Oxygenated and Nitrated Polycyclic Aromatic Hydrocarbons in Ambient Air-Levels, Phase Partitioning, Mass Size Distributions, and Inhalation Bioaccessibility.

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of Σ10OPAHs were 10.0 ± 9.2 ng/m3 in winter and 3.5 ± 1.6 ng/m3 in summer. The gradient to the regional background site exceeded 1 order of magnitude. Σ18NPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM10 size fraction is found to be ≈5% of the total ambient concentration of OPAHs and up to ≈2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.

Application of 96-well plate SPE method for analysis of persistent organic pollutants in low volume blood serum samples.

Though many persistent organic pollutants (POPs) are closely regulated the human population is still exposed to these ubiquitous chemicals from the environment and diet. Safe management and human biomonitoring of POPs is necessary to understand the risk of exposure. Within human biomonitoring the mass of sample is often limited, therefore robust methods using smaller sample amounts are necessary. This study developed a 96-well plate solid phase extraction (SPE) method for determination of selected POPs: polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and non-persistent novel flame retardants (NFRs) in low volume blood serum. Non-destructive clean-up coupling Oasis HLB extraction plate with Phree phospholipid removal plate was employed. Extraction efficiency was determined at low and high concentrations in certified reference materials NIST SRM 1957 and 1958, respectively. Target compounds deviated from certified values on average by 15% and 21% for SRM 1957 and SRM 1958, respectively. Observed limit of detections (LODs) ranged from 0.36 pg/mL (PCB 180) to 66.07 pg/mL (δ-HCH). The applicability for real samples is demonstrated on 48 samples from pregnant women enrolled in the pilot phase of the CELSPAC: TNG study. In total, 30 target compounds were detected in at least one sample. The method developed here provides a fast and reliable analysis of human blood serum with possibility to introduce automation for the sample preparation procedure.

Organochlorine pesticides and polychlorinated biphenyls along an east-to-west gradient in subtropical North Atlantic surface water.

Despite the fact that most persistent toxic substances have hardly been primarily emitted for several decades, their concentrations are only slowly decreasing in the global oceans. Surface seawater samples were collected along a 38°-24° N/28°-67° W transect in the subtropical North Atlantic Ocean. While the concentration levels of hexachlorobenzene (2.1-6.1 pg L-1), dichlorodiphenyltrichloroethane (DDT, up to 2.1 pg L-1) and polychlorinated biphenyls (PCB, 10.8-24.9 pg L-1) were in the same range as observed earlier in the North Atlantic, hexachlorocyclohexane (HCH, 90-627 pg L-1) was found elevated, partly also relative to previous measurements in the same sea region. Hereby, the ratio α-HCH/γ-HCH was very low, 0.09-0.13. Chlordane and endosulfan were found in the range <3.0-11.1 and <5.8-8.8 pg L-1 respectively. DDT metabolites, endrin and related pesticides were found below quantification limits. Spatial pollution patterns in surface seawaters seem to be determined by atmospheric and oceanic transport patterns, rather than by mixing and air-sea equilibrium. The comparison with global multicompartment chemistry-transport model predictions of surface seawater levels indicate underestimated degradation of PCBs and overestimated emissions of endosulfan.