Dissolved silver in European estuarine and coastal waters.

Silver is one of the most toxic elements for the marine microbial and invertebrate community. However, little is known about the distribution and behaviour of dissolved silver in marine systems. This paper reports data on dissolved and sediment-associated silver in European estuaries and coastal waters which have been impacted to different extents by past and present anthropogenic inputs. This is the first extended dataset for dissolved silver in European marine waters. Lowest dissolved silver concentrations were observed in the Gullmar Fjord, Sweden (8.9 +/- 2.9 pM; x +/- 1sigma), the Tamar Estuary, UK (9.7 +/- 6.2 pM), the Fal Estuary, UK (20.6 +/- 8.3 pM), and the Adriatic Sea (21.2 +/- 6.8 pM). Enhanced silver concentrations were observed in Atlantic coastal waters receiving untreated sewage effluent from the city of A Coruna, Spain (243 +/- 195 pM), and in the mine-impacted Restronguet Creek, UK (91 +/- 71 pM). Anthropogenic wastewater inputs were a source of dissolved silver in the regions studied, with the exception of the Gullmar Fjord. Remobilisation of dissolved silver from historically contaminated sediments, resulting from acid mine drainage or sewage inputs, provided an additional source of dissolved silver to the estuaries. The ranges in the log particle-water partition coefficient (K(d)) values of 5-6 were similar for the Tamar and Mero estuaries and agreed with reported values for other estuaries. These high K(d) values indicate the particle reactive nature of silver with oxic sediments. In contrast, low K(d) values (1.4-2.7) were observed in the Fal system, which may have been due to enhanced benthic inputs of dissolved silver coupled to limited scavenging of silver on to sediments rich in Fe oxide.

Isotopic labelling of peptides and isotope ratio analysis using LC-ICP-MS: a preliminary study.

Bradykinin and substance P have been derivatised with cyclic diethylenetriaminepentaacetic anhydride (cDTPA) and subsequently labelled with natural and isotopically enriched Eu(3+). This enabled the detection and relative quantitation of the peptides using element-selective detection by high-performance liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS). Relative quantitation was achieved by differentially labelling two peptide sources, after derivatisation with cDTPA, using natural and enriched (151)Eu respectively. The (151)Eu:(153)Eu isotope ratio was measured and used to calculate the original peptide ratio. The measured ratios came within 5.2% of the known ratio. Derivatisation and chelation reactions were additionally confirmed using LC-ESI-MS.

Delta34S measurements of sulfur by multicollector inductively coupled plasma mass spectrometry.

An accurate and precise method for the determination of delta34S measurements by multicollector inductively coupled plasma mass spectrometry has been developed. Full uncertainty budgets, taking into consideration all the uncertainties of the measurement process, have been calculated. The technique was evaluated by comparing measured values with a range of isotopically enriched sulfur solutions prepared by gravimetric addition of a 34S spike. The gravimetric and measured results exhibited a correlation of R2 >0.999. Repeat measurements were also made after adding Na (up to 420 microg g(-1)) and Ca (up to 400 microg g(-1)) salts to the sulfur standard. No significant deviations in the delta34S values were observed. The Russell correction expression (Ingle, C.; Sharp, B.; Horstwood, M.; Parrish, R.; Lewis, D. J. J. Anal. At. Spectrom. 2003, 18, 219) was used to correct for mass bias on the 34S/32S isotope amount ratio from the mass bias observed for the 30Si/28Si isotope amount ratio. Consistent compensation for instrumental mass bias was achieved. Resolution of the measured delta34S values was better than 1 per thousand after consideration of all uncertainty components. The technique was evaluated for practical applications by measurement of delta34S for a range of mineral waters by pneumatic nebulization sample introduction and the analysis of genuine and counterfeit pharmaceuticals using both laser ablation sample introduction and liquid chromatography. For the former two cases polyatomic interferences were resolved by operating the MC-ICPMS in medium resolution, while for the chromatographic analyses polyatomic interferences were minimized by the use of a membrane desolvator, allowing the instrument to be operated at a resolution of 400.

Derivatisation of carboxylic acid groups in pharmaceuticals for enhanced detection using liquid chromatography with electrospray ionisation tandem mass spectrometry.

Tris(2,4,6-trimethoxyphenyl)phosphonium propylamine bromide (TMPP) has been used for the derivatisation of maleic, fumaric, sorbic and salicylic acids to facilitate determination using liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) in positive ion mode. Detection limits, achieved using multiple reaction monitoring mode, were 2, 4, 0.4 and 540 fmol (5 muL injection) for derivatised fumaric, sorbic, maleic and salicylic acids, respectively. In comparison, detection limits achieved in negative ion mode for the underivatised acids were 24, 51, 2, and 117 fmol, respectively. The method was successfully used for the determination of sorbic acid in a sample of Panadol. The derivatisation of salicylic acid was not as successful, probably due to poor reaction efficiency.