Simon H. Bottrell

Large shifts in the isotopic composition of seawater sulphate across the Permo–Triassic boundary in northern Italy

Carbonate-associated sulphate (CAS) extracted from a Permo–Triassic succession at Siusi in northern Italy is shown to preserve a true seawater-sulphate isotope record. Two periods of increasing δ34S and δ18O in CAS provide evidence for increased oceanic anoxia in the Late Permian and the Early Triassic. These two anoxic episodes are separated by an event characterised by the addition of isotopically light sulphur and oxygen to the oceanic sulphate pool. Simple mass balance calculations suggest that this sulphate originates from the reoxidation of bacterially derived H2S during oceanic mixing, rather than a volcanogenic source. A dramatic fall in CAS-δ18O directly above the P–T boundary, not accompanied by a large change in CAS-δ34S, records an oceanic deoxygenation event probably caused by the release of methane from gas hydrates, subsequently recorded in the carbonate-carbon isotope record. The decline of Early Triassic oceanic anoxia is not recorded by a fall in CAS-δ34S, but is preserved by declining CAS-δ18O. This is because of an increase in the flux of reactive iron to the oceans during the Early Triassic anoxic episode, triggered by the demise of land plants. This permanently removes a greater proportion of light sulphur from the oceanic sulphate reservoir as pyrite, and means that the heavy residual sulphate-sulphur isotope signature of Griesbachian anoxic seawater is preserved as a geochemical ‘fossil’ until the beginning of the Middle Triassic.

Thermochemical sulphate reduction and the generation of hydrogen sulphide and thiols (mercaptans) in Triassic carbonate reservoirs from the Sichuan Basin, China

Abstract The Sichuan Basin in China is a sour petroleum province. In order to assess the origin of H2S and other sulphur compounds as well as the cause of petroleum alteration, data on H2S, thiophene and thiol concentrations and gas stable isotopes (δ34S and δ13C) have been collected for predominantly gas phase petroleum samples from Jurassic, Triassic, Permian and Upper Proterozoic (Sinian) reservoirs. The highest H2S concentrations (up to 32%) are found in Lower Triassic, anhydrite-rich carbonate reservoirs in the Wolonghe Field where the temperature has reached >130 °C. δ34S values of the H2S in the Wolonghe Triassic reservoirs range from +22 to +31‰ and are close to those of Triassic evaporitic sulphate from South China. All the evidence suggests that the H2S was generated by thermochemical sulphate reduction (TSR) locally within Triassic reservoirs. In the Triassic Wolonghe Field, both methane and ethane seem to be involved in thermochemical sulphate reduction since their δ13C values become less negative as TSR proceeds. Thiol concentrations correlate positively with H2S in the Triassic Wolonghe gas field, suggesting that thiol production is associated with TSR. In contrast, elevated thiophene concentrations are only found in Jurassic reservoirs in association with liquid phase petroleum generated from sulphur-poor source rocks. This may suggest that thiophene compounds have not come from a source rock or cracked petroleum. Rather they may have been generated by reaction between localized concentrations of H2S and liquid range petroleum compounds in the reservoir. However, in the basin, thiophene concentrations decrease with increasing vitrinite reflectance suggesting that source maturity (rather than source type) may also be a major control on thiophene concentration.

Volcanism, mass extinction, and carbon isotope fluctuations in the middle permian of China

Middle Permian Extinction A major extinction in the Middle Permian 260 to 270 million years ago preceded the huge end-Permian extinction. Wignall et al. (p. 1179) present a detailed analysis of the Middle Permian event from rocks in southwest China. The extinction coincided with extensive nearby volcanic eruptions. A major drop in carbon isotope values followed the extinction event, implying massive disruption of the carbon cycle. Fossiliferous rocks from southwest China show that a major extinction in the Middle Permian coincided with extensive volcanic eruptions. The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle.

The importance of the relationship between scale and process in understanding long-term DOC dynamics

Concentrations of dissolved organic carbon have increased in many, but not all, surface waters across acid impacted areas of Europe and North America over the last two decades. Over the last eight years several hypotheses have been put forward to explain these increases, but none are yet accepted universally. Research in this area appears to have reached a stalemate between those favouring declining atmospheric deposition, climate change or land management as the key driver of long-term DOC trends. While it is clear that many of these factors influence DOC dynamics in soil and stream waters, their effect varies over different temporal and spatial scales. We argue that regional differences in acid deposition loading may account for the apparent discrepancies between studies. DOC has shown strong monotonic increases in areas which have experienced strong downward trends in pollutant sulphur and/or seasalt deposition. Elsewhere climatic factors, that strongly influence seasonality, have also dominated inter-annual variability, and here long-term monotonic DOC trends are often difficult to detect. Furthermore, in areas receiving similar acid loadings, different catchment characteristics could have affected the site specific sensitivity to changes in acidity and therefore the magnitude of DOC release in response to changes in sulphur deposition. We suggest that confusion over these temporal and spatial scales of investigation has contributed unnecessarily to the disagreement over the main regional driver(s) of DOC trends, and that the data behind the majority of these studies is more compatible than is often conveyed.

Migration and attenuation of agrochemical pollutants: insights from isotopic analysis of groundwater sulphate

Abstract Existing hydrochemical and hydrogeological models of pollution migration and attenuation in the Lincolnshire Limestone aquifer of eastern England have been examined in the light of the results of a groundwater sulphate sulphur isotope investigation. This has allowed the distinction of different sources of sulphate and their relative importance in different parts of the aquifer. The principal sources are 34 S-depleted inputs, derived from the oxidation of pyrite within both the aquifer matrix material and the overlying mudstone deposits, and 34 S-enriched anthropogenic inputs which are derived from acid rain fallout augmented by agrochemicals. Groundwaters sampled over the outcrop zone of the aquifer have sulphate δ 34 S dominated by contemporary acid rain inputs in the recharge waters. A down-dip decrease in the 34 S content of groundwater sulphate over the unconfined and shallow confined areas of the aquifer is indicative of a progressive increase in the significance of pyrite-derived sulphate in the system. The contribution of sulphate from this source is large and indicates that pollution front penetration (previously based on total sulphate concentrations) is more restricted than previously thought. Moreover, the extent of pyrite oxidation is greater than can be accounted for by dissolved O 2 and the additional component corresponds to that which would be expected from reduction of nitrate using pyrite as the electron donor. We suggest that this mechanism is responsible for denitrification in the aquifer, but that it will be ultimately limited by pyrite availability near fissure surfaces where the reaction takes place.

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.

Stable isotope evidence for microbial sulphate reduction at the bed of a polythermal high Arctic glacier

Glacier beds may be host to a range of microbial communities, which drive oxic waters towards anoxia along certain hydrological flowpaths. Chemical and isotopic signatures in meltwaters from Finsterwalderbreen, a polythermal glacier on sedimentary bedrock in Svalbard, show clear evidence for anoxia at the glacier bed. Increases in δ34S and δ18O of sulphate indicate that microbial sulphate reduction has resulted in significant decreases in sulphate concentration. The δ13C of the dissolved inorganic carbon (DIC) is isotopically light (δ13C=−8‰), which is consistent with the use of bedrock kerogen and/or the necromass of sulphide oxidising bacteria as organic substrates for the sulphate-reducing bacteria. Calculated rates of organic carbon mineralisation correspond to ∼10% of the total annual DIC flux of the glacial meltwaters. This microbial ecosystem is chemoautotrophically based, ultimately being sustained by the kerogen and/or bacterial necromass and sulphides in the bedrock. This work suggests that glacier beds can be refugia for life when climatic and/or atmospheric conditions are otherwise inclement and also supports the contention that microbial life is present in subglacial Lake Vostok.

Role of biomineralization as an ultraviolet shield: Implications for Archean life

Cyanobacteria, isolated from the Krisuvik hot spring, Iceland, were mineralized in an iron-silica solution and irradiated with high levels of ultraviolet light. Analysis of the rates of photosynthesis, chlorophyll-a content, and phycocyanin autofluorescence revealed that these mineralized bacteria have a marked resistance to UV compared to nonmineralized bacteria. Naturally occurring sinters composed of iron-silica biominerals collected from

Pyritization of soft-bodied fossils: Beecher's Trilobite Bed, Upper Ordovician, New York State

Although pyrite is ubiquitous in fine-grained, organic, carbon-bearing marine sediments, it is only rarely involved in the preservation of soft-bodied organisms. Beecher9s Trilobite Bed in Upper Ordovician strata of New York State is an exception—it is a classic locality for trilobites having appendages and other soft tissues preserved in pyrite. The relative timing and duration of the formation of pyrite associated with the fossils and their host sediments were determined by use of sulfur isotope ratios. The exoskeleton and appendages of the trilobites show relatively light sulfur isotope values in contrast to the enclosing sediment, which is characterized by a substantial excursion to heavy isotope values. Preservation of soft parts requires rapid burial of carcasses in sediments otherwise low in metabolizable organic matter. In these circumstances, pyrite formation within the sediments is suppressed; thus, concentrations of sulfate and reactive iron are initially high enough to promote early, rapid, and extensive pyritization of nonmineralized tissue.

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.