Crater taphonomy and bombardment rates in the Phanerozoic

Impact structures can be catalogued according to the age of the rocks in which they are now found ("country rocks"). The observed frequency distribution of craters by age of country rock is shown to be statistically indistinguishable from the predictions of a simple model in which it is assumed that the survival time for craters is the same as that for their target rocks. Other models are considered, but do not match the data. A lower limit of the rate of bombardment through the Phanerozoic, based only on documented craters, is 0.13 +/- 0.09 events/ma/10(8) km2 for craters with diameters > or = 10 km and 0.09 +/- 0.08 events/ma/10(8) km2 for craters with diameters > or = 20 km. The data allow, but do not demand, an increase in meteorite flux over the Phanerozoic but do not allow any significant decrease. We estimate that only about 6% of the existing terrestrial impact structures of diameter greater than 10 km have been discovered to date, and only 16% of those with diameter greater than 20 km.     

Comparison of mussels and semi-permeable membrane devices as intertidal monitors of polycyclic aromatic hydrocarbons at oil spill sites

Side-by-side comparisons of polycyclic aromatic hydrocarbon (PAH) concentrations in resident blue mussels (Mytilus trossulus) and in semi-permeable membrane devices (SPMDs) were made at four sites in Prince William Sound, Alaska. SPMDs were deployed for approximately 30 days on the surface of the beach sediment at three tidal elevations on each shore and in 0.5 m deep open pits in the middle intertidal zone. Total PAH (TPAH) concentrations in mussels and in SPMDs were correlated, but the PAH compositions were different. The lower molecular weight PAH were relatively more abundant in the SPMDs than in the mussels at oiled and HA sites. TPAH concentrations in SPMDs deployed in pits and mussels collected adjacent to those pits at oiled sites were higher than in SPMDs and mussels from non-pitted SPMD locations approximately 3-15 m from the pits. Pitting released buried oil making its PAH bioavailable. SPMDs deployed in the supratidal zone (+4.0 m tidal elevation) were exposed to atmospheric contaminants for a large fraction of the deployment time and accumulated primarily pyrogenic (combustion-sourced) PAH from the atmosphere. The SPMD strips supplied by the manufacturer contained significant amounts (approximately 125 ng/strip) of primarily alkylated 2-3 ring PAH. These blank levels make SPMDs unsuitable for shoreline assessments when environmental PAH concentrations are low. Consequently, where available, mussels are recommended for use in assessments of the bioavailability of buried oil residues sequestered in intertidal sediments following an oil spill. Mussels are the preferred monitoring tool when the assessments involve food-chain effects. At locations where the absence of mussels necessitates the use of SPMDs or other passive sampling devices, their limitations need to be carefully considered in the interpretation of results.     

Characterizing aquatic sediment-oil aggregates using in situ instruments

The effects of emulsified crude oil and salinity (15, 30 per thousand ) on the steady state aggregate volume distributions and fractal dimensions were determined for a range of mean velocity gradients, (G(m) =5-50 s(-1)). Aggregation was performed in a 40-L cylindrical tank with a 4-blade paddle mixer. Three-dimensional fractal dimensions (D3) and volume distributions were determined using a procedure integrating data from an electrozone and an in situ light scattering instrument. Two-dimensional fractal dimensions (D2) and derived volume distributions were determined using a recently developed submersible flow cytometer equipped with a digital camera and image analysis software. For latex beads or emulsified crude oil systems, the above listed instruments yielded consistent size distributions and fractal dimensions (D2=1.92 +/- 0.16, D3=2.94 +/- 0.12). Mean volume aggregate diameters determined using the FlowCAM were consistently larger that those determined using the LISST-100 or Coulter Multisizer due to aggregate orientations during measurements. With increasing G(m) values, all colloidal aggregates showed increasing D3 values due to reduced aggregate length. Because of the compactness of all the aggregates (D3 >2), D2 values remained constant at 2. Neither salinity nor sediment type significantly affected D2 values calculated for sediment-crude oil aggregates. However, clay-oil aggregates showed higher D3 values than clay aggregates. This suggests that colloidal oil and mixing shear are the more dominant factors influencing aggregate morphology in nearshore waters. Overall, the data suggests that the analysis methods provide consistent size distribution results. However, because of the shear and salinity of coastal waters, resulting aggregates are too compact to estimate their D3 values using image analysis alone.     

Evidence for gammacerane as an indicator of water column stratification

A new route for the formation of gammacerane from tetrahymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids. Selective cleavage of polysulphide linkages with MeLi/MeI led to formation of 3-methylthiogammacerane, indicating that the gammacerane skeleton is primarily bound via sulphur at position 3, consistent with the idea that tetrahymanol (or the corresponding ketone) is the precursor for gammacerane. Second, upon mild artificial maturation of two sediments using hydrous pyrolysis, gammacerane is released from S-rich macromolecular aggregates by cleavage of the relatively weak C-S bonds. The stable carbon isotopic compositions of gammacerane and lipids derived from primary producers and green sulphur bacteria in both the Miocene Gessoso-solfifera and Upper Jurassic Allgau Formations indicate that gammacerane is derived from bacterivorous ciliates which were partially feeding on green sulphur bacteria. This demonstrates that anaerobic ciliates living at or below the chemocline are important sources for gammacerane, consistent with the fact that ciliates only biosynthesize tetrahymanol if their diet is deprived of sterols. This leads to the conclusion that gammacerane is an indicator for water column stratification, which solves two current enigmas in gammacerane geochemistry. Firstly, it explains why gammacerane is often found in sediments deposited under hypersaline conditions but is not necessarily restricted to this type of deposits. Secondly, it explains why lacustrine deposits may contain abundant gammacerane since most lakes in the temperate climatic zones are stratified during summer.     

A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids

Pyrolysates of high-molecular-weight sedimentary fractions of the Duvernay Formation (Western Canada Basin) are dominated by 1,2,3,4- and 1,2,3,5-tetramethylbenzene, which, generated via beta-cleavage, indicate the presence of diaromatic carotenoids in the macromolecular aggregates. This was substantiated by desulphurization of sulphur-rich aggregates of the polar fraction, which released (partly) hydrogenated carotenoids. Furthermore, these components were important constituents of the aromatic hydrocarbon fractions and related oils. Apart from renieratane and isorenieratane, 1H NMR analysis established the aromatic substitution pattern of the most abundant component present, which was identified as a diaromatic compound with an unprecedented 2,3,6-/3,4,5-trimethyl aromatic substitution pattern. Molecular and isotopic analyses of both soluble and insoluble fractions of organic matter revealed relationships between diagenetically-derived carotenoids found in bitumen and related oils and their precursors incorporated into high-molecular-weight fractions. Aryl isoprenoids, important components in extracts and oils, were apparently derived from thermal cracking of bound diaromatic carotenoids rather than cleavage of free carotenoids as previously suggested. Furthermore, products derived from diaromatic carotenoids were substantially enriched in 13C relative to n-alkanes of algal origin. Together with the characteristic carotenoids, this isotopic enrichment provides evidence of significant contributions from photosynthetic green sulphur bacteria (Chlorobiaceae), which fix carbon via the reversed tricarboxylic acid (TCA) cycle. In spite of the prominence of these molecular signals, the overall isotopic composition of the organic matter indicated that only a very small portion of the preserved organic carbon was derived from the biomass of photosynthetic green sulphur bacteria.     

First measurement of helium on Mars: implications for the problem of radiogenic gases on the terrestrial planets

108 +/- 11 photons of the martian He 584-angstroms airglow detected by the Extreme Ultraviolet Explorer satellite during a 2-day exposure (January 22-23, 1993) correspond to the effective disk average intensity of 43 +/- 10 Rayleigh. Radiative transfer calculations, using a model atmosphere appropriate to the conditions of the observation and having an exospheric temperature of 210 +/- 20 K, result in a He mixing ratio of 1.1 +/- 0.4 ppm in the lower atmosphere. Nonthermal escape of helium is due to electron impact ionization and pickup of He+ by the solar wind, to collisions with hot oxygen atoms, and to charge exchange with molecular species with corresponding column loss rates of 1.4 x 10(5), 3 x 10(4), and 7 x 10(3) cm-2 sec-1, respectively. The lifetime of helium on Mars is 5 x 10(4) years. The He outgassing rate, coupled with the 40Ar atmospheric abundance and with the K:U:Th ratio measured in the surface rocks, is used as input to a single two-reservoir degassing model which is applied to Mars and then to Venus. A similar model with known abundances of K, U, and Th is applied to Earth. The models for Earth and Mars presume loss of all argon accumulated in the atmospheres during the first billion years by large-scale meteorite and planetesimal impacts. The models show that the degassing coefficients for all three planets may be approximated by function delta = delta (0)(t(0)/t)1/2 with delta (0) = 0/1, 0.04, and 0.0125 Byr-1 for Earth, Venus, and Mars, respectively. After a R2 correction this means that outgassing processes on Venus and Mars are weaker than on Earth by factors of 3 and 30, respectively. Mass ratios of U and Th are almost the same for all three planets, while potassium is depleted by a factor of 2 in Venus and Mars. Mass ratios of helium and argon are close to 5 x 10(-9) and 2 x 10(-8) g/g in the interiors of all three planets. The implications of these results are discussed.     

The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons

Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different "modes of occurrence" ("free" hydrocarbon, alkylthiophene, alkylthiolane, alkyldithiane, alkylthiane, and sulphur-bound in macromolecules) may have different biosynthetic precursors which are possibly derived from different biota. It is demonstrated that the mode of occurrence and the carbon isotopic composition of a sedimentary lipid can be used to "reconstruct" its biochemical precursor. This novel approach of recognition of the suite of palaeobiochemicals present during the time of deposition allows for identification of the biological sources with an unprecedented specificity.