Development of a comprehensive analytical method for the determination of chlorinated paraffins in spruce needles applied in passive air sampling.

Conifer needles are used for the monitoring of atmospheric persistent organic pollutants. The objective of the present study was to develop a method for the detection of airborne chlorinated paraffins (CPs) using spruce needles as a passive sampler. The method is based on liquid extraction of the cuticular wax layer followed by chromatographic fractionation and detection of CPs using two different GCMS techniques. Total CP concentrations (sum of short (SCCP), medium (MCCP) and long chain CPs (LCCP)) were determined by EI-MS/MS. SCCP and MCCP levels as well as congener group patterns (n-alkane chain length, chlorine content) could be evaluated using ECNI-LRMS. For the first time, data on environmental airborne CPs on spruce needles taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) are presented providing evidence that spruce needles are a suitable passive sampling system for the monitoring of atmospheric CPs.

Altitude profiles of total chlorinated paraffins in humus and spruce needles from the Alps (MONARPOP).

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. CPs were analyzed in humus and needle samples, which were taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) at sampling sites of 7 different altitude profiles in the Alps. Gas chromatography combined with electron ionization tandem mass spectrometry (EI-MS/MS) was used for the determination of total CPs (sum of short, medium and long chain CPs). CPs were found in all samples; the concentrations varied between 7 and 199 ng g(-1) dry weight (dw) and within 26 and 460 ng g(-1) dw in humus and needle samples, respectively. A clear vertical tendency within the individual altitude profiles could not be ascertained. Within all altitude profiles, elevated concentrations were observed in humus samples taken between 700 and 900 m and between 1300 and 1500 m. In the needle samples no similar correlation could be observed due to higher variation of the data.

Sediment record and atmospheric deposition of brominated flame retardants and organochlorine compounds in Lake Thun, Switzerland: lessons from the past and evaluation of the present.

Chronology of brominated fame retardants (BFRs), a class of currentlywidely used chemicals, was compared to the respective historical profiles of legacy organochlorine compounds in three dated sediment cores from a prealpine lake (Lake Thun, Switzerland). Concentrations of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) started to increase in the 1980s-1990s. In the more recent sediment layers, PBDEs still had steady or increasing concentrations, whereas for HBCDs one sediment core revealed a decreasing trend. In contrast to the contemporary BFRs, concentrations of legacy organochlorines, such as polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and dichlorodiphenyl trichloroethane (DDT), peaked in deeper sediment layers deposited some decades ago. Measurements of atmospheric deposition and evaluation of wastewater discharges pointtoward deposition on the lake surface as a relevant input pathway and wastewater as a minor source of POPs in Lake Thun. The effect of the environmental awareness and the regulations taken in the 1970s to reduce environmental pollution of organochlorines is well reflected in the analyzed sediment cores. The sediment burden closely follows estimated time trends of consumption and emission of PCBs and DDT. The current residues in sediment of BFRs are still lower than the historical peak levels of organochlorines. However, current atmospheric deposition of BFRs is similar to deposition of PCBs. Considering the high amount of BFRs presently stocked in the anthroposphere in flame proofed materials, further measures to reduce emissions during BFRs life cycle are recommended to prevent high environmental pollution as it occurred for the organochlorine compounds.

Historical profiles of chlorinated paraffins and polychlorinated biphenyls in a dated sediment core from Lake Thun (Switzerland).

A dated sediment core from Lake Thun covering the last 120 years was analyzed to get an overview of the historical trend of the chlorinated paraffin (CP) and polychlorinated biphenyl (PCB) deposition, because CPs and PCBs have/had similar applications as plasticizers and flame retardants. Total CP concentrations (sum of short chain (SCCP), medium chain (MCCP), and long chain CPs (LCCP)) showed a steep increase in the 1980s and a more-or-less stable level of 50 ng g(-1) dry weight (dw) since then. The concentration-time profile is in good agreement with the available information on global production data. The quantification of higher chlorinated SCCPs using electron capture negative ionization low resolution mass spectrometry (ECNI-LRMS) revealed an increase in recent years. In addition, the degree of chlorination of SCCPs has strongly increased during the past 40 years, which may indicate its use as an additive for plastics, paints, and coatings. Furthermore, PCBs were analyzed in dated sediment slices. The PCB concentrations (sum of the six indicator congeners) peaked around 1969 (18 ng g(-1) dw) and decreased to 1.3 ng g(-1) dw in the surface layer corresponding to 2004. The peak level of CPs exceeded those of PCBs by about a factor of 3.

Organic pollutants in compost and digestate. Part 2. Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated biphenyls, brominated flame retardants, perfluorinated alkyl substances, pesticides, and other compounds.

Compost and digestate are important recycling fertilizers and have beneficial effects on soil parameters. However, they can contain significant amounts of organic pollutants. Here, the first comprehensive data set on dibenzo-p-dioxins and -furans (PCDD/F), dioxin-like polychlorinated biphenyls (DL-PCB), brominated flame retardants, perfluorinated alkyl substances (PFAS), pesticides, phthalates, nonylphenol and chlorinated paraffins (CP) in source-separated compost and digestate from Switzerland is presented (n = 3-18). The median summation 17PCDD/F and summation 12DL-PCB concentrations were at 3.2 ng I-TEQ kg(-1)dry weight (dw) and 3.0 ng WHO-TEQ kg(-1)dw, respectively. Brominated diphenyl ether 209 (BDE 209) accounted for 72% of the total polyBDE content (10 microg kg(-1)dw). Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) levels were at 100 and 0.51 microg kg(-1)dw, respectively. PFAS were identified for the first time in compost and digestate (median concentration 6.3 microg kg(-1)dw, summation 21compounds). Out of 269 pesticides analysed, 30 fungicides, 14 herbicides, eight insecticides and one acaricide were detected. Di-(2-ethylhexyl)phthalate (DEHP) median concentration accounted for 280 microg kg(-1)dw and nonylphenol was below the detection limit of 1 mg kg(-1)dw. The sum of short and medium chain CP was between 90 and 390 microg kg(-1)dw. The concentrations observed were at or above the levels found in background soils, which are the main recipient of compost and digestate. Where actually applied, compost can contribute considerably to the total input of organic pollutants to the soil. However, on a total Swiss agricultural area base, inputs seem to be limited.