neither the only nor the main responsible for the presence of PCDD/Fs in the samples of environmental matrices collected in the area under direct influence of the plant.     

HCB,PCB, PCDD and PCDF emissions from ships

Since current estimates of hexachlorobenzene (HCB), polychlorinated biphenyls (PCB), dioxins (PCDD) and furans (PCDF) from ships are based on a relatively limited and old data set, an update of these emission factors has been outlined as a target towards improved Swedish emission inventories. Consequently, a comprehensive study was undertaken focusing on these emissions from three different ships during December 2003 to March 2004. Analyses were performed on 12 exhaust samples, three fuel oil samples and three lubricating oil samples from a representative selection of diesel engine models, fuel types and during different “real-world” operating conditions.The determined emissions corresponded reasonably well with previous measurements. The data suggest however that previous PCDD/PCDF emission factors are somewhat higher than those measured here. As expected the greatest emissions were observed during main engine start-up periods and for engines using heavier fuel oils. Total emissions for 2002, using revised emission factors, have been calculated based on Swedish sold marine fuels and also for geographical areas of national importance. In terms of their toxic equivalence (WHO-TEQ), the PCDD/PCDF emissions from ships using Swedish fuels are small (0.37–0.85 g TEQ) in comparison to recent estimates for the national total (ca. 45 g TEQ). Emissions from other land-based diesel engines (road vehicles, off-road machinery, military vehicles and locomotives) are estimated to contribute a further 0.18–0.42 g TEQ. Similarly, HCB and PCB emissions from these sources are small compared to 1995 national emission inventories.     

Estimation of ecotoxicity of petroleum hydrocarbon mixtures in soil based on HPLC–GCXGC analysis

Detailed HPLC–GCXGC/FID (high performance liquid chromatography followed by comprehensive two-dimensional gas chromatography with flame-ionization detection) analysis of oil-contaminated soils was performed to interpret results of selected acute ecotoxicity assays. For the five ecotoxicity assays tested, plant seed germination and Microtox^® were selected as most sensitive for evaluating ecotoxicity of the oil in the soil phase and in the leaching water, respectively. The measured toxicity for cress when testing the soil samples did not correspond to TPH concentration in the soil. A detailed chemical composition analysis of the oil contamination using HPLC–GCXGC/FID allows to better predict the ecotoxicological risk and leaching potential of petroleum hydrocarbons in soil. Cress biomass production per plant was well correlated to the total aromatic hydrocarbon concentration (R² = 0.79, n = 6), while cress seed germination was correlated (R² = 0.82, n = 6) with total concentration of “highly water-soluble aromatic hydrocarbons” (HSaromatics). The observed ecotoxicity of the leaching water for Microtox-bacteria related well to calculated (based on the HPLC–GCXGC/FID results) petroleum hydrocarbon equilibrium concentrations in water.     

Heavy metals, PCDD/F and PCB in sewage sludge samples from two wastewater treatment facilities in Rio de Janeiro State, Brazil

Two sewage sludge samples collected from an urban as well as a rural area in Brazil and one sludge sample originating from the city of Balingen, Baden-Württemberg, South Germany, were investigated in respect to contamination with heavy metals, PCDD/F and PCB. The results were compared to PCDD/F and indicator-PCB mean values found in the region of Baden-Württemberg. The observed toxicity equivalents of PCDD/F found in the Brazilian samples, were below the upper limit specified by German legislation for final disposal or agricultural use in soils. Both the PCB and heavy metal values exceeded this limit. The PCDD/F congener/homologue profiles found in the Brazilian samples indicated that the urban sewage sludge shows a contamination where both chlorophenols and depositional sources appear to be contributing to the contamination pool. The enrichment of highly chlorinated PCDD/F groups in the sludge of semi-rural origin is probably due to transport phenomena effects. For the German sludge sample, depositional sources seem to be the main PCDD/F contamination pathway. Regarding PCB, both Brazilian samples show a homologue profile that indicates a contamination stemming from technical PCB formulations like Clophen A50 and Clophen A60 or equivalent.     

Source identification of PCDD/Fs in agricultural soils near to a Chinese MSWI plant through isomer-specific data analysis

Isomer-specific data were investigated in order to identify the sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in agricultural soils, including Fluvo-aquic and paddy soils, in the vicinity of a Chinese municipal solid waste incineration (MSWI) plant. Homologue and isomer profiles of PCDD/Fs in soils were compared with those of potential sources, including combustion sources, i.e., MSWI flue gas and fly ash; and the impurities in agrochemicals, such as the pentachlorophenol (PCP), sodium pentachlorophenate (PCP-Na) and 1,3,5-trichloro-2-(4-nitrophenoxy) benzene (CNP). The results showed that the PCDD/F isomer profiles of combustion sources and agricultural soils were very similar, especially for PCDFs, although their homologue profiles varied, indicating that all the isomers within each homologue behave identically in the air and soil. Moreover, factor analysis of the isomer compositions among 33 soil samples revealed that the contamination of PCDD/Fs in agricultural soils near the MSWI plant were primarily influenced by the combustion sources, followed by the PCP/PCP-Na and CNP sources. This implication is consistent with our previous findings based on chemometric analysis of homologue profiles of soil and flue gas samples, and identifies PCP/PCP-Na as an additional important source of PCDD/Fs in the local area. This makes the similarities and differences of isomer profiles between Fluvo-aquic and paddy soils more explainable. It is, therefore, advisable to use isomer-specific data for PCDD/F source identifications where possible.     

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.     

Anthropogenic and natural levels of arsenic in PM10 in Central and Northern Chile

A few copper and gold smelters in Chile are behind a large fraction of global arsenic emissions, raising concerns for increased concentrations of arsenic in PM10 in Central and Northern Chile. This concern is amplified by the fact that Northern Chile soils and rivers in general are characterized by a high arsenic content. A monitoring and modeling study has been performed to quantify the regional impact of the smelter emissions. Measured atmospheric arsenic concentrations from 2.4 to 30.7 ng m⁻³ were found at seven rural stations, located tens to hundreds of kilometers away from the nearest smelter. Analyses of topsoil and subsoil samples taken from PM10 monitoring stations revealed levels up to 291 mg kg⁻¹, the highest values found in the northern Atacama desert in Chile. An absolute principal component analysis of selected trace elements in PM10 shows that the regional impact of anthropogenic smelter emissions on airborne arsenic concentrations is more important than the effect of soil dust resuspension. The dominance of the smelter emissions is larger in Central Chile than in the northern parts. The impact of resuspended soil dust on airborne arsenic levels in rural areas was estimated not to exceed 5 ng m⁻³. The model calculations support the dominant role of anthropogenic emissions and give spatial and temporal variations in atmospheric concentrations consistent with the monitored levels at five of the seven stations. At two of the northernmost stations indications were found of unidentified sources other than the smelters and the resuspended soil dust, contributing to about 5 ng m⁻³ of total arsenic levels. The study confirms that a strong control or elimination of arsenic emissions from the smelters would lead to arsenic in PM10 levels in Northern and Central Chile comparable to non-polluted areas in other countries.