Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

Gaseous mercury fluxes from the forest floor of the Adirondacks

The flux of gaseous elemental mercury (Hg⁰) from the forest floor of the Adirondack Mountains in New York (USA) was measured numerous times throughout 2005 and 2006 using a polycarbonate dynamic flux chamber (DFC). The Hg flux ranged between −2.5 and 27.2 ng m⁻² h⁻¹ and was positively correlated with temperature and solar radiation. The measured Hg emission flux was highest in spring, and summer, and lowest in winter. During leaf-off periods, the Hg emission flux was highly dependent on solar radiation and less dependent on temperature. During leaf-on periods, the Hg emission flux was fairly constant because the forest canopy was shading the forest floor. Two empirical models were developed to estimate yearly Hg⁰ emissions, one for the leaf-off period and one for the leaf-on period. Using the U.S. EPA's CASTNET meteorological data, the cumulative estimated emission flux was approx. 7.0 μg Hg⁰ m⁻² year⁻¹.     

Influence of a large steel complex on the spatial distribution of volatile polycyclic aromatic hydrocarbons (PAHs) determined by passive air sampling using membrane-enclosed copolymer (MECOP)

Membrane-enclosed copolymer (MECOPs) samplers containing crystalline copolymers of ethylvinylbenzene-divinylbenzene in polyethylene membranes were used to assess the influence of a steel complex on the level and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in ambient air. MECOPs were deployed at six sites in Pohang, Korea for 37 days (August 9, 2005–September 14, 2005). Fluorene, phenanthrene, anthracene, and fluoranthene were dominant PAHs with the highest contribution of phenanthrene (59%) to the total amount of vapor-phase PAHs. The spatial distribution of total PAHs in the vapor phase ranging from 76 to 1077 ng MECOP⁻¹ and air dispersion modeling suggested that the steel complex was the major PAH source in Pohang. It was revealed that the major wind directions rather than the distance from the steel complex were a significant factor affecting the levels of PAHs at the sampling sites. Finally, we tried to convert MECOP concentrations (ng MECOP⁻¹) to air concentrations (ng m⁻³) with the modified sampling rates (m³ day⁻¹). This study demonstrates again that passive air samplers are useful tools for spatially resolved and time-integrated monitoring of semivolatile organic compounds (SOCs) in ambient air.     

Ammonia fluxes and derived canopy compensation points over non-fertilized agricultural grassland in The Netherlands using the new gradient ammonia—high accuracy—monitor (GRAHAM)

During a measurement period from June till November 2004, ammonia fluxes above non-fertilized managed grassland in The Netherlands were measured with a Gradient Ammonia—High Accuracy—Monitor (GRAHAM). Compared with earlier ammonia measurement systems, the GRAHAM has higher accuracy and a quality control system.Flux measurements are presented for two different periods, i.e. a warm, dry summer period (from 18 July till 15 August) and a wet, cool autumn period (23 September till 23 October). From these measurements canopy compensation points were derived. The canopy compensation point is defined as the effective surface concentration of ammonia. In the summer period (negative) deposition fluxes are observed in the evening, night and early morning due to leaf surface wetness, while in the afternoon emission fluxes are observed due to high canopy compensation points. The mean NH₃-flux in this period was 4 ng m⁻² s⁻¹, which corresponds to a net emission of 0.10 kg N ha⁻¹ over the 28 day sampling period. The NH₃-flux in the autumn period mainly shows (negative) deposition fluxes due to small canopy compensation points caused by low temperatures and a generally wet surface. The mean NH₃-flux in this period is −24 ng m⁻² s⁻¹, which corresponds to a net deposition of 0.65 kg N ha⁻¹ over the 31 day sampling period.Frequency distributions of the NH₃-concentration and flux show that despite higher average ambient NH₃-concentrations (13.3 μg m⁻³ in the summer period vs. 6.4 μg m⁻³ in the autumn period) there are more emission events in the summer period than in the autumn period (about 50% of the time in summer vs. 20% in autumn). This is caused by the high canopy compensation points in summer due to high temperatures and a dry surface. In autumn, deposition dominates due to a generally wet surface that induces low canopy compensation points.For our non-fertilized agricultural grassland site, the derived canopy compensation points (at temperatures between 7 and 29 °C) varied from 0.5 to 29.7 μg m⁻³ and were on an average 7.0 μg m⁻³, which is quite high for non-fertilized conditions and probably caused by high nitrogen inputs in the past or high dry deposition amounts from local sources. The average value for the ratio between NH₄⁺ and H⁺ concentration in the canopy, Γ_c, that was derived from our data was 2200.     

Long-term measurements of SO2 dry deposition over Gansu Province,China

Potassium carbonate sulfation plates, monitored monthly for 11 years from 48 sites in 11 cities in Gansu Province, China, provide a crude estimate of cumulative SO₂ dry depositions. Measured SO₂ dry deposition rates were 1.6–472 mg m⁻² day⁻¹ and had seasonal variations with maxima in winter and minima mainly during summer as a result of higher winter and lower summer SO₂ concentrations. The 11-year monthly average SO₂ dry deposition rates are 23.2–248.97 and 11.7–175.6 mg m⁻² day⁻¹ in the eleven cities in winter and summer, respectively. A monthly average SO₂ deposition velocity was also estimated from 0.06 to 9.72 cm s⁻² in the 11 cities studied with a 11-year average maximum value of about 1.1–2.7 cm s⁻² in April and July and a 11-year average minimum value of about 0.2–1.0 cm s⁻¹ in January. The SO₂ dry deposition velocity also exhibits an increasing with wind speed in basins of less than 500 mm annual precipitation. In contrast, due to influences of the relative humidity in valleys of more than 500 mm annual precipitation, it shows a decreasing trend with wind speed increasing.     

Carbonaceous matter and PBDEs on indoor/outdoor glass window surfaces in Guangzhou and Hong Kong,South China

Organic films, collected from indoor and outdoor window surfaces in Guangzhou and Hong Kong of South China, were analyzed to quantify their organic carbon (OC), elemental carbon (EC), and polybrominated diphenyl ethers (PBDEs) content. The highest concentrations of OC, EC, and BDE-209 were found in Guangzhou with values of 10 000 μg m^?2, 2200 μg m^?2, and 4000 ng m^?2, respectively, and the highest concentration of Σ₇PBDE (sum of BDE-28, -47, -99, -100, -153, -154 and -183) was found in Hong Kong with a value of 25 ng m^?2. In most cases, the concentrations of PBDEs were higher in the exterior films than those in the interior films with BDE-209 as the predominant congener in both cities, suggesting that PBDEs mainly come from ambient environment, and deca-BDE accounts for major PBDE consumption. The growth rates of organic film on window surfaces were fast at the beginning, and reached a consistent level afterwards. The evolution rates ranged from 2.6 to 11 nm day^?1 for “bulk film”, while from 0.06 to 0.92 nm day^?1 for “pure film”. The concentrations of PBDEs on the window surfaces did not increase with the growth time, suggesting that the window surface may provide a good place for photo-degradation of PBDEs.     

Polycyclic aromatic hydrocarbon (PAH) deposition to and exchange at the air-water interface of Luhu, an urban lake in Guangzhou, China

Urban lakes are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs from wet and dry atmospheric deposition. Little was reported on the seasonal patterns of atmospheric deposition of PAHs under Asian monsoon climate. Bulk (dry + wet) particle deposition, air-water diffusion exchange, and vapour wet deposition of PAHs in a small urban lake in Guangzhou were estimated based on a year-round monitoring. The total PAH particle deposition fluxes observed were 0.44-3.46 μg m⁻² day⁻¹. The mean air-water diffusive exchange flux was 20.7 μg m⁻² day⁻¹. The vapour deposition fluxes of PAHs ranged 0.15-8.26 μg m⁻² day⁻¹. Remarkable seasonal variations of particulate PAH deposition, air-water exchange fluxes and vapour wet deposition were influenced by seasonal changes in meteorological parameters. The deposition fluxes were predominantly controlled by the precipitation intensity in wet season whereas by atmospheric concentration in dry season.     

Mobile passive samplers: concept for a novel mode of exposure

Integrative passive sampling with devices such as semipermeable membrane devices generally relies on rigs for month-long static exposures in water. We evaluate here whether mobile exposures of passive samplers can provide reliable estimates of dissolved contaminant concentrations. Mobile exposures were obtained by towing samplers fastened to the end of a benthic trawl net. Significant and reproducible absorption of polycyclic aromatic hydrocarbons during 5 h-long deployments was made possible by high sampling rates resulting from high water turbulences during towing at 1.2-1.5 knots. Sampling rates (72-215 L d⁻¹) estimated from the dissipation of performance reference compounds were supported by in situ calibration with samplers exposed for a 30 days in the vicinity of the test site. Higher fluoranthene and pyrene absorption in samplers exposed to the trawling-induced sediment plume could be attributed to desorption from re-suspended sediments. This mode of exposure has the potential to be used in monitoring programmes.     

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).     

Source apportionment of primary and secondary organic aerosols using positive matrix factorization (PMF) of molecular markers

Monthly average ambient concentrations of more than eighty particle-phase organic compounds, as well as total organic carbon (OC) and elemental carbon (EC), were measured from March 2004 through February 2005 in five cities in the Midwestern United States. A multi-variant source apportionment receptor model, positive matrix factorization (PMF), was applied to explore the average source contributions to the five sampling sites using molecular markers for primary and secondary organic aerosols (POA, SOA). Using the molecular makers in the model, POA and SOA were estimated for each month at each site. Three POA factors were derived, which were dominated by primary molecular markers such as EC, hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs), and which represented the following POA sources: urban primary sources, mobile sources, and other combustion sources. The three POA sources accounted for 57% of total average ambient OC. Three factors, characterized by the presence of reaction products of isoprene, α-pinene and β-caryophyllene, and displaying distinct seasonal trends, were consistent with the characteristics of SOA. The SOA factors made up 43% of the total average measured OC. The PMF-derived results are in good agreement with estimated SOA concentrations obtained from SOA to tracer yield estimates obtained from smog chamber experiments. A linear regression comparing the smog chamber yield estimates and the PMF SOA contributions had a regression slope of 1.01 ± 0.07 and an intercept of 0.19 ± 0.10 μg OC m^?3 (adjusted R² of 0.763, n = 58).     

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.     

Characterization of gaseous pollutant and particulate matter emission rates from a commercial broiler operation part I: Observed trends in emissions

This paper characterizes the emission rates of size fractionated particulate matter, inorganic aerosols, acid gases, ammonia and methane measured over four flocks at a commercial broiler chicken facility. Mean emission rates of each pollutant, along with sampling notes, were reported in this paper, the first in a series of two. Sampling notes were needed because inherent gaps in data may bias the mean emission rates.The mean emission rates of PM₁₀ and PM_2.5 were 5.0 and 0.78 g day^?1 [Animal Unit, AU]^?1, respectively, while inorganic aerosols mean emission rates ranged from 0.15 to 0.46 g day^?1 AU^?1 depending on the season. The average total acid gas emission rate was 0.43 g day^?1 AU^?1 with the greatest contribution from nitrous and nitric acids and little contribution from sulfuric acid (as SO₂).Ammonia emissions were seasonally dependent, with a mean emission rate of 66.0 g day^?1 AU^?1 in the cooler seasons and 94.5 g day^?1 AU^?1 during the warmer seasons. Methane emissions were relatively consistent with a mean emission rate of 208 g day^?1 AU^?1.The diurnal pattern in each pollutant’s emission rate was relatively consistent after normalizing the hourly emissions according to each daily mean emission rate. Over the duration of a production cycle, all the measured pollutants’ emissions increased proportionally to the total live mass of birds in the house, with the exception of ammonia.Interrelationships between pollutants provide evidence of mutually dependent release mechanisms, which suggests that it may be possible to fill data gaps with minimal data requirements. In the second paper (Roumeliotis, T.S., Dixon, B.J., Van Heyst, B.J. Characterization of gaseous pollutants and particulate matter emission rates from a commercial broiler operation part II: correlated emission rates. Atmospheric Environment, 2010.), regression correlations are developed to estimate daily mean emission rates for data gaps and, using the normalized hourly diurnal patterns from this paper, emission factors were generated for each pollutant.     

NOX fluxes from three kinds of agricultural lands in the Yangtze Delta,China

Static chamber method was adopted to measure the surface exchanges of NO and NO₂ between three kinds of agricultural lands and the atmosphere during spring–summer period in the Yangtze Delta, China. The average NO fluxes were 20.9, 27.4 and 21.4 ng N m⁻² s⁻¹, respectively, for cabbage (CA, cultivation of celery occurred along with cabbage), potato (PO) and soybean (SY) fields. The average NO₂ fluxes were −1.12, 0.93 and −0.68 ng N m⁻² s⁻¹, respectively, for the cabbage, potato and soybean fields. Apparently, negative linear correlation was found between the NO₂ fluxes from the CK plot (tilled conventionally but did not cultivate any seeds) and its ambient concentrations, and the compensation point was calculated to be 0.92 ppbv. The total NO emission from the vegetable lands and SY land in this region during spring–summer period was roughly estimated to be 15.9 Gg N, which accounted for about 11.2% of the estimated value of total NO emissions in the July of 1999 from Chinese agricultural fields.     

Observation and origin of organochlorine compounds and polycyclic aromatic hydrocarbons in the free troposphere over central Europe

On Zugspitze (2670 m a.s.l.), Alps, higher concentrations were observed during a winter than during a summer measurement campaign of PAHs, chlorobenzenes (43.6 vs. 2.0 pg m⁻³) and DDTs (3.7 vs. 1.2 pg m⁻³), while hexachlorocyclohexanes and PCBs were found at similar levels. The PCB, HCH and DDT levels are among the lowest ever reported from outside the Arctic. Mostly lower levels were found in samples collected in summer than in winter despite a significant boundary layer air influence, but no such influence on samples collected during the winter campaign. Boundary layer influence was quantified by Lagrangian particle dispersion model retroplume analyses. Photochemical lifetimes corresponding to k_OH < 1.5 × 10⁻¹² cm³ molec⁻¹ s⁻¹ are found for p,p′-DDT, k_OH < 0.75 × 10⁻¹² cm³ molec⁻¹ s⁻¹ for p,p′-DDE and k_OH < 1.0 × 10⁻¹² cm³ molec⁻¹ s⁻¹ for p,p′-DDD.     

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

Two-week average concentrations of ozone (O₃), nitric acid vapor (HNO₃) and ammonia (NH₃) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O₃, 1.0-3.8 μg m⁻³ for HNO₃, and 2.6-5.2 μg m⁻³ for NH₃. Calculated O₃ exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha⁻¹ for maximum values, and 0.4-8 kg N ha⁻¹ for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O₃ human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O₃.     

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K_EVA−W partition coefficients correlate well (r² = 0.87) with Log K_OW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K_EVA−W = 1.04 Log K_OW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.     

Multi-zonal air flow rates in residences in Boston,Massachusetts

In spite of the importance of interzonal air flow for indoor air quality assessment, few studies have characterized these flows. As part of the Boston Exposure Assessment in Microenvironments (BEAM) Study, air flow rates were estimated within 45 residences in the Boston area, most over two seasons. Thirty-five residences had basements, 11 of which also had attached garages, and 10 other residences had common apartment hallways. Air flow rates between zones were calculated using tracer gases (PFTs and SF6) and mass-balance models. Mean air flow rates from the basement to the occupied zone were significantly higher in the winter (174 m³ h⁻¹) than in the summer (67 m³ h⁻¹). The mean percent of the total air flow within the occupied zone of the residence from the basement was 26% (SD=34%) in the summer and 47% (SD=26%) in the winter while the mean percent from apartment hallways was 22% (SD=33%). Residences with garages attached to the basement had higher air flow rates to the adjacent zone (means from 50 to 887 m³ h⁻¹) than those with garages attached directly to the occupied zone (means from 1 to 65 m³ h⁻¹). These data provide a basis for modeling the contribution of indoor sources to concentrations in occupied zones.     

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.