Nitro- and oxy-PAHs in grassland soils from decade-long sampling in central Europe.

Long-term exposure to polycyclic aromatic hydrocarbons (PAHs) and their nitrated (NPAHs) and oxygenated (OPAHs) derivatives can cause adverse health effects due to their carcinogenicity, mutagenicity and oxidative potential. The distribution of PAH derivatives in the terrestrial environment has hardly been studied, although several PAH derivatives are ubiquitous in air and long-lived in soil and water. We report the multi-annual variations in the concentrations of NPAHs, OPAHs and PAHs in soils sampled at a semi-urban (Mokrá, Czech Republic) and a regional background site (Kosetice, Czech Republic) in central Europe. The concentrations of the Σ18NPAHs and the Σ11+2OPAHs and O-heterocycles were 0.31 ± 0.23 ng g-1 and 4.03 ± 3.03 ng g-1, respectively, in Kosetice, while slightly higher concentrations of 0.54 ± 0.45 ng g-1 and 5.91 ± 0.45 ng g-1, respectively, were found in soil from Mokrá. Among the 5 NPAHs found in the soils, 1-nitropyrene and less so 6-nitrobenzo(a)pyrene were most abundant. The OPAHs were more evenly distributed. The ratios of the PAH derivatives to their parent PAHs in Kosetice indicate that they were long-range transported to the background site. Our results show that several NPAHs and OPAHs are abundant in soil and that gas-particle partitioning is a major factor influencing the concentration of several semi-volatile NPAHs and OPAHs in the soils. Complete understanding of the long-term variations of NPAH and OPAH concentrations in soil is limited by the lack of kinetic data describing their formation and degradation.

Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks.

The most commonly used passive air sampler (PAS) (i.e. polyurethane foam (PUF) disk) is cheap, versatile, and capable of accumulating compounds present both in gas and particle phases. Its performance for particle associated compounds is however disputable. In this study, twelve sets of triplicate PUF-PAS were deployed outdoors for exposure periods of 1-12 weeks together with continuously operated active samplers, to characterize sampling efficiency and derive sampling rates (RS) for compounds belonging to 7 SVOC classes (including particle associated compounds). PUF-PAS efficiently and consistently sampled polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and eight novel brominated flame retardant (nBFR) compounds. Low accuracy and lack of sensitivity was observed for most polychlorinated dibenzo-p-dioxins/furans PCDD/Fs and polybrominated diphenyl ethers (PBDEs) (under the conditions of this study), with the exception of some congeners which may be used as qualitative markers for their respective classes. Application of compound specific RS was found crucial for all compounds except PCBs. Sampling efficiency of the particle associated compounds was often low.

Longer-term and short-term variability in pollution of fluvial sediments by dioxin-like and endocrine disruptive compounds.

Changes in pollutant loads in relatively dynamic river sediments, which contain very complex mixtures of compounds, can play a crucial role in the fate and effects of pollutants in fluvial ecosystems. The contamination of sediments by bioactive substances can be sensitively assessed by in vitro bioassays. This is the first study that characterizes detailed short- and long-term changes in concentrations of contaminants with several modes of action in river sediments. One-year long monthly study described seasonal and spatial variability of contamination of sediments in a representative industrialized area by dioxin-like and endocrine disruptive chemicals. There were significant seasonal changes in both antiandrogenic and androgenic as well as dioxin-like potential of river sediments, while there were no general seasonal trends in estrogenicity. Aryl hydrocarbon receptor-dependent potency (dioxin-like potency) expressed as biological TCDD-equivalents (BIOTEQ) was in the range of 0.5-17.7 ng/g, dry mass (dm). The greatest BIOTEQ levels in sediments were observed during winter, particularly at locations downstream of the industrial area. Estrogenicity expressed as estradiol equivalents (EEQ) was in the range of 0.02-3.8 ng/g, dm. Antiandrogenicity was detected in all samples, while androgenic potency in the range of 0.7-16.8 ng/g, dm dihydrotestosterone equivalents (DHT-EQ) was found in only 30 % of samples, most often during autumn, when antiandrogenicity was the least. PAHs were predominant contaminants among analyzed pollutants, responsible, on average, for 13-21 % of BIOTEQ. Longer-term changes in concentrations of BIOTEQ corresponded to seasonal fluctuations, whereas for EEQ, the inter-annual changes at some locations were greater than seasonal variability during 1 year. The inter- as well as intra-annual variability in concentrations of both BIOTEQ and EEQ at individual sites was greater in spring than in autumn which was related to hydrological conditions in the river. This study stresses the importance of river hydrology and its seasonal variations in the design of effective sampling campaigns, as well as in the interpretation of any monitoring results.