Temperature measurements, gas chemistry, and gas hydrates of the Dvurechenskii mud volcano

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.

Impact of salinity and growth phase on alkenone distributions in coastal haptophytes

Batch cultures of Isochrysis galbana (strain CCMP 1323) and Chrysotila lamellosa (strain CCMP 1307) were grown at salinity ca. 10 to ca. 35 and the alkenone distributions determined for different growth phases. UK'37 values decreased slightly with salinity for C. lamellosa but were largely unaffected for I. galbana except during the decline phase. The values decreased with incubation time in both species. The proportion of C37:4, used as proxy for salinity, increased in both species at 0.16-0.20% per salinity unit, except during the stationary phase for I. galbana. C37:4 was much more abundant in C. lamellosa (30-44%) than in I. galbana (4-12%). Although our results suggest that salinity has a direct effect on alkenone distributions, growth phase and species composition will also have a marked impact, complicating the use of alkenone distributions as a proxy for salinity in the marine environment.

Seawater carbonate chemistry and biological processes during experiments with common cuttlefish Sepia officinalis, 2010

Ocean acidification and associated changes in seawater carbonate chemistry negatively influence calcification processes and depress metabolism in many calcifying marine invertebrates. We present data on the cephalopod mollusc Sepia officinalis, an invertebrate that is capable of not only maintaining calcification, but also growth rates and metabolism when exposed to elevated partial pressures of carbon dioxide (pCO2). During a 6 wk period, juvenile S. officinalis maintained calcification under ~4000 and ~6000 ppm CO2, and grew at the same rate with the same gross growth efficiency as did control animals. They gained approximately 4% body mass daily and increased the mass of their calcified cuttlebone by over 500%. We conclude that active cephalopods possess a certain level of pre-adaptation to long-term increments in carbon dioxide levels. Our general understanding of the mechanistic processes that limit calcification must improve before we can begin to predict what effects future ocean acidification will have on calcifying marine invertebrates.

Seawater carbonate chemistry and biological processes during experiments with common cuttlefish Sepia officinalis, 2008

Ocean acidification and associated changes in seawater carbonate chemistry negatively influence calcification processes and depress metabolism in many calcifying marine invertebrates. We present data on the cephalopod mollusc Sepia officinalis, an invertebrate that is capable of not only maintaining calcification, but also growth rates and metabolism when exposed to elevated partial pressures of carbon dioxide (pCO2). During a 6 wk period, juvenile S. officinalis maintained calcification under ~4000 and ~6000 ppm CO2, and grew at the same rate with the same gross growth efficiency as did control animals. They gained approximately 4% body mass daily and increased the mass of their calcified cuttlebone by over 500%. We conclude that active cephalopods possess a certain level of pre-adaptation to long-term increments in carbon dioxide levels. Our general understanding of the mechanistic processes that limit calcification must improve before we can begin to predict what effects future ocean acidification will have on calcifying marine invertebrates.

The analysis and detection of new psychoactive substances in biological matrices

New psychoactive substances (NPSs) have appeared on the recreational drug market at an unprecedented rate in recent years. Many are not new drugs but failed products of the pharmaceutical industry. The speed and variety of drugs entering the market poses a new complex challenge for the forensic toxicology community. The detection of these substances in biological matrices can be difficult as the exact compounds of interest may not be known. Many NPS are sold under the same brand name and therefore users themselves may not know what substances they have ingested. The majority of analytical methods for the detection of NPSs tend to focus on a specific class of compounds rather than a wide variety. In response to this, a robust and sensitive method was developed for the analysis of various NPS by solid phase extraction (SPE) with gas chromatography mass spectrometry (GCMS). Sample preparation and derivatisation were optimised testing a range of SPE cartridges and derivatising agents, as well as derivatisation incubation time and temperature. The final gas chromatography mass spectrometry method was validated in accordance with SWGTOX 2013 guidelines over a wide concentration range for both blood and urine for 23 and 25 analytes respectively. This included the validation of 8 NBOMe compounds in blood and 10 NBOMe compounds in urine. This GC-MS method was then applied to 8 authentic samples with concentrations compared to those originally identified by NMS laboratories. The rapid influx of NPSs has resulted in the re-analysis of samples and thus, the stability of these substances is crucial information. The stability of mephedrone was investigated, examining the effect that storage temperatures and preservatives had on analyte stability daily for 1 week and then weekly for 10 weeks. Several laboratories identified NPSs use through the cross-reactivity of these substances with existing screening protocols such as ELISA. The application of Immunalysis ketamine, methamphetamine and amphetamine ELISA kits for the detection of NPS was evaluated. The aim of this work was to determine if any cross-reactivity from NPS substances was observed, and to determine whether these existing kits would identify NPS use within biological samples. The cross- reactivity of methoxetamine, 3-MeO-PCE and 3-MeO-PCP for different commercially point of care test (POCT) was also assessed for urine. One of the newest groups of compounds to appear on the NPS market is the NBOMe series. These drugs pose a serious threat to public health due to their high potency, with fatalities already reported in the literature. These compounds are falsely marketed as LSD which increases the chance of adverse effects due to the potency differences between these 2 substances. A liquid chromatography tandem mass spectrometry (LC-MS/MS) method was validated in accordance with SWGTOX 2013 guidelines for the detection for 25B, 25C and 25I-NBOMe in urine and hair. Long-Evans rats were administered 25B-, 25C- and 25I-NBOMe at doses ranging from 30-300 µg/kg over a period of 10 days. Tail flick tests were then carried out on the rats in order to determine whether any analgesic effects were observed as a result of dosing. Rats were also shaved prior to their first dose and reshaved after the 10-day period. Hair was separated by colour (black and white) and analysed using the validated LC-MS/MS method, assessing the impact hair colour has on the incorporation of these drugs. Urine was collected from the rats, analysed using the validated LC-MS/MS method and screened for potential metabolites using both LC-MS/MS and quadrupole time of flight (QToF) instrumentation.

Development of the gas chromatograph – mass spectrometer to investigate volatile species in the lunar soil for the Luna-Resurs mission

Since the analysis of the lunar rocks and soil samples, brought to Earth by the Apollo missions, it is believed that the Moon has a waterless nature and also other volatile species are strongly depleted. Advancement in analysis techniques helped to identify water and other volatile species in lunar volcanic glasses. Additionally, recent lunar space missions detected water and volatile organic compounds in the region of the lunar poles where permanently shadowed craters are existing. All known lunar soil samples available on Earth come from the lunar near side, close to the equator. To verify the most recent measurement results and to enhance the knowledge of the geological history of the Moon it is of high interest to perform in situ measurements on the lunar poles. For this reason the Russian space agency, Roskosmos, developed aprogram for the scientific exploration of the lunar poles. The Gas Analysis Package (GAP) is part of the selected scientific payload aboard the Luna-Resurs Lander. This instrument uses pyrolytic cells and will apply laser spectroscopy, gas chromatography and mass spectrometry to detect and analyze volatile components trapped in the lunar soil. An existing ion optical design of a compact reflectron type time-of-flight mass spectrometer, originally built for the MEAP/P-BACE balloon mission, was chosen as a part of the GAP instrument. The scope of this thesis is the development of the interface between gas chromatography (GC) and this Neutral Gas Mass Spectrometer (NGMS) to perform coupled GC-MS measurements. In the first part of this thesis the interfacing concept was developed and verified by coupling the NGMS prototype to gas chromatography. The second part of this thesis is devoted to the development of the NGMS flight version.

Measuring the Impact of Melaleuca quinquenervia Biochar Application on Soil Quality, Plant Growth, and Microbial Gas Flux

Biochar has been heralded a mechanism for carbon sequestration and an ideal amendment for improving soil quality. Melaleuca quinquenervia is an aggressive and wide-spread invasive species in Florida. The purpose of this research was to convert M. quinquenervia biomass into biochar and measure how application at two rates (2% or 5% wt/wt) impacts soil quality, plant growth, and microbial gas flux in a greenhouse experiment using Phaseolus vulgaris L. and local soil. Plant growth was measured using height, biomass weight, specific leaf area, and root-shoot ratio. Soil quality was evaluated according to nutrient content and water holding capacity. Microbial respiration, as carbon dioxide (CO2), was measured using gas chromatography. Biochar addition at 5% significantly reduced available soil nutrients, while 2% biochar application increased almost all nutrients. Plant biomass was highest in the control group, p2 flux decreased significantly in both biochar groups, but reductions were not long term.

Retention and degradation of organics in Rundle waste shale/retort water mixtures

Batch, column and field lysimeter studies have been conducted to evaluate the concept of codisposal of retort water with Rundle (Queensland, Australia) waste shales. The batch studies indicated that degradation of a significant proportion of the total organic load occurs if the mixture is seeded with soil or compost. These results are compared with those from laboratory column studies and from the field lysimeter at the Rundle site. G.c.-m.s. analysis of some of the eluants indicated that significant degradation of the base-neutral fraction occurs even if no soil seed is added, and that degradation of this fraction was higher under anaerobic conditions.

Characterisation and source identification of selected pollutants in house dust

House dust is a heterogeneous matrix, which contains a number of biological materials and particulate matter gathered from several sources. It is the accumulation of a number of semi-volatile and non-volatile contaminants. The contaminants are trapped and preserved. Therefore, house dust can be viewed as an archive of both the indoor and outdoor air pollution. There is evidence to show that on average, people tend to stay indoors most of the time and this increases exposure to house dust. The aims of this investigation were to: " assess the levels of Polycyclic Aromatic Hydrocarbons (PAHs), elements and pesticides in the indoor environment of the Brisbane area; " identify and characterise the possible sources of elemental constituents (inorganic elements), PAHs and pesticides by means of Positive Matrix Factorisation (PMF); and " establish the correlations between the levels of indoor air pollutants (PAHs, elements and pesticides) with the external and internal characteristics or attributes of the buildings and indoor activities by means of multivariate data analysis techniques. The dust samples were collected during the period of 2005-2007 from homes located in different suburbs of Brisbane, Ipswich and Toowoomba, in South East Queensland, Australia. A vacuum cleaner fitted with a paper bag was used as a sampler for collecting the house dust. A survey questionnaire was filled by the house residents which contained information about the indoor and outdoor characteristics of their residences. House dust samples were analysed for three different pollutants: Pesticides, Elements and PAHs. The analyses were carried-out for samples of particle size less than 250 µm. The chemical analyses for both pesticides and PAHs were performed using a Gas Chromatography Mass Spectrometry (GC-MS), while elemental analysis was carried-out by using Inductively-Coupled Plasma-Mass Spectroscopy (ICP-MS). The data was subjected to multivariate data analysis techniques such as multi-criteria decision-making procedures, Preference Ranking Organisation Method for Enrichment Evaluations (PROMETHEE), coupled with Geometrical Analysis for Interactive Aid (GAIA) in order to rank the samples and to examine data display. This study showed that compared to the results from previous works, which were carried-out in Australia and overseas, the concentrations of pollutants in house dusts in Brisbane and the surrounding areas were relatively very high. The results of this work also showed significant correlations between some of the physical parameters (types of building material, floor level, distance from industrial areas and major road, and smoking) and the concentrations of pollutants. Types of building materials and the age of houses were found to be two of the primary factors that affect the concentrations of pesticides and elements in house dust. The concentrations of these two types of pollutant appear to be higher in old houses (timber houses) than in the brick ones. In contrast, the concentrations of PAHs were noticed to be higher in brick houses than in the timber ones. Other factors such as floor level, and distance from the main street and industrial area, also affected the concentrations of pollutants in the house dust samples. To apportion the sources and to understand mechanisms of pollutants, Positive Matrix Factorisation (PMF) receptor model was applied. The results showed that there were significant correlations between the degree of concentration of contaminants in house dust and the physical characteristics of houses, such as the age and the type of the house, the distance from the main road and industrial areas, and smoking. Sources of pollutants were identified. For PAHs, the sources were cooking activities, vehicle emissions, smoking, oil fumes, natural gas combustion and traces of diesel exhaust emissions; for pesticides the sources were application of pesticides for controlling termites in buildings and fences, treating indoor furniture and in gardens for controlling pests attacking horticultural and ornamental plants; for elements the sources were soil, cooking, smoking, paints, pesticides, combustion of motor fuels, residual fuel oil, motor vehicle emissions, wearing down of brake linings and industrial activities.

Plasma metabolomics reveals biomarkers of the atherosclerosis

Atherosclerotic cardiovascular disease remains the leading cause of morbidity and mortality in industrialized societies. The lack of metabolite biomarkers has impeded the clinical diagnosis of atherosclerosis so far. In this study, stable atherosclerosis patients (n=16) and age- and sex-matched non-atherosclerosis healthy subjects (n=28) were recruited from the local community (Harbin, P. R. China). The plasma was collected from each study subject and was subjected to metabolomics analysis by GC/MS. Pattern recognition analyses (principal components analysis, orthogonal partial least-squares discriminate analysis, and hierarchical clustering analysis) commonly demonstrated plasma metabolome, which was significantly different from atherosclerotic and non-atherosclerotic subjects. The development of atherosclerosis-induced metabolic perturbations of fatty acids, such as palmitate, stearate, and 1-monolinoleoylglycerol, was confirmed consistent with previous publication, showing that palmitate significantly contributes to atherosclerosis development via targeting apoptosis and inflammation pathways. Altogether, this study demonstrated that the development of atherosclerosis directly perturbed fatty acid metabolism, especially that of palmitate, which was confirmed as a phenotypic biomarker for clinical diagnosis of atherosclerosis.

Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives : A review

The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis. (C) 2013 Elsevier B. V. All rights reserved.

Desorption electrospray ionisation mass spectrometry reveals in situ modification of a hindered amine light stabiliser resulting from direct N–OR bond cleavage

Detection and characterisation of structural modifications of a hindered amine light stabiliser (HALS) directly from a polyester-based coil coating have been achieved by desorption electrospray ionisation mass spectrometry (DESI-MS) for the first time. In situ detection is made possible by exposing the coating to an acetone vapour atmosphere prior to analysis. This is a gentle and non-destructive treatment that allows diffusion of analyte to the surface without promoting lateral migration. Using this approach a major structural modification of the HALS TINUVIN®123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) was discovered where one N-ether piperidine moiety (N-OC8H17) is converted to a secondary piperidine (N–H). With the use of 2-dimensional DESI-MS imaging the modification was observed to arise during high curing temperatures (ca. 260 °C) and under simulated physiological conditions (80 °C, full solar spectrum). It is proposed that the secondary piperidine derivative is a result of a highly reactive aminyl radical intermediate produced by N–O homolytic bond cleavage. The nature of the bond cleavage is also suggested by ESR spin-trapping experiments employing α-phenyl-N-tert-butyl nitrone (PBN) in toluene at 80 °C. The presence of a secondary piperidine derivative in situ and the implication of N–OR competing with NO–R bond cleavage suggest an alternative pathway for generation of the nitroxyl radical—an essential requirement in anti-oxidant activity that has not previously been described for the N-ether sub-class of HALS.

Novel use of faecal sterols to assess human faecal contamination in Antarctica : a likelihood assessment matrix for environmental monitoring

Wastewater containing human sewage is often discharged with little or no treatment into the Antarctic marine environment. Faecal sterols (primarily coprostanol) in sediments have been used for assessment of human sewage contamination in this environment, but in situ production and indigenous faunal inputs can confound such determinations. Using gas chromatography with mass spectral detection profiles of both C27 and C29 sterols, potential sources of faecal sterols were examined in nearshore marine sediments, encompassing sites proximal and distal to the wastewater outfall at Davis Station. Faeces from indigenous seals and penguins were also examined. Faeces from several indigenous species contained significant quantities of coprostanol but not 24-ethylcoprostanol, which is present in human faeces. In situ coprostanol and 24-ethylcoprostanol production was identified by co-production of their respective epi isomers at sites remote from the wastewat er source and in high total organic matter sediments. A C 29 sterols-based polyphasic likelihood assessment matrix for human sewage contamination is presented, which distinguishes human from local fauna faecal inputs and in situ production in the Antarctic environment. Sewage contamination was detected up to 1.5 km from Davis Station.