SHRIMP U–Pb ages of diagenetic and hydrothermal xenotime from the Archaean Witwatersrand Supergroup of South Africa

SHRIMP dating of xenotime overgrowths on detrital zircon grains can constrain maximum durations since diagenesis and therefore provide minimum dates of sediment deposition. Thus, xenotime dating has significant economic application to Precambrian sediment-hosted ore deposits, such as Witwatersrand Au–U, for which there are no precise depositional ages. The growth history of xenotime in the Witwatersrand Supergroup is texturally complex, with several phases evident. The oldest authigenic xenotime ²⁰⁷Pb/²⁰⁶Pb age obtained in sandstone underlying the Vaal Reef is 2764 ± 5 Myr (1 σ), and most likely represents a mixture of diagenetic and hydrothermal growth. Nevertheless, this represents the oldest authigenic mineral age yet recorded in the sequence and provides a minimum age of deposition. Other xenotime data record a spread of ages that correspond to numerous post-diagenetic thermotectonic events (including a Ventersdorp event at ≈ 2720 Ma) up to the ≈2020 Ma Vredefort event.     

Stable carbon-isotopic compositions of lipids isolated from the ammonia-oxidizing chemoautotroph Nitrosomonas europaea

For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in ¹³C relative to CO₂ dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in ¹³C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in ¹³C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in ¹³C by 26–30‰ relative to dissolved CO₂. Since CO₂ at aquatic oxyclines is often depleted in ¹³C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.     

Anthropogenic trace metals in sediment and settling particulate matter on a high-energy continental shelf (Sydney,Australia)

The anthropogenic contribution of trace metals to settling particulate matter (SPM) and surficial sediments was determined on the high-energy continental shelf adjacent to Sydney, Australia. Settling particulate matter and surficial sediment was collected in the vicinity of a major sewage outfall and at five control sites on the middle shelf (80-100 m water depth). Sediment traps were deployed on 10 occasions for up to 2 weeks during the summer and winter of 1995 and SPM was analyzed for Ag, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Cobalt, Fe, Mn and Ni act conservatively in SPM and in sediments regionally and are used as normalizing elements to determine anthropogenic enrichment. Surficial sediments and SPM are enriched in Ag, Cr, Cu, Pb and Zn near a major ocean outfall and at four of the five control sites, although sewage particles contribute < 5% of trace metals in the total sample. Silver is the most sensitive trace metal tracer for establishing the presence of sewage particulate matter. Sewage particulate matter flux near the outfall was estimated using a two end-member mixing model and is below 0.5 g m(-2) day(-1) during all deployment periods. The mean sewage particulate matter flux at sampling locations 30 km and 60 km north of the outfall are <0.13 g m(-2) day(-1) and <0.01 g m(-2) day(-1), respectively, indicating an efficient dispersal of anthropogenic material on this high energy continental shelf.     

Cloning of a chub metallothionein cDNA and development of competitive RT-PCR of chub metallothionein mRNA as a potential biomarker of heavy metal exposure

Metallothionein has been assayed in a range of aquatic animal tissues as an indicator of metal exposure. We sequenced chub (Leuciscus cephalus) metallothionein cDNA which showed over 90% homology to common carp, goldfish and stone loach and 77% homology to rainbow trout sequences for metallothionein. We then used the extended primer method to develop an accurate quantitative competitive RT-PCR assay for metallothionein mRNA. RT-PCR was used to measure metallothionein mRNA in feral chub from a range of field sites, with different levels of heavy metal pollution, in the West Midlands, UK. Measurements were complemented by analysis of liver and gill metallothionein protein by capillary electrophoresis. There was no significant difference in the metallothionein protein levels between fish of different rivers and there was no evidence of elevation of mRNA at the sites of highest metal exposure. The level of metal exposure (e.g. zinc, nickel and cadmium each ranging between 15 and 28 microg/l ) at the pH (7.5-8.5) of these rivers appears insufficient to elevate hepatic or gill metallothionein in chub. A lack of elevation of hepatic metallothionein mRNA in chub exposed to zinc, copper and manganese for 24 h and 10 days in the laboratory also suggests a non-responsiveness of this species.     

Storms and shoreline retreat in the southern Gulf of St. Lawrence

Storms play a major role in shoreline recession on transgressive coasts. In the southern Gulf of St. Lawrence (GSL), southeastern Canada, long-term relative sea-level rise off the North Shore of Prince Edward Island has averaged 0.3 m/century over the past 6000 years (>0.2 m/century over 2000 years). This has driven long-term coastal retreat at mean rates >0.5 m/a but the variance and details of coastal profile response remain poorly understood. Despite extensive sandy shores, sediment supply is limited and sand is transferred landward into multidecadal to century-scale storage in coastal dunes, barrier washover deposits, and flood-tidal delta sinks. Charlottetown tide-gauge records show mean relative sea-level rise of 3.2 mm/a (0.32 m/century) since 1911. A further rise of 0.7±0.4 m is projected over the next 100 years. When differenced from tidal predictions, the water-level data provide a 90-year record of storm-surge occurrence. Combined with wind, wave hindcast, and sea-ice data, this provides a catalogue of potentially significant coastal storms. We also document coastal impacts from three recent storms of great severity in January and October 2000 and November 2001. Digital photogrammetry (1935–1990) and shore-zone surveys (1989–2001) show large spatial and temporal variance in coastal recession rates, weakly correlated with the storm record, in part because of wave suppression or coastal protection by sea ice. Large storms cause rapid erosion from which recovery depends in part on local sand supply, but barrier volume may be conserved by washover deposition. Barrier shores with dunes show high longshore and interdecadal variance, with extensive multidecadal healing of former inlet and overwash gaps. This reflects recovery from an episode of widespread overwash prior to 1935, possibly initiated by intense storms or groups of storms in the latter half of the 19th century. With evidence from the storms of 2000–2001, this points to the importance of storm clustering on scales of weeks to years in determining erosion vulnerability, as well as the need for a long-term, large-scale perspective in assessing coastal stability. The expected acceleration in relative sea-level rise, together with projections of increasing storm intensity and greatly diminished winter ice cover in the southern GSL, implies a significant increase in coastal erosion hazards in future.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.     

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.