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Here today, gone tomorrow? integrated experimentation and geochemical modeling in studies of archaeological diagenetic change.

The factors which influence the survival or otherwise of archaeological materials in the burial environment must be understood to allow systematic interpretation of the archaeological record. Studies of postdepositional change, or diagenesis, are therefore essential. The dynamic nature of terrestrial burial environments and the complexity of aqueous fluid-mediated transformation mechanisms have hindered detailed diagenetic research to date. The novel use of integrated experimental and geochemical modeling strategies has the potential to make progress toward a quantified understanding of the diagenesis of inorganic and bioinorganic archaeological materials. We describe current work that is attempting to develop this approach.

Journal Article↗

Thermodynamic analysis of an antibody functional epitope.

We have probed the relative contribution of polar and nonpolar interactions to antibody-antigen interaction by measuring the effect of single amino acid substitutions in an humanized anti-p185HER2 antibody (hu4D5-5) on the thermodynamics of antigen binding. First we mapped the functional epitope by complete alanine-scan mutagenesis of the antibody complementarity-determining region (CDR). Four residues, H91 in VL and R50, W95, and Y100a in VH, make large contributions to the free energy of binding (delta delta G > 3 kcal mol-1) and have delta delta G > delta delta H. These residues are clustered in a shallow pocket on the antibody surface in the X-ray structure determined for hu4D5 Fv. The majority of other CDR residues make less energetically important contributions (delta delta G < 1 kcal mol-1) to binding but have delta delta H > delta delta G, suggesting that the wild-type side chain does contact antigen but the loss in entropy, perhaps through restriction of side-chain conformational freedom, offsets the favorable enthalpic term. Effects of Phe and Ala substitutions on the delta G and delta Cp of antigen binding indicate that the favorable contribution of antibody tyrosine residues to binding results primarily from burial of the aromatic ring in the interface with antigen. Burial of the phenyl ring has a favorable delta H at 25 degrees C but at least for one site (VL-Y92) is opposed by delta S. This latter feature is inconsistent with the thermodynamics predicted for the hydrophobic effect based on hydrocarbon-transfer experiments.(ABSTRACT TRUNCATED AT 250 WORDS)

Antibodies↗

Core formation in apomyoglobin: probing the upper reaches of the folding energy landscape.

An acid-destabilized form of apomyoglobin, the so-called E state, consists of a set of heterogeneous structures that are all characterized by a stable hydrophobic core composed of 30-40 residues at the intersection of the A, G, and H helices of the protein, with little other secondary structure and no other tertiary structure. Relaxation kinetics studies were carried out to characterize the dynamics of core melting and formation in this protein. The unfolding and/or refolding response is induced by a laser-induced temperature jump between the folded and unfolded forms of E, and structural changes are monitored using the infrared amide I' absorbance at 1648-1651 cm(-1) that reports on the formation of solvent-protected, native-like helix in the core and by fluorescence emission changes from apomyoglobin's Trp14, a measure of burial of the indole group of this residue. The fluorescence kinetics data are monoexponential with a relaxation time of 14 micros. However, infrared kinetics data are best fit to a biexponential function with relaxation times of 14 and 59 micros. These relaxation times are very fast, close to the limits placed on folding reactions by diffusion. The 14 micros relaxation time is weakly temperature dependent and thus represents a pathway that is energetically downhill. The appearance of this relaxation time in both the fluorescence and infrared measurements indicates that this folding event proceeds by a concomitant formation of compact secondary and tertiary structures. The 59 micros relaxation time is much more strongly temperature dependent and has no fluorescence counterpart, indicating an activated process with a large energy barrier wherein nonspecific hydrophobic interactions between helix A and the G and H helices cause some helix burial but Trp14 remains solvent exposed. These results are best fit by a multiple-pathway kinetic model when U collapses to form the various folded core structures of E. Thus, the results suggest very robust dynamics for core formation involving multiple folding pathways and provide significant insight into the primary processes of protein folding.

Animals↗

Intermediates in the refolding of ribonuclease at subzero temperatures. 3. Multiple folding pathways.

The kinetics of refolding of ribonuclease A have been measured at -15 degrees C by monitoring the intrinsic fluorescence and absorbance signals from the six tyrosine residues. For each probe multiphasic kinetics were observed. The burial of tyrosine residues, as determined by the change in absorbance at 286 nm, revealed four phases, whereas the kinetics of refolding monitored by fluorescence revealed only two phases. The rates of the transients detected by fluorescence were independent of pH. One of the faster transients detected by delta A286 involved a decrease in absorbance, which is consistent with solvent exposure, rather than burial, and suggests the possibility of an abortive partially folded intermediate in the earlier stages of folding. Double-jump unfolding assays were used to follow the buildup and decay of an intermediate in the refolding reaction at -15 degrees C. At both pH* 3.0 and pH* 6.0 the maximum concentration of the intermediate was 25-30% of the total protein. The existence of a second pathway of slow folding was inferred from the difference in rate of formation of native enzyme and breakdown of the observed intermediate, and by computer simulations. In addition, the unfolding assay demonstrated that 20% of the unfolded protein was converted to native at a much faster rate, consistent with observations in aqueous solution that 80% of unfolded ribonuclease A consists of slow-folding species. Kinetics and amplitude data from these and other refolding experiments with different probes were used to develop possible models for the pathway of refolding. The simplest system consistent with the results for the slow-refolding species involves two parallel pathways with multiple intermediates on each of them. Several independent lines of evidence indicate that about 30% of the unfolded state refolds by the minor pathway, in which the slowest observed phase is attributed to the isomerization of Pro-93. The major pathway involves 50% of the unfolded state; the reason why it refolds slowly is not apparent. A native-like intermediate is formed considerably more rapidly in the major slow-refolding pathway, compared to the minor pathway.

Freezing↗

Equilibrium folding of the core histones: the H3-H4 tetramer is less stable than the H2A-H2B dimer.

To compare the stability of structurally related dimers and to aid in understanding the thermodynamics of nucleosome assembly, the equilibrium stabilities of the recombinant wild-type H3-H4 tetramer and H2A-H2B dimer have been determined by guanidinium-induced denaturation, using fluorescence and circular dichroism spectroscopies. The unfolding of the tetramer and dimer are highly reversible. The unfolding of the H2A-H2B dimer is a two-state process, with no detected equilibrium intermediates. The H3-H4 tetramer is unstable at moderate ionic strengths (mu approximately 0.2 M). TMAO (trimethylamine-N-oxide) was used to stabilize the tetramer; the stability of the H2A-H2B dimer was determined under the same solvent conditions. The equilibrium unfolding of H3-H4 was best described by a three-state mechanism, with well-folded H3-H4 dimers as a populated intermediate. When compared to H2A-H2B, the H3-H3 tetramer interface and the H3-H4 histone fold are strikingly less stable. The free energy of unfolding, in the absence of denaturant, for the H3-H4 and H2A-H2B dimers are 12.4 and 21.0 kcal mol(-)(1), respectively, in 1 M TMAO. It is postulated that the difference in stability between the histone dimers, which contain the same fold, is the result of unfavorable tertiary interactions, most likely the partial to complete burial of three salt bridges and burial of a charged hydrogen bond. Given the conservation of these buried interactions in histones from yeast to mammals, it is speculated that the H3-H4 tetramer has evolved to be unstable, and this instability may relate to its role in nucleosome dynamics.

Chromatography, Gel↗

Large heat capacity change in a protein-monovalent cation interaction.

Current views about protein-ligand interactions state that electrostatic forces drive the binding of charged species and that burial of hydrophobic and polar surfaces controls the heat capacity change associated with the reaction. For the interaction of a protein with a monovalent cation the electrostatic components are expected to be significant due to the ionic nature of the ligand, whereas the heat capacity change is expected to be small due to the size of the surface area involved in the recognition event. The physiologically important interaction of Na+ with thrombin was studied over the temperature range from 5 to 45 degrees C and the ionic strength range from 50 to 800 mM. These measurements reveal an unanticipated result that bears quite generally on studies of molecular recognition and protein folding. Binding of Na+ to thrombin is characterized by a modest dependence on ionic strength but a large and negative heat capacity change of -1.1 +/- 0.1 kcal mol-1 K-1. The small electrostatic coupling can be explained in terms of a minimal perturbation of the ionic atmosphere of the protein upon Na+ binding. The large heat capacity change, however, is difficult to reconcile with current views on the origin of this effect from surface area changes or large folding transitions coupled to binding. It is proposed that this change is linked to burial of a large cluster of water molecules in the Na+ binding pocket upon Na+ binding. Due to their reduced mobility and highly ordered structure, water molecules sequestered in the interior of a protein must have a lower heat capacity compared to those on the surface of a protein or in the bulk solvent. Hence, a binding or folding event where water molecules are buried may result in significant heat capacity changes independent of changes in exposed hydrophobic surface or coupled conformational transitions.

Binding Sites↗

Enhanced protein thermostability by Ala-->Aib replacement.

The introduction into peptide chains of alpha-aminoisobutyric acid (Aib) has proven to stabilize the helical structure in short peptides by restricting the available range of polypeptide backbone conformations. In order to evaluate the potential stabilizing effect of Aib at the protein level, we have studied the conformational and stability properties of Aib-containing analogs of the carboxy-terminal subdomain 255-316 of thermolysin. Previous NMR studies have shown that this disulfide-free 62-residue fragment forms a dimer in solution and that the global 3D structure of each monomer (3 alpha-helices encompassing residues 260-274, 281-295, and 301-311) is largely coincident with that of the corresponding region in the X-ray structure of intact thermolysin. The Aib analogs of fragment 255-316 were prepared by a semisynthetic approach in which the natural fragment 255-316 was coupled to synthetic analogs of peptide 303-316 using V8-protease in 50% (v/v) aqueous glycerol [De Filippis, V., and Fontana, A. (1990) Int. J. Pept. Protein Res. 35, 219-227]. The Ala residue in position 304, 309, or 312 of fragment 255-316 was replaced by Aib, leading to the singly substituted fragments Ala304Aib, Ala309Aib, and Ala312Aib. Moreover, fragment Ala304Aib/Ala309Aib with a double Ala-->Aib exchange in positions 304 and 309 was produced. Far- and near-UV circular dichroism measurements demonstrated that both secondary and tertiary structures of the natural fragment 255-316 are fully retained upon Ala-->Aib substitution(s). Thermal unfolding measurements, carried out by recording the ellipticity at 222 nm upon heating, showed that the melting temperatures (Tm) of analogs Ala304Aib and Ala309Aib were 2.2 and 5.4 degrees C higher than that of the Ala-containing natural species (Tm = 63.5 degrees C), respectively, whereas the Tm of the Ala312Aib analog was lowered by -0.6 degree C. The enhanced stability of the Ala304Aib analog can be quantitatively explained on the basis of a reduced backbone entropy of unfolding due to the restriction of the conformational space allowed to Aib in respect to Ala, while the larger stabilization observed for the Ala309Aib analog can be accounted for by both entropic and hydrophobic effects. In fact, whereas Ala304 is a surface residue, Ala309 is shielded from the solvent, and thus the enhanced stability of fragment Ala309Aib is also due to the burial of an additional -CH3 group with respect to the natural fragment. The slightly destabilizing effect of the Ala-->Aib exchange in position 312 appears to derive from unfavorable strain energy effects, since phi and psi values for Ala312 are out of the allowed angles for Aib. Of interest, the simultaneous incorporation of Aib at positions 304 and 309 leads to a significant and additive increase of +8 degrees C in Tm. The results of this study indicate that the rational incorporation of Aib into a polypeptide chain can be a general procedure to significantly stabilize proteins.

Alanine↗

Long-term recovery of PCB-contaminated surface sediments at the Sangamo-westonl Twelvemile Creek/lake Hartwell Superfund Site.

Natural recovery of contaminated sediments relies on burial of contaminated sediments with increasingly clean sediments over time (i.e., natural capping). Natural capping reduces the risk of resuspension of contaminated surface sediments, and it reduces the potential for contaminant transport into the food chain by limiting bioturbation of contaminated surface or near-surface sediments. This study evaluated the natural recovery of surface sediments contaminated with polychlorinated biphenyls (PCBs) at the Sangamo-Weston/Twelvemile Creek/Lake Hartwell Superfund Site (Lake Hartwell), Pickens County, SC. The primary focus was on sediment recovery resulting from natural capping processes. Total PCB (t-PCB), lead-210 (210Pb), and cesium-137 (137Cs) sediment core profiles were used to establish vertical t-PCB concentration profiles, age date sediments, and determine surface sedimentation and surface sediment recovery rates in 18 cores collected along 10 transects. Four upgradient transects in the headwaters of Lake Hartwell were impacted by historical sediment releases from three upgradient sediment impoundments. These transects were characterized by silt/ clay and sand layering. The highest PCB concentrations were associated with silt/clay layers (1.8-3.5% total organic carbon (TOC)), while sand layers (0.05-0.32% TOC) contained much lower PCB concentrations. The historical sediment releases resulted in substantial burial of PCB-contaminated sediment in the vicinity of these four cores; each core contained less than 1 mg/kg t-PCBs in the surface sand layers. Cores collected from six downgradient Lake Hartwell transects consisted primarily of silt and clay (0.91-5.1% TOC) and were less noticeably impacted by the release of sand from the impoundments. Vertical t-PCB concentration profiles in these cores began with relatively low PCB concentrations at the sediment-water interface and increased in concentration with depth until maximum PCB concentrations were measured at approximately 30-60 cm below the sediment-water interface, ca. 1960-1980. Maximum t-PCB concentrations were followed by progressively decreasing concentrations with depth until the t-PCB concentrations approached the detection limit, where sediments were likely deposited before the onset of PCB use at the Sangamo-Weston plant. The sediments containing the maximum PCB concentrations are associated with the period of maximum PCB release into the watershed. Sedimentation rates averaged 2.1 +/- 1.5 g/(cm2 yr) for 12 of 18 cores collected. The 1994 Record of Decision cleanup requirement is 1.0 mg/kg; two more goals (0.4 and 0.05 mg/kg t-PCBs) also were identified. Average surface sedimentation requirements to meet the three goals were 1.4 +/- 3.7, 11 +/- 4.2, and 33 +/- 11 cm, respectively. Using the age dating results, the average recovery dates to meet these goals were 2000.6 +/- 2.7, 2007.4 +/- 3.5, and 2022.7 +/- 11 yr, respectively. (The 95% prediction limits for these values also are provided.) Despite the reduction in surface sediment PCB concentrations, PCB concentrations measured in largemouth bass and hybrid bass filets continue to exceed the 2.0 mg/kg FDA fish tolerance level.

Aluminum Silicates↗

Prion degradation in soil: possible role of microbial enzymes stimulated by the decomposition of buried carcasses.

This study is part of a European project focused on understanding the biotic and abiotic mechanisms involved in the retention and dissemination of transmissible spongiform encephalopathies (TSE) infectivity in soil in order to propose practical recommendations to limit environmental contamination. A 1-year field experiment was conducted with lamb carcasses buried in a pasture soil at three depths (25, 45, and 105 cm). Microbial community response to carcasses was monitored through the potential proteolytic activity and substrate induced respiration (SIR). Soil above carcasses and control soil exhibited low proteolytic capacity, whatever the depth of burial. Contrastingly, in soil beneath the carcasses, proteolysis was stimulated. Decomposing carcasses also stimulated SIR, i.e., microbial biomass, suggesting that proteolytic populations specifically developed on lixiviates from animal tissues. Decomposition of soft tissues occurred within 2 months at subsurface while it lasted at least 1 year at deeper depth where proteolytic activities were season-dependent. The ability of soil proteases to degrade the beta form of prion protein was shown in vitro and conditions of burial relevant to minimize the risk of prion protein dissemination are discussed.

Animals↗

Salt-dependent heat capacity changes for RNA duplex formation.

Two short non-self-complementary RNA duplexes have been probed extensively to assess whether the heat capacity change (DeltaCP) for RNA duplex formation is sensitive to the solution ionic strength. Isothermal titration calorimetry data for duplex formation were collected as a function of temperature to obtain the DeltaCP values under each condition. Ionic strength was varied by repeating the measurements in the presence of 0.1-1.5 M added NaCl. In both cases, the DeltaCP for duplex formation was shown to have a significant dependence on the solution ionic strength, varying linearly with the log of the added NaCl. In each case, the DeltaCP became more negative at high ionic strength. Heat capacity changes have been much better studied in the area of protein folding where DeltaCP is not strongly dependent upon ionic strength but instead depends primarily on the burial of hydrophobic surface. Whereas hydrophobic burial is almost certainly involved in RNA duplex formation as well, the polyanionic nature of the backbone and the associated ion condensation effects are almost certainly a contributor to the observed ionic strength dependence of DeltaCPs for duplex formation. These data also hint at the possibility that nearest neighbor effects may be evident in the heat capacity changes associated with nucleic acid folding.

Base Sequence↗

Molecular dynamics simulation of laser desorption of a fragment of protein kinase A from two MALDI matrices.

We have carried out molecular dynamics simulations to study the desorption of a dephosphorylated fragment of protein kinase A from two matrices, sinapic acid (SA) and 2,5-dihydroxybenzoic acid (DHB), after laser excitation. We have examined the results as a function of the laser fluence and of the burial depth of the guest peptide in the matrices. In most cases, we found that the energy transferred from the matrix to the guest peptide was not sufficiently large to fragment the peptide. Exceptions occurred when the peptide was more buried. This finding suggested that protein analytes might be less likely to break into smaller fragments if they were placed closer to the surface of the matrix. We have also examined how likely the guest peptide could form small clusters with the matrix molecules and found that the results depended on the degree of burial of the peptide, on the laser fluence, and on which matrix was used. Generally, stable clusters were more likely to be formed for guest peptides that were more buried, at a lower laser fluence, and in the SA rather than the DHB matrix. In addition, we found that the DHB matrix was broken down more easily by the laser than the SA matrix.

Adsorption↗

Increased thermohaline stratification as a possible cause for an ocean anoxic event in the Cretaceous period.

Ocean anoxic events were periods of high carbon burial that led to drawdown of atmospheric carbon dioxide, lowering of bottom-water oxygen concentrations and, in many cases, significant biological extinction. Most ocean anoxic events are thought to be caused by high productivity and export of carbon from surface waters which is then preserved in organic-rich sediments, known as black shales. But the factors that triggered some of these events remain uncertain. Here we present stable isotope data from a mid-Cretaceous ocean anoxic event that occurred 112 Myr ago, and that point to increased thermohaline stratification as the probable cause. Ocean anoxic event 1b is associated with an increase in surface-water temperatures and runoff that led to decreased bottom-water formation and elevated carbon burial in the restricted basins of the western Tethys and North Atlantic. This event is in many ways similar to that which led to the more recent Plio-Pleistocene Mediterranean sapropels, but the greater geographical extent and longer duration (approximately 46 kyr) of ocean anoxic event 1b suggest that processes leading to such ocean anoxic events in the North Atlantic and western Tethys were able to act over a much larger region, and sequester far more carbon, than any of the Quaternary sapropels.

Animals↗

The long-term carbon cycle, fossil fuels and atmospheric composition.

The long-term carbon cycle operates over millions of years and involves the exchange of carbon between rocks and the Earth's surface. There are many complex feedback pathways between carbon burial, nutrient cycling, atmospheric carbon dioxide and oxygen, and climate. New calculations of carbon fluxes during the Phanerozoic eon (the past 550 million years) illustrate how the long-term carbon cycle has affected the burial of organic matter and fossil-fuel formation, as well as the evolution of atmospheric composition.

Atmosphere↗

Reburial of fossil organic carbon in marine sediments.

Marine sediments act as the ultimate sink for organic carbon, sequestering otherwise rapidly cycling carbon for geologic timescales. Sedimentary organic carbon burial appears to be controlled by oxygen exposure time in situ, and much research has focused on understanding the mechanisms of preservation of organic carbon. In this context, combustion-derived black carbon has received attention as a form of refractory organic carbon that may be preferentially preserved in soils and sediments. However, little is understood about the environmental roles, transport and distribution of black carbon. Here we apply isotopic analyses to graphitic black carbon samples isolated from pre-industrial marine and terrestrial sediments. We find that this material is terrestrially derived and almost entirely depleted of radiocarbon, suggesting that it is graphite weathered from rocks, rather than a combustion product. The widespread presence of fossil graphitic black carbon in sediments has therefore probably led to significant overestimates of burial of combustion-derived black carbon in marine sediments. It could be responsible for biasing radiocarbon dating of sedimentary organic carbon, and also reveals a closed loop in the carbon cycle. Depending on its susceptibility to oxidation, this recycled carbon may be locked away from the biologically mediated carbon cycle for many geologic cycles.

Carbon↗

Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals.

The marine sedimentary record exhibits evidence for episodes of enhanced organic carbon burial known as 'oceanic anoxic events' (OAEs). They are characterized by carbon-isotope excursions in marine and terrestrial reservoirs and mass extinction of marine faunas. Causal mechanisms for the enhancement of organic carbon burial during OAEs are still debated, but it is thought that such events should draw down significant quantities of atmospheric carbon dioxide. In the case of the Toarcian OAE (approximately 183 million years ago), a short-lived negative carbon-isotope excursion in oceanic and terrestrial reservoirs has been interpreted to indicate raised atmospheric carbon dioxide caused by oxidation of methane catastrophically released from either marine gas hydrates or magma-intruded organic-rich rocks. Here we test these two leading hypotheses for a negative carbon isotopic excursion marking the initiation of the Toarcian OAE using a high-resolution atmospheric carbon dioxide record obtained from fossil leaf stomatal frequency. We find that coincident with the negative carbon-isotope excursion carbon dioxide is first drawn down by 350 +/- 100 p.p.m.v. and then abruptly elevated by 1,200 +/- 400 p.p.m.v, and infer a global cooling and greenhouse warming of 2.5 +/- 0.1 degrees C and 6.5 +/- 1 degrees C, respectively. The pattern and magnitude of carbon dioxide change are difficult to reconcile with catastrophic input of isotopically light methane from hydrates as the cause of the negative isotopic signal. Our carbon dioxide record better supports a magma-intrusion hypothesis, and suggests that injection of isotopically light carbon from the release of thermogenic methane occurred owing to the intrusion of Gondwana coals by Toarcian-aged Karoo-Ferrar dolerites.

Atmosphere↗

Lay diagnosis of causes of death for monitoring AIDS mortality in Addis Ababa, Ethiopia.

Lay diagnoses of death collected at burial sites were validated against two 'gold standards': the hospital discharge diagnosis of causes of death obtained by a surveillance of hospital deaths (including autopsy results) and the physician review of verbal autopsies (VAs) that were carried out for a sample of cemetery records. The diagnostic indicators of the lay diagnoses were then used to provide estimates of the share of AIDS-attribuTable mortality. The verbal autopsy results provide an independent estimate of the percentage of AIDS deaths. From a total of 21,274 burial records, 2546 hospital discharge diagnoses, 1480 outcomes of autopsies and 200 adult verbal autopsies were gathered over a period of 1 year starting from February 2001. Independent of the gold standard, lay diagnoses such as lung disease and cold have a specificity of about 90% and a combined sensitivity of about 55% in determining AIDS mortality. Without a significant loss in specificity, the sensitivity increases to 60-65% when diarrhoea, TB, herpes zoster and mental or nerve problem are included. We thus conclude that even in the presence of a reluctance to talk of HIV/AIDS, lay diagnosis of causes of death can be used for monitoring AIDS mortality. Lung disease and cold, in particular, have become well-known euphemisms for AIDS in the community. The share of AIDS deaths in the adult population (20-54) is estimated at 68%, without noticeable differences between men and women. Our results confirm the high impact of HIV/AIDS on mortality as was estimated by epidemiological projections for Addis Ababa.

Acquired Immunodeficiency Syndrome↗

Stability of Ca-montmorillonite hydrates: a computer simulation study.

Classic simulations are used to study interlayer structure, swelling curves, and stability of Ca-montmorillonite hydrates. For this purpose, NP(zz)T and muP(zz)T ensembles are sampled for ground level and given burial conditions. For ground level conditions, a double layer hydrate having 15.0 A of basal spacing is the predominant state for relative vapor pressures (p/p0) ranging 0.6-1.0. A triple hydrate counting on 17.9 A of interlaminar distance was also found stable for p/p0 = 1.0. For low vapor pressures, the system may produce a less hydrated but still double layer state with 13.5 A or even a single layer hydrate with 12.2 A of interlaminar distance. This depends on the established initial conditions. On the other hand, the effect of burial conditions is two sided. It was found that it enhances dehydration for all vapor pressures except for saturation, where swelling is promoted.

Journal Article↗

Examination of hypotheses for the Permo-Triassic boundary extinction by carbon cycle modeling.

The biological extinction that occurred at the Permian-Triassic boundary represents the most extensive loss of species of any known event of the past 550 million years. There have been a wide variety of explanations offered for this extinction. In the present paper, a number of the more popular recent hypotheses are evaluated in terms of predictions that they make, or that they imply, concerning the global carbon cycle. For this purpose, a mass balance model is used that calculates atmospheric CO2 and oceanic delta13C as a function of time. Hypotheses considered include: (i) the release of massive amounts of CO2 from the ocean to the atmosphere resulting in mass poisoning; (ii) the release of large amounts of CO2 from volcanic degassing; (iii) the release of methane stored in methane hydrates; (iv) the decomposition and oxidation of dead organisms to CO2 after sudden mass mortality; and (v) the long-term reorganization of the global carbon cycle. The modeling indicates that measured short-term changes in delta13C at the boundary are best explained by methane release with mass mortality and volcanic degassing contributing in secondary roles. None of the processes result in excessively high levels of atmospheric CO2 if they occurred on time scales of more than about 1,000 years. The idea of poisoning by high levels of atmospheric CO2 depends on the absence of subthermocline calcium carbonate deposition during the latest Permian. The most far-reaching effect was found to be reorganization of the carbon cycle with major sedimentary burial of organic matter shifting from the land to the sea, resulting in less burial overall, decreased atmospheric O2, and higher atmospheric CO2 for the entire Triassic Period.

Journal Article↗