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Atmospheric pressure chemical ionisation liquid chromatography/multi-stage ion trap mass spectrometry (APCI-LC/MS(n)) has been applied to the study of intact bacteriohopanepolyols. Spectral characterisation of bacteriohopanepolyols of known structure present in bacterial extracts (Zymomonas mobilis and a fermenter containing methanotrophs including Methylococcus capsulatus) has revealed greater structural detail than previous liquid chromatography/mass spectrometry (LC/MS) methods and identified characteristic fragmentations indicative of numerous biohopanoid structures. Analysis of a Recent sedimentary extract from Lake Druzhby (Antarctica) has demonstrated the power of this technique to detect biohopanoids in complex samples including at least partial characterisation of previously unknown composite structures.

Atmospheric pressure chemical ionization liquid chromatography-tandem mass spectrometry (APCI LC-MS/MS) of tetraether lipid cores of archaeal origin reveals distinct dissociation pathways for three classes of core lipid extracted from Methanobacter thermautotrophicus. Within these classes, two isobaric tetraether lipids, one a scarcely reported lipid constituent of M. thermautotrophicus and the other an artefact formed during extraction from cultured cells, were identified and distinguished via their MS 2 spectra. APCI LC-MS/MS discriminates different tetraether core lipid types and isobaric species and reveals the mass of the constituent biphytanyl chains within the tetraether cores, albeit without full elucidation of their structures. Furthermore, the method allows direct estimation of the relative proportions of tetraether core lipids from chromatographic peak area measurement, allowing rapid profiling of these compounds in microbiological and environmental extracts. (J Am Soc Mass Spectrom 2009, 20, 51-59)

Bleaching of corals by loss of symbiotic dinoflagellate algae and/or photosynthetic pigments is commonly triggered by elevated temperatures coupled with high irradiance, and is a first-order threat to coral reef communities. In this study, a high-resolution high-performance liquid chromatography method integrated with mass spectrometry was applied to obtain the first definitive identification of chlorophyll and carotenoid pigments of three clades of symbiotic dinoflagellate algae ( Symbiodinium ) in corals, and their response to experimentally elevated temperature and irradiance. The carotenoids peridinin, dinoxanthin, diadinoxanthin (Dn), diatoxanthin (Dt) and b -carotene were detected, together with chlorophylls a and c 2 , and phaeophytin a , in all three algal clades in unstressed corals. On exposure to elevated temperature and irradiance, three coral species ( Montastrea franksi and Favia fragum with clade B algae, and Montastrea cavernosa with clade C) bleached by loss of 50-80% of their algal cells, with no significant impact to chlorophyll a or c 2 , or peridinin in retained algal cells. One species ( Agaricia sp. with clade C) showed no significant reduction in algal cells at elevated temperature and irradiance, but lost substantial amounts of chlorophyll a and carotenoid pigments, presumably through photo-oxidative processes. Two coral species ( Porites astreoides and Porites porites both bearing clade A algae) did not bleach. The impact of elevated temperature and irradiance on the levels of the photoprotective xanthophylls (Dn + Dt) and b -carotene varied among the corals, both in pool size and xanthophyll cycling, and was not correlated to coral bleaching resistance.

Little is known about the response of terrestrial East Antarctica to climate changes during the last glacial–interglacial cycle. Here we present a continuous sediment record from a lake in the Larsemann Hills, situated on a peninsula believed to have been ice-free for at least 40,000 yr. A mutli-proxy data set including geochronology, diatoms, pigments and carbonate stable isotopes indicates warmer and wetter conditions than present in the early part of the record. We interpret this as Marine Isotope Stage 5e after application of a chronological age-depth model and similar ice core evidence. Dry and cold conditions are inferred during the last glacial, with lake-level minima, floristic changes towards a shallow water algal community, and a greater biological receipt of ultraviolet radiation. During the Last Glacial Maximum and Termination I the lake was perennially ice-covered, with minimal snowmelt in the catchment. After ca. 10,500 cal yr B.P., the lake became seasonally moated or ice-free during summer. Despite a low accumulation rate, the sediments document some Holocene environmental changes including neoglacial cooling after ca. 2450 cal yr B.P., and a gradual increase in aridity and salinity to the present.

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The high explosives trinitrotoluene, nitroglycerine, pentaerythritol tetranitrate and hexahydro-1,3,5-trinitro-1,3,5-triazine are efficiently ionised under negative ion atmospheric pressure chemical ionisation (APCI) conditions. The limit of detection is improved, in some cases by several orders of magnitude, by complexation with chlorine demonstrating this to be a highly suitable method for enhancing the detection capabilities for explosives. The spectra produced from introduction of the analytes in a liquid matrix, with and without chlorine present, contain a number of ions that arise through secondary processes including breakdown and adduct formation. Sample introduction into an APCI source in air, via a heated-plate inlet with a supplementary feed of dichloromethane, produces improved response for the chloride adducts of the analytes and minimises their decomposition during analysis. The tandem mass spectra produced from the chloride adducts are simple. Optimisation of the trapping parameters of the ion trap detector enhances selected transitions, yields highly reproducible spectra and improves the limits of detection for MS/MS analysis.