Abstract. The ice nucleation of bioaerosols (bacteria, pollen, spores, etc.) is a topic of growing interest, since their impact on ice cloud formation and thus on radiative forcing, an important parameter in global climate, is not yet fully understood. Here we show that pollen of different species strongly differ in their ice nucleation behaviour. The average freezing temperatures in laboratory experiments range from 240 to 255 K. As the most efficient nuclei (silver birch, Scots pine and common juniper pollen) have a distribution area up to the Northern timberline, their ice nucleation activity might be a cryoprotective mechanism. Far more intriguingly, it has turned out that water, which has been in contact with pollen and then been separated from the bodies, nucleates as good as the pollen grains themselves. The ice nuclei have to be easily-suspendable macromolecules located on the pollen. Once extracted, they can be distributed further through the atmosphere than the heavy pollen grains and so presumably augment the impact of pollen on ice cloud formation even in the upper troposphere. Our experiments lead to the conclusion that pollen ice nuclei, in contrast to bacterial and fungal ice nucleating proteins, are non-proteinaceous compounds.

The photochemistry of halides in sea spray aerosol, on salt pans, and on other salty surfaces leads to a formation of reactive halogen species. We investigated the photochemical formation of atomic chlorine (Cl) and bromine (Br) in the gas phase in the presence of laboratory-modeled salt pans consisting of sodium chloride doped with iron(III) chloride hexahydrate (0.5 and 2 wt %). The samples were spread on a Teflon sheet and exposed to simulated sunlight in a Teflon smog chamber in purified, humidified air in the presence of a test mixture of hydrocarbons at the ppb level to determine Cl, Br, and OH formation by the radical clock method. Driven by the photolytic reduction of Fe(III) to Fe(II), the production rates of the Fe(III)-doped NaCl salt samples (up to10(7) atoms cm(-3) s(-1)) exceeded the release of Cl above a pure NaCl sample by more than an order of magnitude in an initially O3-free environment at low NOX. In bromide-doped samples (0.5 wt % NaBr), a part of the Cl release was replaced by Br when Fe(III) was present. Additions of sodium sulfate, sodium oxalate, oxalic acid, and catechol to NaCl/FeCl3 samples were found to restrain the activation of chloride.

Pyrrolidinophenones represent one emerging class of newly encountered drugs of abuse, also known as 'new psychoactive substances', with stimulating psychoactive effects. In this work, we report on the detection of the new designer drug α-pyrrolidinohexiophenone (α-PHP) and its phase I and II metabolites in a human urine sample of a drug abuser. Determination and structural elucidation of these metabolites have been achieved by liquid chromatography electrospray ionisation quadrupole time-of-flight mass spectrometry (LC-ESI-QTOF-MS). By tentative identification, the exact and approximate structures of 19 phase I metabolites and nine phase II glucuronides were elucidated. Major metabolic pathways revealed the reduction of the ß-keto moieties to their corresponding alcohols, didesalkylation of the pyrrolidine ring, hydroxylation and oxidation of the aliphatic side chain leading to n-hydroxy, aldehyde and carboxylate metabolites, and oxidation of the pyrrolidine ring to its lactam followed by ring cleavage and additional hydroxylation, reduction and oxidation steps and combinations thereof. The most abundant phase II metabolites were glucuronidated ß-keto-reduced alcohols. Besides the great number of metabolites detected in this sample, α-PHP is still one of the most abundant ions together with its ß-keto-reduced alcoholic dihydro metabolite. Monitoring of these metabolites in clinical and forensic toxicology may unambiguously prove the abuse of the new designer drug α-PHP.

Environmental context. Inorganic, natural aerosols (sea-salt, mineral dust, glacial flour) and contributions of anthropogenic components (fly ash, dust from steel production and processing, etc.) contain iron that can be dissolved as Fe III in saline media. This study investigates photochemical processes in clouds and aerosols producing gas-phase Cl as a function of salt-and gas-phase composition employing a simulation chamber. Atomic Cl may contribute to the oxidative capacity of the troposphere, and our findings imply local sources.Abstract. Artificial sea-salt aerosol, containing Fe III at various compositions, was investigated in a simulation chamber (made of Teflon) for the influence of pH and of the tropospheric trace gases NO 2 , O 3 and SO 2 on the photochemical activation of chloride. Atomic chlorine (Cl) was detected in the gas phase and quantified by the radical clock technique. Dilute brines with known Fe III content were nebulised until the relative humidity reached 70-90 %. The resulting droplets (most abundant particle diameter: 0.35-0.46 mm, initial surface area: up to 3 Â 10 À2 cm 2 cm À3) were irradiated with simulated sunlight, and the consumption of a test mixture of hydrocarbons was evaluated for Cl, Br and OH. The initial rate of atomic Cl production per aerosol surface increased with Fe III and was ,1. . The observed production of atomic Cl is discussed with respect to pH and speciation of the photolabile aqueous Fe III complexes.