Determination of phosphine and other fumigants in air samples by thermal desorption and 2D heart-cutting gas chromatography with synchronous SIM/Scan mass spectrometry and flame photometric detection.

Fumigants and volatile industrial chemicals are particularly hazardous to health when a freight container is fumigated or the contaminated material is introduced into its enclosed environment. Phosphine is now increasingly used as a fumigant, after bromomethane--the former fumigant of choice--has been banned by the Montreal Protocol. We have enhanced our previously established thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method by integrating a second gas chromatographic dimension and a flame photometric detector to allow the simultaneous detection of phosphine and volatile organic compounds (VOCs), providing a novel application. A thermal desorption system is coupled to a two dimensional gas chromatograph using both mass spectrometric and flame photometric detection (TD-2D-GC-MS/FPD). Additionally, the collection of mass spectrometric SIM and Scan data has been synchronised, so only a single analysis is now sufficient for qualitative scanning of the whole sample and for sensitive quantification. Though detection limits for the herewith described method are slightly higher than in the previous method, they are in the low µL m(-3) range, which is not only below the respective occupational exposure and intervention limits but also allows the detection of residual contamination after ventilation. The method was developed for the separation and identification of 44 volatile substances. For 12 of these compounds (bromomethane, iodomethane, dichloromethane, 1,2-dichlorethane, benzene, tetrachloromethane, 1,2-dichloropropane, toluene, trichloronitromethane, ethyl benzene, phosphine, carbon disulfide) the method was validated as we chose the target compounds due to their relevance in freight container handling.

Halogenated hydrocarbon pesticides and other volatile organic contaminants provide analytical challenges in global trading.

Protection against infestation of a container cargo by alien species is achieved by mandatory fumigation with pesticides. Most of the effective fumigants are methyl and ethyl halide gases that are highly toxic and are a risk to both human health and the environment. There is a worldwide need for a reliable and robust analytical screening procedure for these volatile chemicals in a multitude of health and environmental scenarios. We have established a highly sensitive broad spectrum mass spectrometry method combined with thermal desorption gas chromatography to detect, identify and quantify volatile pesticide residues. Using this method, 1201 random ambient air samples taken from freight containers arriving at the biggest European ports of Hamburg and Rotterdam were analyzed over a period of two and a half years. This analytical procedure is a valuable strategy to measure air pollution from these hazardous chemicals, to help in the identification of pesticides in the new mixtures/formulations that are being adopted globally and to analyze expired breath samples after suspected intoxication in biomonitoring.

Essential and non-essential elements in tissues of harbour porpoises (Phocoena phocoena) stranded on the coasts of the North and Baltic Seas between 2004-2006.

This study on harbour porpoises (Phocoena phocoena) stranded along the coasts of the Eastern North and Western Baltic Sea as well as in the river Elbe during 2004-2006, evaluated concentrations of 20 essential and non-essential elements (Ag, Al, As, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) in liver and muscle samples. Tissue samples of 22 porpoises were taken during post-mortem investigations at the Research and Technology Centre (FTZ) in Büsum, Germany. A multi element method utilizing microwave accelerated acid digestion for sample preparation and collision/reaction cell inductively coupled plasma mass spectrometry (CC-ICP-MS) was used for element quantification. All 20 elements investigated could be determined in liver and muscle tissues except for Al in muscle samples. Furthermore the concentrations in liver tissues were higher compared to muscle tissues. While sex specific differences were observed only for Cu concentrations in liver tissue, age-dependent relationships were obtained for nine elements. Differences between juveniles and adults were found for Ag, Al, Co, Mn, Mo, Se, Sn, Pb, and V concentrations in liver, as well as Sn concentrations in muscle tissues. Furthermore, As and Sn concentrations in liver and muscle showed differences between the stranding locations. This multi-element study on harbour porpoises gives baseline information to concentrations of essential and non-essential elements in tissue to develop reference ranges for health status determination as well as the assessment of the pollutant body burden.