Sources of dioxins in the United Kingdom: the steel industry and other sources

Several countries have compiled national inventories of dioxin (polychlorinated dibenzo-p-dioxin [PCDD] and polychlorinated dibenzofuran [PCDF]) releases that detail annual mass emission estimates for regulated sources. High temperature processes, such as commercial waste incineration and iron ore sintering used in the production of iron and steel, have been identified as point sources of dioxins. Other important releases of dioxins are from various diffuse sources such as bonfire burning and domestic heating. The PCDD/F inventory for emissions to air in the UK has decreased significantly from 1995 to 1998 because of reduced emissions from waste incinerators which now generally operate at waste gas stack emissions of 1 ng I-TEQ/Nm3 or below. The iron ore sintering process is the only noteworthy source of PCDD/Fs at integrated iron and steelworks operated by Corus (formerly British Steel plc) in the UK. The mean waste gas stack PCDD/F concentration for this process is 1,2 ng I-TEQ/Nm3 based on 94 measurements and it has been estimated that this results in an annual mass release of approximately 38 g I-TEQ per annum. Diffuse sources now form a major contribution to the UK inventory as PCDD/Fs from regulated sources have decreased, for example, the annual celebration of Bonfire Night on 5th November in the UK causes an estimated release of 30 g I-TEQ, similar to that emitted by five sinter plants in the UK.     

Steps towards a European dioxin emission inventory

The results of a project aiming at collection and evaluation of information regarding the industrial and non-industrial emission sources for dioxins and furans (PCDD/PCDF) in 17 European Countries (EU 15, CH, N) are presented. An overview about national documents covering dioxin emission inventories for the period 1990-1995 is given. Some data on emissions associated with residual materials, waste and waste water are presented additionally. Based on the air emission data contained in these documents the most important emission sources were determined which are assumed to cover about 90% of the overall emissions. For the selected sources and for all 17 countries new estimates of the atmospheric PCDD/PCDF emissions were derived from average emission factors and statistical activity rates for the year 1994. As a result, on the European scale the largest annual PCDD/PCDF emission is assessed to be released from municipal waste incineration, quite closely followed by emissions from iron ore sintering. Considerable releases of dioxins and furans--based, however, on highly uncertain data--are further assessed for domestic burning, accidental fires and (former) use of contaminated wood preservatives (pentachlorophenol). A lower but still significant emission is further assigned to the sector of non-ferrous metal production; particular processes used in this branch proved to generate very high PCDD/PCDF flue gas concentrations.     

Isomeric analysis of PCDD/PCDF in waste incinerator fly ash by GC-MS/MS

The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.     

The dioxin/POPs legacy of pesticide production in Hamburg: Part 2—waste deposits and remediation of Georgswerder landfill

α-HCH, β-HCH, and γ-HCH (lindane) were listed as persistent organic pollutants in the Stockholm Convention. Therefore, they need to be globally addressed including the wastes remaining from historic use and production. While at most lindane production sites the unintentionally produced 85 % HCH waste isomers have been deposited, at a former pesticide factory in Hamburg-Moorfleet HCH waste isomers have been recycled from 1953 to 1984 by thermal decomposition to chlorobenzenes and resulted in high polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/PCDF)-contaminated residues. The management of the PCDD/PCDF-contaminated waste from the former pesticide factory in Hamburg has been assessed and quantified. Based on past accredited PCDD/PCDF measurements, the registered 3,700 tonnes of disposed thermal HCH decomposition residue contained 333 to 854 kg of PCDD/PCDF toxicity equivalent (I-TEQ) in 53–102 tonnes total sum of PCDD/PCDF. The wastes have been deposited together with other wastes in landfills in Hamburg and other parts of Germany. For the Georgswerder landfill (Hamburg), where approximately 50 % of the PCDD/PCDF is disposed, current and previous situation and remediation activities are described. While PCDD/PCDF leaching from the landfill is controlled and incinerated, more water soluble organochlorines (vinyl chloride, cis-1,2-dichlorethene, chlorobenzenes) and benzene remain as a challenge for groundwater management. A comprehensive aftercare program has been established and will need to be operated by future generations including renewal of containment systems. Former lindane/HCH productions need—in addition to HCH deposits—to be assessed for possible recycling practice of HCH and related PCDD/PCDF-containing deposits. This could systematically be addressed within the Stockholm Convention implementation.     

Air and soil dioxin levels at three sites in Italy in proximity to MSW incineration plants

Levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in both air and soil samples were measured at three different sites in Italy, in proximity to three municipal solid waste incinerators (MSWIs) to determine baseline contamination and the contributory role of incinerator emissions. At the first site, located in an agricultural, cattle-breeding, typically flattish area of the Po Valley, the dioxin concentrations had already been measured before the start-up of the new MSWI. These dioxin concentrations were then again measured after two years of continual operation of the incinerator. Despite the presence of the plant, the PCDD/Fs concentrations appear not to have been affected and were found to be in a range of 22-125 fg I-TEQ m(-3) in the air samples and 0.7-1.5 pg I-TEQ g(-1) in the soil samples. The second site is located in an industrial district of the Veneto Region, in the surroundings of an old MSWI that is not equipped with Best Available Technology (BAT) dioxin removal system. The PCDD/Fs concentrations in the air samples were between 144 and 337 fg I-TEQ m(-3). This is a typical range of values for industrial areas, while the soil samples showed contamination levels between 1.1 and 1.4 pg I-TEQ g(-1). The third site lies in the Adige Valley, near a MSWI that has been equipped with BAT for flue gas cleaning. The observed values ranged from 10 to 67 fg I-TEQ m(-3) for the air samples and 0.08-1.2 pg I-TEQ g(-1) for the soil samples. The contributory factors of the varying characteristics of the different areas together with the types of technology adopted at each MSWI plant are discussed. The PCDD/Fs levels are subsequently compared with established values from previous studies.     

Correlation coefficients between the dioxin levels in mother's milk and the distances to the nearest waste incinerator which was the largest source of dioxins from each mother's place of residence in Tokyo, Japan

BACKGROUND: To observe the relationship between the PCDD/F and Co-PCB levels in samples of human breast milk and nearby waste incinerators in Tokyo, Japan. METHODS: Breast milk was taken from 240 mothers residing in Tokyo, Japan to measure and analyze the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) contained in the fat. Individual milk samples (about 50 ml) were obtained from the mothers 30 days after delivery, between the months of June and September in 1999 and 2000. A map of Tokyo was used to measure the distances between each mother's place of residence and the closest public and industrial waste incinerators. RESULTS: The distances to the nearest waste incinerators bore no apparent correlations with the congeners of PCDD/Fs and Co-PCBs. The distances were also uncorrelated with the mean toxic equivalent quantities (TEQs) of PCDD/Fs (the sum of PCDDs and PCDFs), Co-PCBs, and the total PCDD/Fs and Co-PCBs. CONCLUSIONS: Although waste incinerators were the largest source of dioxins in Japan at the time of the study, the dioxins levels of mother's milk bore no apparent relationships with the distances between the mothers' domiciles and the nearest waste incinerators. In this study, several meaningful factors were not taken into account, namely, the wind direction, the level of dioxin emitted from each incinerator, the level of environmental pollution of dioxins, and the average time the mothers stayed at home each day. A full understanding of these points awaits future studies.     

Characteristics of dioxin emissions at startup and shutdown of MSW incinerators

Dioxin concentrations from municipal waste incinerators in Japan and elsewhere often show low concentrations that comply with legal limits (in this paper, the term "dioxin" designates WHO-TEQ: PCDD/Fs+dioxin-like PCB). However, such data is usually generated under normal steady state operational conditions, and there has been little investigation of releases occurring during startup and shutdown. It is important, therefore, to ascertain quantitatively emissions in an unsteady state (startup and shutdown) in order to correctly evaluate the relationship between emissions from a facility and the surrounding environment. The present study aimed to examine dioxin emissions of a continuously operated incinerator at startup and shutdown, and estimating the time period of greatest emission, and the processes causing dioxin generation. The startup process was divided into five stages and the shutdown into two; at each stage, dioxins in the flue gas were measured at the boiler outlet and the stack. From the concentration of dioxins and the flue gas volume at each stage, the amount of dioxins at startup and shutdown were calculated, and these were compared with that under steady state conditions. Dioxin concentration at the stack under steady state conditions was a very low level, while those at startup and shutdown were higher. In the case where dioxin concentration under a steady state is a low level like in this study, it is indicated that the total annual dioxin emission from a facility could be attributed to the startup periods.     

Correlation of PCDD/PCDF and CO values in a MSW incinerator--indication of memory effects in the high temperature/cooling section

The correlation of PCDD/PCDF levels with the CO emissions in a full-scale municipal waste incinerator was assessed during a four-week measurement effort. PCDD/PCDF concentrations in fly ashes-containing more than 99% of the total PCDD/PCDF burden of the fluidized bed incinerator (FBI)-were measured and compared with the emitted CO concentrations. The CO concentration during the sampling time showed no significant correlation to the PCDD/ PCDF amount in fly ash (R2 = 0.078). However, a comparison of the time integrated CO concentration several hours before sampling lead to a correlation with the PCDD/PCDF burden. Maximum correlation was found for the time integrated CO values of 3 and 4 h before sampling (R2 = 0.467 and R2 = 0.457 respectively). This indicates a memory effect in the high temperature cooling section of several hours. Possible mechanisms leading to the memory effect are discussed. The correlation of PCDD/PCDF with CO concentration demonstrate that the combustion conditions play an important role for PCDD/PCDF formation in FBIs. However the variability in the correlation of CO to PCDD/PCDF levels show that other factors have a significant influence on PCDD/PCDF formation.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.     

Dioxin/POPs legacy of pesticide production in Hamburg: Part 1—securing of the production area

α-Hexachlorocyclohexane (HCH), β-HCH, and γ-HCH (lindane) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention. Therefore, the chemicals need to be globally addressed, including the disposal of historic wastes. At most sites, the approximately 85 % of HCH waste isomers were dumped. At a former lindane factory in Hamburg and some other factories the HCH, waste was recycled producing residues with high polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) levels. The soil and ground water under the former pesticide factory was/is highly contaminated with HCH (260 tons), chlorobenzenes (550 tons), and PCDD/PCDF (6 kg toxic equivalents (TEQ)). This contamination did not result from disposal operations but from spillages and leakages during the 30 years of the factory's production history. A containment wall has been constructed around the production area to prevent the dispersal of the pollutants. The ground water is managed by a pump and treat system. Over the last 15 years, approximately 10–30 tons of this pollution reservoir has been pumped and incinerated. For the contaminated production buildings, specific assessment and demolition technologies have been applied. In addition to their HCH waste isomer deposition, former lindane/HCH productions need to be assessed for possible recycling practice of HCH and related PCDD/PCDF contamination of the production area and buildings. Since such recycling activities have taken place at several factories in different countries, the experience of assessment and management of the described production area and contaminated buildings could be valuable. Such assessment could be addressed within the frame of the Stockholm Convention.     

Serum PCDD/F concentration distribution in residents living in the vicinity of an incinerator and its association with predicted ambient dioxin exposure

The aim of this study was to evaluate the serum polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) concentration distribution in residents living in the vicinity of an incinerator and its association with annual ambient dioxin exposure predicted by an atmospheric dispersion model. A municipal waste incinerator in Northern Taiwan was chosen for this study. This incinerator had been in operation for 6 years at the time of this study. Using the incinerator site as the center, based on the simulated ambient annual average PCDD/F concentrations. Ninety-five volunteers, all live within a radius of 5 km from the incinerator for at least 5 years, who had no occupational exposure potential, were selected based on the population distribution in each district. The average serum PCDD/F concentration for these subjects living within four zones was about 14 pg I-TEQ/g lipid. The serum distribution levels of people of the four study zones, however, were not consistent with the predicted ambient levels. Results also suggest that ambient exposure might not be the most important contributor to serum concentrations when compared to other exposure sources, such as dietary intake.     

Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Various Industrial Sources

Abstract

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm³ (N represents normal conditions at 0 °C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm³). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 μg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 μg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Dioxin mass balance in a municipal waste incinerator

A dioxin mass balance in an Spanish municipal waste incinerator (MWI) is presented. Input and output inventories from two sampling collection episodes including the analysis of PCDD/PCDF in urban solid waste (USW), stack gas emissions, fly ash and slag are reported. In one collection the levels of USW were around 8 pg I-TEQ/g and non-thermal destruction was observed overall. In the other collection the levels of USW were higher (around 64 pg I-TEQ/g) and the dioxin balance revealed a thermal destruction. Analysis of the different waste materials (textile, organic, plastic, wood and paper) was performed separately and the textile samples presented the highest levels.     

Dioxin emissions from waste incinerators

Mechanisms that have been proposed to account for the emission of PCDD/PCDF from municipal waste incinerators were evaluated in the light of extensive experimental data obtained from the Quebec City municipal solid waste incinerator by Environment Canada. It was found that PCDD/PCDF emissions were closely related to the quantity of material entrained by the combustion gases.     

Occurrence, possible sources, and temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and sediment from the lower Yangtze River basin, Jiangsu and Shanghai areas of Eastern China

The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing–Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing–Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R?=?0.474, P?<?0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in the Kanto Region, Japan

The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.     

Dioxins in adipose tissue of non-occupationally exposed persons in France: correlation with individual food exposure

We evaluated individual adipose tissue (subcutaneous lipomas) dioxin contamination in non-occupationally exposed persons living in France (adult patients undergoing a surgical ablation of benign lipomas), in relation to the corresponding individually evaluated mean daily dietary dioxin intake (DDDI). The diet survey (questionnaire) included information on consumption of meat, fish, milk and dairy products, from which the individual DDDI was calculated. Sixteen subjects participated in this study. DDDI ranged between 1.06 and 3.31 pg I-TEQ/kg body weight, bw (mean value: 2.05+/-0.72). Adipose tissue polychlorinated dibenzo-p-dioxins (PCDD)/polychlorinated dibenzofurans (PCDF) levels ranged between 18.5 and 76.9 pg I-TEQ/g lipids (mean value: 35.6+/-14.8). No relation was found between the DDDI and adipose tissue PCDD/PCDF concentrations. The mean DDDI in France does not fundamentally differ from those found in other industrialised countries, is within the range of 1-4 pg I-TEQ/kg/day recently suggested by WHO-ECEH/ICPS for the tolerable daily intake of dioxins. Adipose tissue PCDD/PCDFs levels are similar to levels in other European countries and USA without relation to sex or age, and can be considered representative European background concentrations. Globalisation of alimentary production leads to a similar food exposure in Western European countries, in spite of dioxins accidental selective contaminations that are epiphenomenon and thus do not have any impact in human dioxin background levels.     

Dioxins and furans in emissions from medical waste incinerators

Dioxins and furans were detected in emissions from eight medical waste incinerators tested in California. Total uncontrolled emissions ranged from 363 to 11, 811 nanograms per dry standard cubic meter. The most effective of three wet scrubbers achieved an emissions control efficiency of 95 percent for total PCDD and PCDF. A baghouse was less than 30 percent efficient in removing PCDD and PCDF from the incinerator emissions.     

Verification of dioxin formation in a catalytic oxidizer

Emissions and inlet concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) have been measured from a catalytic oxidizer and a thermal oxidizer. The catalyst inlet temperature was 427 degrees C. The thermal oxidizer operating temperature was 791 degrees C. Data of the toxic dioxin and furan congeners are reported. Important results of this field study are: (1) the catalytic oxidizer in this study produced an increase in PCDD/PCDF congener concentration of almost 10-fold from the inlet to the outlet (stack), thus verifying results of a previous study that evaluated only PCDD/PCDF emissions. All congeners increased from inlet to the stack. (2) The thermal oxidizer had little effect on PCDD/PCDF levels. There was a decrease in four of the congeners and an increase in 13 congeners. (3) Ambient air was the main source of PCDD/PCDFs in the stack emissions of the thermal oxidizer in this study. Laboratory investigations are needed to understand how PCDD/PCDFs are formed (and emitted) under conditions of this study.