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11.
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.  相似文献   
12.
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).  相似文献   
13.
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.  相似文献   
14.
Sea Beam and Deep-Tow were used in a tectonic investigation of the fast-spreading (151 mm yr-1) East Pacific Rise (EPR) at 19°30 S. Detailed surveys were conducted at the EPR axis and at the Brunhes/Matuyama magnetic reversal boundary, while four long traverses (the longest 96 km) surveyed the rise flanks. Faulting accounts for the vast majority of the relief. Both inward and outward facing fault scarps appear in almost equal numbers, and they form the horsts and grabens which compose the abyssal hills. This mechanism for abyssal hill formation differs from that observed at slow and intermediate spreading rates where abyssal hills are formed by back-tilted inward facing normal faults or by volcanic bow-forms. At 19°30 S, systematic back tilting of fault blocks is not observed, and volcanic constructional relief is a short wavelength signal (less than a few hundred meters) superimposed upon the dominant faulted structure (wavelength 2–8 km). Active faulting is confined to within approximately 5–8 km of the rise axis. In terms of frequency, more faulting occurs at fast spreading rates than at slow. The half extension rate due to faulting is 4.1 mm yr-1 at 19°30 S versus 1.6 mm yr-1 in the FAMOUS area on the Mid-Atlantic Ridge (MAR). Both spreading and horizontal extension are asymmetric at 19°30 S, and both are greater on the east flank of the rise axis. The fault density observed at 19°30 S is not constant, and zones with very high fault density follow zones with very little faulting. Three mechanisms are proposed which might account for these observations. In the first, faults are buried episodically by massive eruptions which flow more than 5–8 km from the spreading axis, beyond the outer boundary of the active fault zone. This is the least favored mechanism as there is no evidence that lavas which flow that far off axis are sufficiently thick to bury 50–150 m high fault scarps. In the second mechanism, the rate of faulting is reduced during major episodes of volcanism due to changes in the near axis thermal structure associated with swelling of the axial magma chamber. Thus the variation in fault spacing is caused by alternate episodes of faulting and volcanism. In the third mechanism, the rate of faulting may be constant (down to a time scale of decades), but the locus of faulting shifts relative to the axis. A master fault forms near the axis and takes up most of the strain release until the fault or fault set is transported into lithosphere which is sufficiently thick so that the faults become locked. At this point, the locus of faulting shifts to the thinnest, weakest lithosphere near the axis, and the cycle repeats.  相似文献   
15.
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.  相似文献   
16.
17.
The Quaternary Eburru volcanic complex in the south-central Kenya Rift consists of pantelleritic trachytes and pantellerites. The phenocryst assemblage in the trachytes is sanidine + fayalite + ferrohedenbergite + aenigmatite ± quartz ± ilmenite ± magnetite ± pyrrhotite ± pyrite. In the pantellerites, the assemblage is sanidine + quartz + ferrohedenbergite + fayalite + aenigmatite + ferrorichterite + pyrrhotite ± apatite, although fayalite, ferrohedenbergite and ilmenite are absent from more evolved rocks (e.g. with SiO2 > 71%). QUILF temperature calculations for the trachytes range from 709 to 793 °C and for the pantellerites 668–708 °C, the latter temperatures being among the lowest recorded for peralkaline silicic magmas. The QUILF thermobarometer demonstrates that the Eburru magmas crystallized at relatively low oxidation states (ΔFMQ + 0.5 to − 1.6) for both trachytes and pantellerites. The trachytes and pantellerites evolved along separate liquid lines of descent, the trachytes possibly deriving from a more mafic parent by fractional crystallization and the pantellerites from extreme fractionation of comenditic magmas.  相似文献   
18.
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).  相似文献   
19.
20.
Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H2O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe3+/Fe2+ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO2 were imposed (NNO + 1.5 for the 1.5 wt% H2O series, NNO + 2.3 for the 4.5 wt% H2O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H2O) and 1185°C, 16 kbar (4.5 wt% H2O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H2O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H2O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H2O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H2O would require a H2O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H2O.  相似文献   
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