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Air and seawater samples were taken simultaneously to investigate the distribution and air-sea gas exchange of phthalates in the Arctic onboard the German Research Ship FS Polarstern. Samples were collected on expeditions ARK XX1&2 from the North Sea to the high Arctic (60 degrees N-85 degrees N) in the summer of 2004. The concentration of sigma6 phthalates (dimethyl phthalate (DMP), diethyl phthalate (DEP), di-i-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), butylbenzyl phthalate (BBP), and diethylhexyl phthalate (DEHP)) ranged from 30 to 5030 pg L(-1) in the aqueous dissolved phase and from 1110 to 3090 pg m(-3) in the atmospheric gas phase. A decreasing latitudinal trend was present in the seawater and to a lesser degree in the atmosphere from the Norwegian coast to the high Arctic. Overall, deposition dominated the air-sea gas exchange for DEHP, while volatilization from seawater took place in the near-coast environment. The estimated net gas deposition of DEHP was 5, 30, and 190 t year(-1) for the Norwegian Sea, the Greenland Sea, and the Arctic, respectively. This suggests that atmospheric transport and deposition of phthalates is a significant process for their occurrence in the remote Atlantic and Arctic Ocean.

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A comparison of different nebulisers for direct hyphenation of capillary and nano liquid chromatography (Cap-LC, Nano-LC) and quadrupole-based collision cell inductively coupled plasma mass spectrometry (CC-ICP-MS) for phosphorylation profiling of tryptic protein digests is described. Helium was used as cell gas and specially tuned instrumental conditions were used to achieve background minimisation at the mass of phosphorus, because of kinetic energy discrimination of the interfering polyatomic ions. The proposed set-up is based on a modified capillary electrophoresis interface and a home-made 4 mL spray chamber. It enables the use of gradient conditions with a highly concentrated organic mobile phase as often used in protein phosphorylation analysis, without the need to apply membrane desolvation for removal of the organic phase or further background minimisation. No significant signal suppression or other negative effects caused by the organic mobile phase occur, because of the low flow rates used in Cap-LC and the robust plasma conditions of the CC-ICP-MS instrument. A tryptic digest of beta-casein was investigated as model compound to demonstrate the applicability of the proposed set-up for phosphorylation profiling in protein analysis using quadrupole based collision-cell ICP-MS as phosphorus-specific detector. Detection limits for phosphorylated peptides down to the sub picomole level were obtained. As a complementary technique, electrospray ionisation tandem mass spectrometry (ESI-MS-MS) with data base searching was used for further characterisation of the phosphorylated peptides detected.

Six trace contaminants (acesulfame (ACE), sucralose (SUC), carbamazepine (CBZ), diatrizoic acid (DTA), 1H-benzotriazole (BTZ) and its 4-methyl analogue (4-TTri)) were traced from wastewater treatment plants (WWTPs) to receiving waters and further to riverbank filtration (RBF) wells to evaluate their prediction power as potential wastewater markers. Furthermore, the persistence of some compounds was investigated in advanced wastewater treatment by soil aquifer treatment (SAT). During wastewater treatment in four conventional activated sludge WWTPs ACE, SUC, and CBZ showed a pronounced stability expressed by stable concentration ratios in influent (in) and effluent (out) (ACE/CBZ: in45, out40; SUC/CBZ: in1.8, out1.7; and ACE/SUC: in24, out24). In a fifth WWTP, additional treatment with powdered activated carbon led to a strong elimination of CBZ, BTZ, and 4-TTri of about 80% and consequently to a distinctive shift of their ratios with unaffected compounds. Data from a seven month monitoring program at seven sampling locations at the rivers Rhine and Main in Germany revealed the best concentration correlation for ACE and CBZ (r(2) = 0.94) and also a good correlation of ACE and CBZ concentrations to BTZ and 4-TTri levels (r(2) = 0.66 to 0.82). The comparison of ratios at different sampling sites allowed for the identification of a CBZ point source. Furthermore, in Switzerland a higher consumption of SUC compared to Germany can be assumed, as a steadily increasing ACE/SUC ratio along the river Rhine was observed. In RBF wells a good correlation (r(2) = 0.85) was again observed for ACE and CBZ. Both also showed the highest stability at a prolonged residence time in the subsurface of a SAT field. In the most peripheral wells ACE and CBZ were still detected with mean values higher than 36 µg L(-1) and 1.3 µg L(-1), respectively. Although SUC concentrations in wastewater used for SAT decreased by more than 80% from about 18 µg L(-1) to 2.1 µg L(-1) and 3.5 µg L(-1) in these outlying wells, the compound was still adequate to indicate a wastewater impact in a qualitative way.

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