Heike Kaupp

Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition

Abstract Concurrent measurements of polychlorinated dibenzo- p -dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) in different size fractions of atmospheric particulate matter are presented for a winter and a summer sampling period. The PCDD/Fs and PAHs were primarily associated with particles of μ m aerodynamic diameter. The particle size distributions were similar for the compounds within each substance group and, surprisingly, also between the PCDD/Fs and PAHs. Changes in the particle size distribution of particle mass were reflected in the particle size distributions of the PCDD/Fs and PAHs. The data were employed to identify those particle size fractions dominating the wet and dry particle bound deposition of PCDD/Fs and PAHs and, furthermore, to assess the relative contributions of wet and dry deposition to the total particle bound deposition fluxes. The calculations indicate that coarse particles contribute most to the dry deposition while, in contrast, the wet deposition of the PCDD/Fs and PAHs is dominated by fine particles. Furthermore, it is estimated that in Bayreuth wet deposition dominates the total particle bound deposition of PCDD/Fs and PAHs.

Baseline contamination assessment for a new resource recovery facility in Germany part II: atmospheric concentrations of PCDD/F

The atmospheric levels of PCDD/Fs in both the gas and particle phases were measured continuously over 1 year at 7 sites in the outskirts of Augsburg, Germany, and at a rural site 15 km from the city. The homologue and congener patterns in the total air samples were similar among the different stations and stayed constant throughout the whole year. The PCDD/F levels were about two times higher at the sampling points on the edge of the city than at the remote location. There was a pronounced temporal variability of the total air concentrations, with levels in winter that were 9 times higher than the levels in summer. The gas/particle partitioning was characterised by higher gaseous fractions for more volatile compounds and higher ambient temperatures. It was concluded that the ambient air concentrations of the PCDD/Fs are determined by on-going local and regional emissions, with seasonal (winter) sources contributing the vast majority of the emissions fluxes.

Baseline contamination assessment for a new resource recovery facility in Germany. Part 1: Concept

Abstract This paper presents the scientific concept and experimental background for a series of papers describing a study of the baseline concentrations of environmental contaminants around a new resource recovery facility in Augsburg, Germany. The primary aim of this study was to evaluate the effects of the waste combustion emissions of the facility on the levels of contaminants in the surrounding area. This paper briefly reviews previous studies on this subject and then presents the concept used for this study. The concept focused on measuring ambient air concentrations. and the siting of the sampling stations. the sampling strategy and the chemicals analysed are described. The results of the initial baseline contaminant assessment, which yielded valuable insights into the emironmental behaviour of the chemicals. will be presented in a series of subsequent papers, each focusing on a separate group of chemicals. The results of the post-start-up monitoring will be presented at a later date.

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmospheric particulate matter with respect to particle size

Abstract The occurrence of polychlorinated dibenzo- p -dioxins and dibenzofurans (PCDD/Fs) in different size fractions of atmospheric particulate matter was investigated using a five-stage multijet low pressure cascade impactor backed up by a glass fibre fibrer. Three runs were conducted during the summer at a rural location in Germany. Approximately 90% of the PCDD/Fs were found on particles with aerodynamic diameters μ m. The PCDD/F homologue group patterns were very similar on all particle size fractions of a particular run, which indicates that the particle-mediated behaviour will be similar for all PCDD/Fs. The concentrations of PCDD/Fs on the smaller atmospheric particles lay at the lower end of the range in incinerator fly ash published in the literature.

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk.

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.

Testing of a sampling system and analytical method for determination of semivolatile organic compounds in ambient air

Abstract A sampling system and analytical procedure for determining PCDD/Fs, PCBs, HCB, and PAHs in ambient air was tested. The reproducibility of the concentrations and the gas/particle partitioning was ± 10% for most compounds. The removal of gaseous compounds on the XAD resin trap was greater than 99%. The adsorption of gaseous substances on the glass fiber filter was negligible for compounds primarily found in the gas phase, but could not be ruled out for compounds found mainly on particles.

Baseline contamination assessment for a new resource recovery facility in Germany: Part VI: Levels and profiles of polycyclic aromatic hydrocarbons (PAH) in ambient air

Total PAH levels in ambient air were analysed at seven urban and one rural sites in or near Augsburg, Germany, for one year. The concentrations varied during the seasons with the highest levels in winter. Ratios and profiles of PAH underwent a seasonal change, too. The variation was more marked for the group of the semivolatile PAFI (3-, 4-ring PAH, benzo[b], [k]fluoranthene). The seasonal changes reflect the changes in the contributions of the possible sources like residential heating and traffic to the PAH levels but they are also the result of a higher atmospheric reactivity of PAH during the summer months. The latter was presumably the reason why anthracene and benz[a]anthracene could not be detected in the gas phase in summer. Phenanthrene, fluoranthene and coronene dominated the PAH profiles in summer and are presumably tracers for traffic emissions. A chemical mass balance calculation done with the profile of six particulate (5-, 6-ring) PAH showed that residential heating and traffic each contributed roughly 50% to the ambient PAH levels in winter. Ratios and profiles of semivolatile PAH appear to be promising tools for estimating the contributions of the different sources more precisely.

Baseline contamination assessment for a new resource recovery facility in Germany. Part IV: Atmospheric concentrations of polychlorinated biphenyls and hexachlorobenzene

Abstract The atmospheric levels of hexachlorobenzene (HCB) and polychlorinated biphenyls (PCBs) were measured continuously over almost 1 year at 8 sites near the southern German city of Augsburg. The PCB profiles were similar at all locations, but the levels were about two times higher at sampling points on the edge of the city than at a more remote location. Whereas the PCB profile in the total air varied with time, the profile in the gas phase was very constant over the whole year at all stations. A pronounced annual cycle in the gaseous levels of the PCBs was observed, with levels in summer that were up to 5 times higher than levels in winter. The data were fully consistent with the hypothesis that the concentrations of PCBs in the atmosphere are determined by volatilization of PCB residues stored in soils and other sorbents on the earths surface. The same behaviour as for the PCBs was also observed for HCB. Equations for the gaseous concentrations of these compounds as a function of temperature were derived and found to explain 90% of the variability in the monitoring data. However, the enthalpies of phase change estimated from the data were about two times less than the enthalpies of vaporization of the compounds. Although there are a number of possible explanations for this observation, more research into the exchange of semivolatile organic contaminants between the atmosphere and the earths surface is needed to establish why the enthalpies of phase change are so much lower than expected.

A method for analysing polycyclic aromatic hydrocarbons (PAHS) in plant samples

Abstract A method was developed for the cleanup of maize samples prior to PAH analysis. The cleanup consists of two steps: (1) gel permeation chromatograpy on a porous styrene/divinylbenzene copolymer (Bio Beads SX8, Bio Rad Laboratories) and (2) further cleanup on silica gel. Quantification was performed with high resolution gas chromatography / high resolution mass spectrometry (HRGC/HRMS) using deuterated internal standards. The recoveries for a 12 C-PAH standard mixture of 14 compounds (n=3) were approximately 100% exept for Perylene and Indeno(1,2,3-cd)pyrene. The analysis of three samples of maize leaves, each in parallel, gave highly reproducible results. In no case were interferences during the HRGC/HRMS measurements observed. The cleanup method is therefore regarded as very effective, reproducible, relatively inexpensive and sufficiently fast.

A sampling device for semivolatile organic compounds in ambient air

Abstract A filter/adsorbent sampler is presented which reduces handling problems and contamination risks associated with using XAD-resins as gas traps for semivolatile organic compounds. Since Soxhlet extraction is used in most routine analyses for SOC, the sampler employs a standard Soxhlet cartridge containing XAD. This allows adsorbent precleaning, air sampling and adsorbent extraction in one vessel without transfering the resin.