Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Risk-based decision-making for drilling waste discharges using a fuzzy synthetic evaluation technique

Offshore petroleum drilling wastes contain toxic substances that are potentially harmful to the marine ecosystem. Despite environmentally benign characteristics, wastes associated with synthetic-based fluids still contain a certain amount of pollutants due to contamination with formation oil and the presence of trace heavy metals in barite, which may pose risk when discharged into the marine environment. A framework is presented here for a decision support system for the selection of the best drilling waste discharge option. Uncertainties in the quantification of risk, cost and technical feasibility are expressed by fuzzy numbers. An analytical hierarchy process with a technique called fuzzy synthetic evaluation is employed to determine the best management alternative (discharge scenario).     

Assessment of cytochrome P450 1A in harbour seals (Phoca vitulina) using a minimally-invasive biopsy approach

Biomarkers of organochlorine exposure, such as the induction of cytochrome P450 1A (CYP1A), can be used to assess the impact of environmental contaminants on the health of free-ranging marine mammal populations. The objective of the present study was to measure CYP1A in skin and liver biopsies obtained from live harbour seals (Phoca vitulina). Twelve harbour seal pups, aged three to five weeks, were captured from the Fraser River estuary, British Columbia, Canada, and temporarily held in captivity. Skin ( approximately 60 mg) and liver ( approximately 40 mg) biopsies, obtained while seals were under general anaesthesia, yielded sufficient tissue for the measurement of CYP1A by immunoblot analysis and ethoxyresorufin O-deethylase activity. A short-term exposure experiment, in which harbour seals (n=3) were treated orally with beta-naphthoflavone (BNF), resulted in increased hepatic and cutaneous CYP1A protein levels, consistent with observations in other mammals. This study is the first to measure CYP1A in skin and liver biopsies from live harbour seals and to report in vivo BNF-associated CYP1A induction in a marine mammal. The results demonstrate that microsamples collected using minimally-invasive techniques can provide toxicologically-relevant information form marine mammals.     

Present day serpentinization in New Caledonia,Oman and Yugoslavia

Geochemical evidence for modern low-temperature serpentinization has been found in three new localities. Apparently the low-temperature reactions are a common mode of formation of the lizardite-chrysotile and brucite assemblage. Possibly the ¹⁸O content of serpentine formed at low temperatures is in part inherited from the pyroxene and olivine.     

Helium isotopes in ferromanganese crusts from the central Pacific Ocean

Helium isotopes have been measured in samples of two ferromanganese crusts (VA13/2 and CD29-2) from the central Pacific Ocean. With the exception of the deepest part of crust CD29-2 the data can be explained by a mixture of implanted solar- and galactic cosmic ray-produced (GCR) He, in extraterrestrial grains, and radiogenic He in wind-borne continental dust grains. ⁴He concentrations are invariant and require retention of less than 12% of the in situ He produced since crust formation. Loss has occurred by recoil and diffusion. High ⁴He in CD29-2 samples older than 42 Ma are correlated with phosphatization and can be explained by retention of up to 12% of the in situ-produced ⁴He. ³He/⁴He of VA13/2 samples varies from 18.5 to 1852 R_a due almost entirely to variation in the extraterrestrial He contribution. The highest ³He/⁴He is comparable to the highest values measured in interplanetary dust particles (IDPs) and micrometeorites (MMs). Helium concentrations are orders of magnitude lower than in oceanic sediments reflecting the low trapping efficiency for in-falling terrestrial and extraterrestrial grains of Fe-Mn crusts. The extraterrestrial ³He concentration of the crusts rules out whole, undegassed 4-40 μm diameter IDPs as the host. Instead it requires that the extraterrestrial He inventory is carried by numerous particles with significantly lower He concentrations, and occasional high concentration GCR-He-bearing particles.     

Discrete element modelling of the influence of cover strength on basement-involved fault-propagation folding

A discrete element model is used to investigate the influence of sedimentary cover strength on the development of basement-involved fault-propagation folds. We find that uniformly weak cover best promotes the development of classical, trishear-like fault-related folds showing marked anticlinal thinning and synclinal thickening, with cover dips increasing downwards towards the fault tip. Uniformly strong cover results in more rounded fold forms with only minor hinge thickening/thinning and significant basement fault-propagation into the sedimentary cover. Heterogeneous, layered, cover sequences with marked differences in strength promote the development of more complex and variable fold forms, with a close juxtaposition of brittle and macroscopically ductile features, which diverge from the predictions of simple kinematic models. In these structures the upper layers are often poor indicators of deeper structure. In addition, we find that in layered cover sequences fault-propagation into the cover is a complex process and is strongly buffered by the weaker cover units.     

Investigating the scale of structural controls on chlorinated hydrocarbon distributions in the fractured-porous unsaturated zone of a sandstone aquifer in the UK

Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).