Human exposure to dioxins through diet in Italy

We have measured the content of polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (together defined as “dioxins”) in 269 samples of food of animal origin collected through the regional veterinary services, covering the national territory. Quantification of the dioxins was accomplished by isotope dilution method, and toxic equivalents (TEQ) were calculated. The average daily food intake was obtained from two main sources: national data collected by the National Institute of Nutrition, and data from an ongoing cohort study on diet and cancer including 40, 000 Italian subjects.

The mean value of dioxins measured in food of animal origin was 0.144 ± 0.266 pg-TEQ/g (range: 0.003–1.655 pg-TEQ/g). Fish was the item with the highest content. The estimated intake of dioxins with main food items of animal origin is presented. The major contribution to dioxins intake with food comes from cow milk and fish consumption. These results are in agreement with what observed in studies conducted in other countries, such as Germany, Finland, Japan, Spain, and are below the limits set by the European legislation.     

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.     

A national inventory to estimate release of polychlorinated dibenzo-p-dioxins and dibenzofurans in Portugal

Taking into account current environmental concerns, the main objective of this work focused a national inventory aiming to estimate the amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) released in Portugal in 2006. The methodology used was based on the Standardized Toolkit for Identification and Quantification of Dioxins and Furan Releases, developed by UNEP Chemicals, in 2005. The method allows the assessment of the amount of PCDD/PCDF released into the environment along five vectors involving air, water, land, products and residues. Facing some difficulties mainly regarding to the availability of data for some activities known to produce PCDD/PCDF, three scenarios (Sc1 to Sc3) corresponding to lower, central and upper estimates were established. The Sc1 scenario (lower estimate) includes the situations where in case of doubt or scarce information, reduced or none emission values were assumed, Sc2 refers to a central estimate, which is believed to be the most realistic for the Portuguese situation, while Sc3 corresponds to the worst case (upper estimate). The results obtained pointed out that the total amount of PCDD/PCDF emitted in Portugal during the period under analysis was in the range of 51.2–217.9 g TEQ year⁻¹, with the most likely value of 95.2 g TEQ year⁻¹ achieved under the Sc2 scenario. This study also showed that the methodology developed by UNEP Chemicals is a very simple one, and the main difficulty is the availability of data. The main indicators calculated in this study were 8.98 μg TEQ/(year person) by taking into account the total amount of PCDD/PCDF released, and 3.63 μg TEQ/(year person) when only air emissions were considered.     

Assessment of exposure to PCB 153 from breast feeding and normal food intake in individual children using a system approach model

Investigators have typically relied on a single or few discrete time points as measures of polychlorinated biphenyl (PCB) body burden, however health effects are more likely to be the result of integrative exposure in time, optionally expressed as an area under the time curve (AUC) of PCB serum concentration. Using data from a subgroup of 93 infants from a birth cohort in eastern Slovakia—a region highly polluted by PCBs—we fit a system type model, customized to our longitudinal measures of serum PCB concentrations in cord, 6, 16, and 45 month blood specimens. The most abundant congener, PCB 153, was chosen for modeling purposes. In addition to currently used methods of exposure assessment, our approach estimates a concentration time profile for each subject, taking into account mean residence time of PCB 153 molecules in the body, duration of breast feeding, hypothetical PCB 153 concentration in steady-state without breast feeding and alternately without normal food intake. Hypothetical PCB 153 concentration in steady-state without normal food intake correlates with AUC (r = 0.84, p < 0.001) as well as with duration of breast feeding (r = 0.64, p < 0.001). It makes possible to determine each subject’s exposure profile expressed as AUC of PCBs serum concentration with a minimum model parameters. PCB body burden in most infants was strongly associated with duration of breast feeding in most, but not all children, was apparent from model output.     

Dietary assessment of human exposure to PBDEs in South Korea

This study was conducted to measure the concentration of PBDEs in various food stuffs from Korea and to estimate levels of PBDE intake from food for the Korean population according to geographical location and age. 20 types of food samples were collected from four heavily populated cities (Seoul, Gwangju, Daejeon, Pusan) and one rural city (Gangneung) and were analyzed for 19 polybrominated diphenyl ether congeners (BDE 15, 17, 28, 33, 47, 49, 66, 71, 85, 99, 100, 119, 126, 138, 153, 154, 183, and 209).No significant differences in total PBDE levels in foods were found among four large cities (Gwangju; 10.91 ng g^?1 wet weight (ww), Seoul; 7.66 ng g^?1 ww, Daejeon; 6.91 ng g^?1 ww, Pusan; 6.87 ng g^?1 ww) and one rural city (Gangneung; 8.72 ng g^?1 ww). Daily dietary intake of PBDEs does not appear to be related to the extent of urbanization.Total dietary intake of PBDE for the average general population was 72.30 ng d^?1 (not detected (ND) = 0) which was similar to other countries. In all food groups, the largest contribution to PBDE intake was from fish and shellfish (48.96 ng d^?1). Total PBDE consumed per kilogram of body weight was estimated to range from 2.70 ng kg^?1 d^?1 for infants 1 through 2 years of age to 0.85 ng kg^?1 d for 65 years and older and was highest in young children and decreased with increasing age.     

Dietary intake of PCDD/Fs and dioxin-like PCBs from the Chinese total diet study in 2007

Concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in 96 food composite samples from eight varieties of food groups from the Chinese total diet study (TDS) in 2007. The concentrations of samples, expressed as WHO toxic equivalents (TEQ), ranged from 0.001 pg TEQ g^?1 to 0.85 pg TEQ g^?1 (fresh weight). Dietary intake of PCDD/Fs and dl-PCBs of 12 age/gender subgroups of the Chinese population subsequently estimated ranges from 15.4 pg TEQ kg^?1 bw month^?1 to 38.7 pg TEQ kg^?1 bw month^?1 for average population and from 68.5 pg TEQ kg^?1 bw month^?1 to 226.1 pg TEQ kg^?1 bw month^?1 for high consumers (the 97.5th percentile). Dietary exposure of children (mean: 32.5 pg TEQ kg^?1 bw month^?1) is significantly higher than that of the adults (mean: 21.5 pg TEQ kg^?1 bw month^?1) (p < 0.01) presumably due to more food consumed by children relative to their body weight compared to adults. There is no difference of dietary exposure, expressed as pg TEQ kg^?1 bw, found between different genders. Across various regions in China, there are large differences of dietary exposure of adult population and pattern of contribution of food groups to total exposure due to different contamination level and food habits. Dietary exposures of average population of various subgroups were all below the PTMI recommended by JECFA, but those of higher consumers were found exceeding or comparable to the PTMI.     

Blood levels of PCDDs,PCDFs, and coplanar PCBs in Yusho mothers and their descendants: Association with fetal Yusho disease

Maternal exposure to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) may result in adverse health effects in their children. In Japan in 1968, an accidental human exposure to rice oil contaminated with PCDDs, PCDFs, and PCBs, led to the development of Yusho disease. Yusho mothers delivered descendants with low birth weights and hyperpigmented skin and mucosa, which are characteristic of fetal Yusho disease (FYD). The Yusho cohort was used to evaluate the effect of maternal exposure to PCDDs, PCDFs, and PCBs on the development of FYD. Blood samples, obtained from 64 Yusho mothers (117 descendants: 10 with FYD and 107 without FYD), were analyzed for congeners of seven PCDDs, 10 PCDFs, and four coplanar PCBs. We investigated the association between the maternal estimated blood levels of dioxins at delivery and the risk of fetal Yusho disease. We also studied the differences in dioxin blood levels in 24 mother–descendant pairs (5 with FYD and 19 without FYD). The estimated levels of total PCDD TEQ, total PCDF TEQ, total coplanar PCB TEQ, and total TEQ in the maternal blood at delivery were associated with significantly increased risk of FYD. The odds ratios, which present the risk of FYD for a 10-fold increase in blood dioxin, were largest for 1,2,3,6,7,8-HexaCDD (odds ratio = 28.6, 95% confidence interval = 1.67–489.9, p = 0.02). The levels of 1,2,3,6,7,8-HexaCDD in both the Yusho mothers and their descendants with FYD were higher than the levels in those without FYD. These findings suggest that 1,2,3,6,7,8-HexaCDD is the most important causative congener for the development of FYD.     

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.     

Mobile sources of atmospheric polycyclic aromatic hydrocarbons in a roadway tunnel

Amounts of polycyclic aromatic hydrocarbons (PAHs) and oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) in samples collected from the air, from the dust on a guardrail, and from the soils on a tunnel roadway at five sampling sites in a regular roadway tunnel were chemically analyzed in order to determine their sources. Among the 23 PAHs found in the air samples, pyrene was found in the highest concentration (43±7.2 ng/m³), followed by fluoranthene (26±4.3 ng/m³). Among 20 oxy-PAHs found in the air samples, anthraquinone was found in the greatest amount (56±3.9 ng/m³). The average concentration of the major PAHs found in the guardrail dust samples were 6.9±0.77 μg/g for pyrene, 5.5±0.76 μg/g for fluoranthene, and 2.6±0.30 μg/g for phenanthrene. The average concentration of the major oxy-PAHs found in the guardrail dust samples were 9.2±3.5 μg/g for anthraquinone and 1.4±0.50 μg/g for 2-methylanthraquinone. The average concentration of the major PAHs found in the soil samples were 1.1±0.31 μg/g for fluoranthene, 0.92±0.21 μg/g for pyrene, and 0.72±0.16 μg/g for phenanthrene. The average concentration of the major oxy-PAHs found in the soil samples were 1.2±0.88 μg/g for anthraquinone, 0.18±0.04 μg/g for 4-biphenylcarboxaldehyde, and 0.13±0.08 μg/g for 2-methylanthraquinone. The BeP ratios calculated from the results suggest that most PAHs found in the samples collected from the roadway tunnel were from automobile exhaust gases.     

The composition and sources of PM2.5 organic aerosol in two urban areas of Chile

Fine particle (PM_2.5) samples were collected, using a charcoal diffusion denuder, in two urban areas of Chile, Santiago and Temuco, during the winter and spring season of 1998. Molecular markers of the organic aerosol were determined using GC/MS. Diagnostic ratios and molecular tracers were used to investigate the origin of carbonaceous aerosols. As main sources, road and non-road engine emissions in Santiago, and wood burning in Temuco were identified. Cluster analysis was used to compare the chemical characteristics of carbonaceous aerosols between the two urban environments. Distinct differences between Santiago and Temuco samples were observed. High concentrations of isoprenoid (30–69 ng m⁻³) and unresolved complex mixture (UCM) of hydrocarbons (839–1369 ng m⁻³) were found in Santiago. High concentrations of polynuclear aromatic hydrocarbons (751±304 ng m⁻³) and their oxygenated derivatives (4±2 ng m⁻³), and of n-alk-1-enes (16±13 ng m⁻³) were observed in Temuco.     

Wintertime size distribution of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the urban environment: Street- vs rooftop-level measurements

The size distribution of ambient air particles and associated organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) including hexachlorocyclohexanes (HCHs), DDT and metabolites, etc., was investigated at a traffic-impacted site of Thessaloniki, Greece. Investigation took place during wintertime of 2006 at two heights above ground: at the street level (1.5 m) and at the rooftop level (15 m). Size-resolved samples (<0.95 μm, 0.95–1.5 μm, 1.5–3 μm, 3–7.5 μm and >7.5 μm) were concurrently collected from the two height levels using five-stage high volume cascade impactors. At both heights, particle mass exhibited bimodal distribution with peaks in the 0.95–1.5 μm and the 3–7.5 μm size fractions, whereas most organic pollutants exhibited one peak at 0.95–1.5 μm. Apart from the 0.95–1.5 μm fraction, particle concentrations of all size ranges were significantly higher at the street level than at the rooftop as a result of more intensive vehicular emissions and road dust resuspension. On the contrary, the concentrations of most organic pollutants did not differentiate significantly between the two elevations.     

Polychlorinated biphenyl spatial patterns in San Francisco Bay forage fish

Industrialized waterways frequently contain nearshore hotspots of legacy polychlorinated biphenyl (PCB) contamination, with uncertain contribution to aquatic food web contamination. We evaluated the utility of estuarine forage fish as biosentinel indicators of local PCB contamination across multiple nearshore sites in San Francisco Bay. Topsmelt (Atherinops affinis) or Mississippi silverside (Menidia audens) contamination was compared between 12 targeted sites near historically polluted locations and 17 probabilistically chosen sites representative of ambient conditions. The average sum of 209 PCB congeners in fish from targeted stations (441 ± 432 ng g^?1 wet weight, mean ± SD) was significantly higher than probabilistic stations (138 ± 94 ng g^?1). Concentrations in both species were comparable to those of high lipid sport fish in the Bay, strongly correlated with spatial patterns in sediment contamination, and above selected literature thresholds for potential hazard to fish and wildlife. The highest concentrations were from targeted Central Bay locations, including Hunter’s Point Naval Shipyard (1347 ng g^?1; topsmelt) and Stege Marsh (1337 ng g^?1; silverside). Targeted sites exhibited increased abundance of lower chlorinated congeners, suggesting local source contributions, including Aroclor 1248. These findings indicate that current spatial patterns in PCB bioaccumulation correlate with historical sediment contamination due to industrial activity. They also demonstrate the utility of naturally occurring forage fish as biosentinels of localized PCB exposure.     

Methane emission from free-ranging sheep: a comparison of two measurement methods

Methane emissions from a flock of 14, 1-year old sheep grazing on a grass and legume pasture were measured using a micrometeorological mass-balance method and a sulphur hexaflouride (SF₆) tracer technique. The former measured the mean emission, over 45 min intervals, from all the sheep within a fenced 24 m×24 m enclosure, from the enrichment of methane (CH₄) in air as it passed over the sheep. The tracer technique measured emissions from a subset of 7 individual animals over 24 h periods from measurements of CH₄ and SF₆ concentrations in air exhaled by the sheep, and from the known rate of release of SF₆ from small permeation tubes placed in the animals’ rumens. Both methods gave highly similar results for 4 out of 5 days. When the species composition of dietary intake was steady during the last two days of measurement, the mean emission rate from the mass-balance method was 11.9±1.5 (SEM) g CH₄ sheep^-1 d^-1, while the rate from the tracer technique was 11.7±0.4 (SEM) g CH₄ sheep^-1 d^-1. These rates are for sheep with mean live mass of 27 kg, with a measured dry matter intake of 508 g sheep^-1 d^-1 and pasture dry matter digestibility of 69.5%. There was close agreement between these measurements and estimates from algorithms used to predict methane emissions from sheep for the Australian National Greenhouse Gas Inventory.     

High concentrations of persistent organic pollutants including PCBs,DDT, PBDEs and PFOS in little brown bats with white-nose syndrome in New York,USA

White-nose syndrome (WNS) is a condition associated with white fungal growth on ears, wings, and nose of hibernating bats; this condition has recently resulted in high bat mortality in the northeastern United States. Nevertheless, the pathogenesis of morbidity and mortality are still unknown. Elevated exposure to toxic contaminants could be a contributing factor via the consequent immunosuppression and endocrine disruption. In this study, diseased little brown bats (Myotis lucifugus) were collected from several hibernacula in eastern New York State in 2008. Fat tissues of bats were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), and organochlorine pesticides (OCPs; DDT, chlordanes, HCB, and HCH), and liver was analyzed for perfluorinated compounds (PFCs). A reference population of little brown bats, not affected by WNS, was also collected from a cave in Kentucky for the analysis of trace organic contaminants. Concentration of PCBs in fat tissues of bats from New York ranged from 1900 ng g^?1 to 35 000 ng g^?1, lipid wt, with the highest concentrations found in bats collected from caves in Albany County. High concentrations of PCBs were also found in bats from Kentucky (17 100–18 400 ng g^?1, lipid wt). Total PBDE concentrations in fat tissues ranged from 520 ng g^?1 to 10 900 ng g^?1, lipid wt, in bats from New York and from 4300 ng g^?1 to 13 000 ng g^?1, lipid wt, in bats from Kentucky. High concentrations of DDT (26 900 ng g^?1, lipid wt), chlordanes (6350 ng g^?1, lipid wt), and HCB (260 ng g^?1, lipid wt) were found in bats from New York. Concentrations of hexabromobiphenyl congener 153 (PBB 153) in bats from New York ranged from 8.6 ng g^?1 to 12 4000 ng g^?1, lipid wt. Concentrations of PFCs were on the order of a few tens to a few hundreds of nanograms per gram liver, on a wet weight basis. Overall, high concentrations of PCBs, PBDEs, DDT, and chlordanes were found in fat tissues of diseased bats from New York, although the concentrations in bats from non-diseased, reference population, from Kentucky were also high.     

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.     

Food contamination by C20–C50 mineral paraffins from the atmosphere

Most foods from plant origin usually contain 1–10 mg/kg (dry weight) of non-resolved isomeric alkanes in the range of the n-alkanes C₂₀–C₅₀ which are assumed to be residues from mineral oil products (in addition to the natural paraffins). In edible vegetable oils, concentrations may exceed 100 mg/kg. Since it was suspected that this contamination was mostly of environmental origin, particulate matter from air was analysed for the same range of paraffins. In a road tunnel, around 5 μg/m³ of such paraffins were found, corresponding to about 3% of the fine dust (PM10). The composition corresponded to that found in the particulate matter from the exhaust of diesel engines, which in turn largely corresponded to engine (lubricating) oil. In Swiss cities, the C₂₀–C₅₀ mineral paraffins in the PM10 from ambient air amounted to 0.1–1.5 μg/m³ (about 1% of the dust) and seemed to primarily originate from incomplete combustion of heating and diesel oil, lubricating oil, and road tar debris. On the countryside, the concentrations were around 0.03 μg/m³ (0.3% of the dust). Soil contained 0.5–10 mg/kg of these paraffins. The similarity of the molecular weight (volatility) distribution suggests that the food contamination with paraffins, is mostly from the air. A substantial proportion probably consists of lubricating oil. If this hypothesis is confirmed, measures should be investigated to reduce this contamination.     

PCDDs/PCDFs in ambient air (<1 fg m−3) – The CTDEP long term sampling (30 d) method

The Connecticut Department of Environmental Protection (CTDEP) commenced monitoring for PCDDs/PCDFs (polychlorinated dibenzodioxins and polychlorinated dibenzofurans) in ambient air in 1987 and adopted the long term (30 d) sampling approach in 1993. The CTDEP method represents the first use of isotopically labeled PCDDs/PCDFs as field surrogates to monitor the behavior of native PCDDs/PCDFs present in actual ambient air samples. This feature first introduced in 1987 was later adopted by US EPA in revisions to sampling methods for PCDDs/PCDFs in ambient air (EPA Method TO9A) as well as development of EPA Reference Method 23 for measurement of PCDDs/PCFDs in stationary source emissions. Results are provided here for a total of twenty-three (23) samples (reported as pairs) representing twelve (12) 30 d sampling events conducted at a site located in metropolitan Hartford CT. Samples were collected in winter months during calendar years 2002–2008. PCDDs/PCDFs concentration data (pg m⁻³) are reported as both congener sums (Cl₄–Cl₈) and 2378-substitued congeners. Total PCDDs/PCDFs concentrations for these twelve (12) sampling events ranged from 0.68 pg m⁻³ (2003) to 4.18 pg m⁻³ (2004) with a mean concentration of 2.04 pg m⁻³.Method performance was monitored through use of collocated samples, in field isotopically labeled compounds, isotopically labeled laboratory applied internal standards and field blank samples. Method performance consistently exceeded goals established in USEPA Method TO9A for these same parameters. Average recoveries of in field labeled PCDDs/PCDFs ranged from 97.5% to 104.2%. Average (mean) recoveries for each of the ten (10) isotopically labeled internal standards ranged from 77.0% (¹³C-OCDF) to 95.5% (¹³C-2,3,7,8-TCDF). Method precision defined as % RPD data for collocated sampler pairs ranged from 8% to 14% for PCDDs and from 5% to 12% for PCDFs. The mean RPD for all PCDDs/PCDFs combined is 9.6%. Field monitoring results demonstrate method sensitivity for all PCDDs/PCDFs congeners and 2378-substituted congeners to be well below concentrations typically found for these compounds in ambient air (all reported data represent measured concentrations). Quantities (pg) found in field blanks represent the major determinant to achieving further enhancements in method sensitivity for selected congeners (OCDD < 42 fg m⁻³; 1,2,3,4,6,7,8-HpCDD < 5.7 fg m⁻³; and 1,2,3,4,6,7,8-HpCDF < 2.1 fg m⁻³). The CTDEP method represents a highly sensitive and reliable technique for monitoring of PCDDs/PCDFs congeners and other persistent organic pollutants (POPs) at ultra trace levels in ambient air (fg m⁻³).     

Water-soluble organic nitrogen (WSON) in size-segregated atmospheric particles over the Eastern Mediterranean

Atmospheric water-soluble organic nitrogen (WSON) was determined on size-segregated aerosol particles collected during a two years period (2005–2006) in a remote marine location in the Eastern Mediterranean (Finokalia, Crete island). Average concentration of WSON was 5.5 ± 3.9 nmol m^?3 and 11.6 ± 14.0 nmol m^?3 for coarse (PM_1.3-10) and fine (PM_1.3) mode respectively, corresponding to 13% of Total Dissolved Nitrogen (TDN) in both modes. Air masses origin and correlation with tracers of natural and anthropogenic sources indicate that combustion process (biomass burning and fossil fuel) and African dust play an important role in regulating levels of WSON in both coarse and fine aerosol fractions. Chemical speciation of organic nitrogen pool was attempted by analyzing 47 fine aerosol samples (PM₁) for 17 free amino acids (N-FAA), dimethylamine (DMA) and trimethylamine (TMA). The average concentration of N-FAA was 0.5 ± 0.5 nmol m^?3, while the average concentration of DMA was 0.2 ± 0.8 nmol m^?3, TMA was below detection limit. The percentage contribution of N-FAA and DMA to WSON was 2.1 ± 2.3% and 0.9 ± 3.4%, respectively.     

Use of passive samplers to measure atmospheric ammonia levels in a high-density industrial hog farm area of eastern North Carolina

Hog concentrated animal feeding operations (CAFOs) in North Carolina release ammonia (NH₃), hydrogen sulfide, VOCs, and particulate matter to the atmosphere. These operations are located mainly in the NC coastal plain and can create potential health hazards for nearby human populations. Limited work has been performed to measure NH₃ at the community level to assess potential human exposure. In an effort to address this issue, a study was designed to measure NH₃ levels near hog CAFOs and community locations (i.e. homes and schools) in Eastern NC.NH₃ was collected using passive diffusion tubes in triplicate exposed primarily in weekly intervals. Sampling occurred from October 2003 to May 2004 (20 sites) and from July 2004 to October 2004 (23 sites) at varying distances from hog CAFOs in close proximity to homes and schools. Average weekly NH3 levels were measured as mass (μg NH₃-N) and converted to concentration (ppb). Mean level of 13.8 ppb near homes and schools (<2 km) was 4–12 times greater than ambient background levels (1–3 ppb), reaching as high as 80 ppb. Exposed sites (<2 km from a hog CAFO) had a mean level of 12.8 ppb which was over 2 times higher than the mean level of 5.5 ppb at less exposed sites (>2 km from a hog CAFO).The study establishes that passive sampling can be effectively used to measure average atmospheric ammonia levels at community locations near hog CAFOs in Eastern NC. The collected data indicate the relative exposure for human populations who live near a hog CAFO. The closer a populace is to the hog CAFO, the more intense the exposure. These results require more validation in the field by comparison to a reference method.     

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.