an oscillating trend in phanerozoic non skeletal carbonate mineralogy textural and compositional data on ancient ooids and cements suggest the existence of an oscillating phanerozoic temporal trend in non skeletal carbonate mineralogy the trend shows good correlation with eustatic climatic oscillations proposed by others the most likely mechanism appears to be plate tectonically influenced oscillations in pco2 the vapour pressure of co2 rather than change in oceanic mg ca ratio

reevaluating the carbon sink due to sedimentary carbonate formation in modern marine sediments abstract previous attempts to quantify the amount of sedimentary carbonate precipitation in modern marine sediments have been derived from the flux of calcium into the sediments due to diffusion under assumed steady state the application of fick s first law and then extrapolation of these site specific rates to the global ocean sediment column this approach is limited however as much of the ocean floor has not been sampled we take a machine learning approach to update and refine the estimate of the amount of sedimentary carbonate precipitation as well as define whether sedimentary carbonate precipitation is driven by organoclastic microbial sulfate reduction or anaerobic methane oxidation we identify areas where there is sedimentary carbonate formation using machine learning based upon oceanic physical and chemical properties including bathymetry temperature water depth distance from shore and tracers of primary production and data from the global odp iodp database our results suggest that the total amount of sedimentary carbonate formation is much lower than previous estimates at 1 35 0 5 10 11 mol c yr we suggest that this rate is a lower estimate and discuss why machine learning approaches may always produce lower bound estimates of global processes our calculations suggest that the formation of sedimentary carbonate today is mainly driven by anaerobic methane oxidation 77 with the remainder attributed to organoclastic sulfate reduction we use our machine learning results to speculate the impact that sedimentary carbonate precipitation may have had on the carbon isotope composition of the surface dissolved inorganic carbon reservoir over earth history

water column euxinia and wildfire evidence during deposition of the upper famennian hangenberg event horizon from the holy cross mountains central poland a palynological study of the uppermost famennian section from kowala quarry holy cross mountains central poland allowed recognition of two miospore zones lv retispora lepidophyta apiculiretusispora verrucosa and ln retispora lepidophyta verrucosisporites nitidus based on palynology and sedimentology the black shale within the upper part of the section is identified as equivalent to the hangenberg black shale which is known globally this black shale contains compounds characteristic of photic zone euxinia including isorenieratane and its derivatives such compounds are absent in the organic poor marls and shales occurring below the ln zone and are present only as traces in the layers just above the black shale indicating fluctuations in the oxygen minimum zone during uppermost famennian sedimentation palynofacies show high amounts of amorphous organic matter and prasinophyte concentrations in the black shale and a subsequent significant decrease of amorphous organic matter concomitant with a rapid increase of terrestrial input mainly miospores with common tetrads in the layers above the black shale this supports the relatively rapid change in the taxonomic composition of phytoplankton caused by fluctuations of the chemocline the whole succession corresponds to one sea level rise and fall the presence of high concentrations of peri condensed polycyclic aromatic hydrocarbons and large amounts of small charcoal particles at the hangenberg event horizon indicate the occurrence of wildfires such observations suggest that atmospheric o2 levels had exceeded the critical threshold of 13 above which wildfires may occur by latest famennian time

intratest oxygen isotope variability in the planktonic foraminifer n pachyderma real vs apparent vital effects by ion microprobe abstract intratest oxygen isotope variations in the planktonic foraminifer neogloboquadrina pachyderma sinistral left coiling from north atlantic core top and multi net samples were assessed by ion microprobe analysis from 2 to 6 m spots with precision and accuracy better than 0 7 in 18 o 2 sd within a single foraminiferal test from a core top sample comprising both ontogenetic calcite and outer crust 18 o values vary from 0 5 to 3 7 pdb exceeding the range of equilibrium 18 o in the specimens habitat by a factor of three the isotopic difference between the ontogenetic calcite and the crust averages 1 8 neither of the two types of foraminiferal calcite precipitates in equilibrium with ambient seawater the ontogenetic calcite exhibits a negative vital effect 18 o m e 18 o measured 18 o equilibrium ranging from 0 5 to 1 the largest negative fractionation is associated to the inner walls of juvenile chambers in contrast a positive vital effect of about 0 8 was observed in the crust with respect to the highest equilibrium 18 o values at water depths below 200 m hence two vital effects that are opposite in sign are effective within a single foraminiferal test indicating that whole test values of this species are highly sensitive to the degree of encrustation and amplify or attenuate environmental signals the negative vital effect of the ontogenetic calcite was verified by ion microprobe analysis of four nonencrusted net sampled specimens reflecting three different depth intervals intra ontogenetic oxygen isotope ratios in these juvenile tests range from 0 6 to 3 0 and exhibit a negative vital effect even larger than that observed in core top samples based on these data the large range of apparent vital effects reported for this foraminiferal species can be assessed by a mass balance calculation assuming that the degree of encrustation is variable

manganese authigenesis in the landsort deep baltic sea abstract manganese mineralogy because of its redox sensitivity is a valuable parameter for interpreting water column anoxia and sediment diagenesis in the baltic and especially the landsort deep the relatively widespread occurrence of mn carbonates and the unique observations of authigenic mn sulphides in sedimentary environments need to be accounted for within the models proposed for mn authigenesis in diverse settings in this study stratigraphic changes in the geochemistry and mineralogy are documented in two gravity cores using petrographic microscopy xrd sem eds analyses of c and s content 13 c isotopes icp ms cation determinations and electron microprobe element profiling the lamination in the bottom sediments of the landsort deep suggests essentially continuous anoxic conditions at the sediment surface during the last ca 4500 14 c years the most striking variations in the sediments are related to the occurrence of two mn ii precipitate rich sapropel intervals recent and 1390 1990 14 c years bp sapropel deposition is associated with relatively slow detrital sedimentation allowing the concentration of organic matter the sediment c org content is influenced by the variations in the primary production as well as the supply of terrestrial c org but a major control appears to be detrital dilution the precipitation of mn carbonate as individual aggregates of spherical particles dispersed within clayey sediment matrix and as laminae with semi seasonal cyclicity is believed to be largely induced by the high alkalinity in connection with organic matter deposition and degradation where h 2 s has exceeded fe availability mns has also precipitated most commonly as well developed hexagonal crystals but also as the cubic variety alabandite which has not previously been reported from a sedimentary environment an expansion of the anoxic bottom water conditions during sapropel deposition is interpreted by correlation with laminated intervals on the slope of the deep basin budget calculations for the supply of mn to the basin during mn rich sapropel formation can be better balanced by the addition of mn from dissolution of oxides formed prior to the anoxic expansion the importance of alkalinity for the precipitation of mn carbonates and sulphides does not exclude the need for considerable mn concentrations but the model argued in several recently published studies stressing mn availability as the major control does not seem appropriate for the landsort deep and may be too restrictive in many other settings as well

local overprints on the global carbonate δ13c signal in devonian carboniferous boundary successions of south china abstract an integrated study of the litho bio and chemostratigraphy of the devonian carboniferous boundary at four sections qilinzhai malanbian gedongguan and long an in south china was undertaken in order to better understand paleoenvironmental changes and controls on 13 c carb variation during the hangenberg crisis sedimentological data record a major regression in the middle siphonodella praesulcata zone which coincided with the hangenberg extinction he in south china our new 13 c carb data document a negative 13 c carb shift near the base of the middle s praesulcata zone which may have been related to the he prior to and during the he respiration of organic matter contributed abundant 12 c enriched dissolved inorganic carbon dic to the restricted nanning carbonate platform resulting in a negative vertical 13 c dic gradient in the study area in the upper s praesulcata zone all four sections exhibit a positive 13 c carb shift suggesting that a vigorous biological pump existed in the aftermath of the latest devonian glaciation however peak 13 c carb values differ markedly among the study sections suggesting that local carbon cycling processes played an important role during the initial post glacial transgression

geochemical evidence for euxinia during the late devonian extinction events in the michigan basin u s a abstract several mass extinction events occurred in the late devonian but the trigger for these events remains elusive in this study geochemical evidence in the late devonian antrim shale michigan basin u s a records episodic euxinia contemporaneous with these extinction events diagnostic changes in iron proxy data and elevated trace metal enrichments correspond to the kellwasser crisis in this study carbon sulfur iron and trace metal geochemistry preserved in the antrim formation validates the establishment and expansion of euxinic conditions associated with the kellwasser crisis and the frasnian famennian boundary the strength of the sequential extraction iron mineral data presented here in concert with trace metal and sulfur isotope proxies provides definitive signatures of euxinia when other data may be more ambiguous in regard to paleoredox conditions during the time of the frasnian famennian boundary extensive sulfide oxidation at the chemocline the result of fe limiting conditions within the basin provides an alternative explanation for the oceanic decline in 34 s so 4 during and following the frasnian famennian event our geochemical evidence indicating the presence of anoxia in the michigan basin is consistent with data from other globally distributed locations euxinia should be considered a key driver for these global extinction events and possibly others such as the hangenberg event in the late devonian

the hyper enrichment of v and zn in black shales of the late devonian early mississippian bakken formation usa abstract black shales of the late devonian to early mississippian bakken formation are characterized by high concentrations of organic carbon and the hyper enrichment 500 to 1000s of mg kg of v and zn deposition of black shales resulted from shallow seafloor depths that promoted rapid development of euxinic conditions vanadium hyper enrichments which are unknown in modern environments are likely the result of very high levels of dissolved h2s 10 mm in bottom waters or sediments because modern hyper enrichments of zn are documented only in framvaren fjord norway it is likely that the biogeochemical trigger responsible for zn hyper enrichment in framvaren fjord was also present in the bakken basin with framvaren fjord as an analogue we propose a causal link between the activity of phototrophic sulfide oxidizing bacteria related to the development of photic zone euxinia and the hyper enrichment of zn in black shales of the bakken formation

phanerozoic atmospheric oxygen new results using the geocarbsulf model modifications of the geocarbsulf model for phanerozoic atmospheric oxygen have been made to account for new carbon isotopic data reconsideration of the fractionation of carbon isotopes between carbonate and organic matter deposited in sediments and different rates of weathering of volcanic rocks versus granitic rocks results indicate distinctly higher o2 values than geocarbsulf for the mesozoic and cenozoic lack of an appreciable drop in o2 below 15 percent at any time and a small late cenozoic decline of o2 to the present

tetraether lipids from the southern yellow sea of china implications for the variability of east asia winter monsoon in the holocene to better understand the origin and distribution of organic matter om in the yellow sea ys and to delineate potential interactions between the atmosphere and the marine system during the holocene we reconstructed terrestrial input and temperature variation for the last 8 8 ka bp using glycerol dialkyl glycerol tetraethers gdgts obtained from a 4 4 m sediment core ysc 1 from the southern ys the archaea derived isoprenoid gdgts igdgts were dominated by gdgt 0 and crenarchaeol the igdgts and bacteria derived branched gdgts bgdgts correlated well and varied in opposition to the bit branched vs isoprenoid tetraether index this may be due to varying river runoff and influence of the ys coastal current yscc and ys warm current yswc related to the east asia winter monsoon eawm which made the bit proxy less suitable for tracing soil om input to the ys tex86 tetraether index of tetraethers consisting of 86 carbons derived sea surface temperature values sst varied from 9t o 16c close to the sst in the ys cold season the mbt cbt methylation of branched tetraethers and cyclization of branched tetraethers derived continental temperature ranged from 10 to 19 c indicating an annual mean air temperature for the middle and low drainage basin of the ys these two temperature records were decoupled but both correlated with the variation in the eawm suggesting an intimate link between eawm and temperature variation in east asia

traces in the dark sedimentary processes and facies gradients in the upper shale member of the upper devonian lower mississippian bakken formation williston basin north dakota u s a abstract black organic rich rocks of the upper shale member of the upper devonian lower mississippian bakken formation a world class petroleum source rock in the williston basin of the united states and canada contain a diverse suite of mudstone lithofacies that were deposited in distinct facies belts the succession consists of three discrete facies associations fas these comprise 1 siliceous mudstones 2 quartz and carbonate bearing laminated mudstones and 3 macrofossil debris bearing massive mudstones these fas were deposited in three facies belts that reflect proximal to distal relationships in this mudstone system the macrofossil debris bearing massive mudstones fa 3 occur in the proximal facies belt and contain erosion surfaces some with overlying conodont and phosphate lithoclast lag deposits mudstones with abundant millimeter scale siltstone laminae showing irregular lateral thickness changes and shell debris in the medial facies belt quartz and carbonate bearing laminated mudstones dominate exhibiting sub millimeter thick siltstone layers with variable lateral thicknesses and localized mudstone ripples in the distal siliceous mudstone facies belt radiolarites radiolarian bearing mudstones and quartz and carbonate bearing laminated mudstones dominate overall total organic carbon toc contents range between about 3 and 10 wt with a general proximal to distal decrease in toc content abundant evidence of bioturbation exists in all fas and the lithological and toc variations are paralleled by changes in burrowing style and trace fossil abundance while two horizontal traces and two types of fecal strings are recognized in the proximal facies belt only a single horizontal trace fossil and one type of fecal string characterize mudstones in the distal facies belt radiolarites intercalated into the most distal mudstones are devoid of traces and fecal strings bedload transport processes likely caused by storm induced turbidity currents were active across all facies belts suspended sediment settling from near the ocean surface however most likely played a role in the deposition of some of the mudstones and was probably responsible for deposition of the radiolarites the distribution pattern of high toc sediments in proximal and lower toc deposits in some distal facies is interpreted as a function of higher accumulation rates during radiolarian depositional events leading to a decrease in suspension derived organic carbon in radiolarite laminae the presence of burrows in all fas and nearly all facies in the upper bakken shale member indicates that dysoxic conditions prevailed during its deposition this study shows that in intracratonic high toc mudstone successions such as the upper bakken shale member bed load processes most likely dominated sedimentation and conditions promoted a thriving infaunal benthic community as such deposition of the upper bakken shale member through dynamic processes in an overall dysoxic environment represents an alternative to conventional anoxic depositional models for world class source rocks

macrostrat a platform for geological data integration and deep time earth crust research characterizing the lithology age and physical chemical properties of rocks and sediments in the earths upper crust is necessary to fully assess energy water and mineral resources and to address many fundamental questions in the earth sciences although a large number of geological maps regional geological syntheses and sample based measurements have been produced there is no openly available database that integrates rock record derived data while facilitating large scale quantitative characterization of the volume age and material properties of the upper crust here we describe macrostrat a relational geospatial database and supporting cyberinfrastructure that is designed to enable quantitative spatial and geochronological analyses of the entire assemblage of surface and subsurface sedimentary igneous and metamorphic rocks macrostrat now contains general comprehensive summaries of the age and properties of 33 903 lithologically and chronologically defined geological units distributed across 1 474 regions in north and south america the caribbean new zealand and the deep sea sample derived data including fossil occurrences in the paleobiology database more than 180 000 geochemical and outcrop derived measurements and more than 2 1 million bedrock geologic map units from over 170 map sources are linked to specific macrostrat units and or lithologies macrostrat has generated numerous quantitative results and its data infrastructure is being used in several independently developed mobile applications however it is necessary to expand geographic coverage and to refine age models and material properties to arrive at a more precise characterization of the upper crust globally

seafloor precipitated carbonate fans in the neoproterozoic rainstorm member johnnie formation death valley region usa cm sized carbonate seafloor fans occur in the neoproterozoic rainstorm member of the johnnie formation death valley usa the fans formed in a mixed carbonate clastic succession near storm wave base at the base of parasequences on a storm dominated ramp petrographic observations indicate that the fans were originally precipitated as aragonite and later inverted to calcite during diagenesis although not directly dated the rainstorm member preserves a large magnitude negative carbon isotopic anomaly down to 11 pdb tentatively correlated to the largest known carbon isotope excursion found in many stratigraphic successions around the world between 585 ma and 550 ma thus the age distribution of seafloor aragonite fans in neoproterozoic strata appears more widespread than previously thought occurring in strata significantly younger than the last widespread neoproterozoic glaciation rainstorm member carbonate fans and oolitic units representing time correlative shallower environments record similar carbon isotope ratios during the negative carbon isotopic anomaly the carbon isotopic homogeneity displayed between fans and other carbonate sediments implies that waters across the shelf were well mixed rather than stratified during the late neoproterozoic isotopic anomaly in addition the similarity of carbon isotope ratios shared among fans along a stratigraphic horizon on a m to cm scales suggests that the local source of alkalinity required for fan growth was derived from a well mixed reservoir likely seawater rather than local diagenetic fluids increased alkalinity and the presence of inhibitors to carbonate nucleation perhaps fe2 under anoxic conditions likely fostered precipitation of aragonite crystal fans on the seafloor

bakken madison petroleum systems in the canadian williston basin part 2 molecular markers diagnostic of bakken and lodgepole source rocks abstract the uppermost devonian mississippian bakken formation black shale and the mississippian lodgepole formation carbonate represent two of the most important source rocks in the canadian williston basin quantitative analyses of both saturated and aromatic hydrocarbon fractions reveal significant differences in the relative distributions and absolute concentrations for a wide range of molecular markers between the extracts of the two source units among others the bakken shales are characterized by their high relative abundance of trimethyl aryl and diaryl isoprenoids likely derived from green sulfur bacteria chlorobiaceae in contrast the lodgepole carbonates at similar maturity levels display a c35 homohopane prominence and abundant benzohopanes ring d monoaromatic 8 14 secohopanes and a tetracyclic monoaromatic hydrocarbon the distinctive nature of molecular marker fingerprints diagnostic of the two source rocks is clearly related to their different organic inputs and depositional environments additionally the large difference in the absolute concentrations of these compounds observed in both source units may potentially lead to biased geochemical interpretations if strictly conventional saturate based biomarker approaches were used for oil oil and oil source correlation

glacioeustasy meteoric diagenesis and the carbon cycle during the middle carboniferous middle carboniferous carbonates in the western u s have undergone pleistocene bahamas style meteoric diagenesis that may be associated with expanding late paleozoic ice sheets fourteen stratigraphic sections from carbonate platforms illustrate the regional distribution and variable intensity of physical and chemical diagenesis just below the middle carboniferous unconformity these sections contain top negative carbon isotope excursions that terminate in regional exposure surfaces that are associated with some combination of karst towers desiccation cracks fabric destructive recrystallization or extensive root systems the timing of the diagenesis is synchronous with similarly scaled top negative carbon isotope excursions observed by others in england kazakhstan and china the mass flux of negative carbon required to generate similar isotopic profiles across the areal extent of middle carboniferous platform carbonates is a significant component of the global carbon cycle we present a simple carbon box model to illustrate that the 13c of dissolved inorganic carbon in the ocean could be elevated by 1 4 as isotopically light carbon from the weathering of terrestrial organic matter reacts with exposed platforms before reaching the ocean and atmosphere these results represent an improvement on global biogeochemical models that have struggled to provide a congruent solution to the high 13c of the late paleozoic icehouse

carbon isotopes and the rise of atmospheric oxygen new data for the isotopic composition of carbon in carbonate sediments deposited between 2 6 and 1 6 ga indicate that the value of 13c in these sediments underwent a very large positive excursion between 2 22 and 2 06 ga a reassessment of the earlier 13c data for carbonate sediments shows that this excursion was probably worldwide and that it was preceded and followed by several hundred million years during which the 13c of carbonate sediments differed little from that of modern carbonates the large 13c excursion between 2 22 and 2 06 ga was probably related to an abnormally high rate of organic carbon deposition which generated an abnormally high rate of o2 production we estimate that the total excess o2 produced during the excursion was between 12 and 22 times the present atmospheric o2 inventory the 13c data therefore suggest that the o2 content of the atmosphere increased very significantly between 2 22 and 2 06 ga this inference is supported strongly by several other lines of evidence

a new ecological severity ranking of major phanerozoic biodiversity crises a new ecological severity ranking of the major phanerozoic biodiversity crises is proposed in which the capitanian crisis is ranked lesser than the frasnian late devonian but greater than the serpukhovian end mississippian and the famennian end devonian crisis is ranked as equal in ecological impact to the hirnantian end ordovician two new decouplings between taxonomic severity and ecological severity are revealed in these analyses the capitanian and famennian crises in which the ecological impact of the biodiversity loss was markedly different from the magnitude of the biodiversity loss these analyses also reveal that the great devonian interchange gdi invasive species event in the givetian biodiversity crisis may provide an important palaeoecological analog for the study of present day extinction and homogenization in ecosystems produced by modern invasive species

deciphering the upper famennian hangenberg black shale depositional environments based on multi proxy record abstract presented for the first time in this paper are the results of a detailed multi proxy investigation conducted on the hangenberg black shale hbs from the polish part of the laurussian shelf which provide details about the environmental conditions in existence during deposition of the shale and the role played by anoxic conditions in the mass extinction events that occurred at the end of the devonian times inorganic and organic redox indicators indicate that bottom water redox conditions changed periodically from being mainly anoxic euxinic to oxic or being partially depleted in oxygen u th values above 1 25 ni co values above 7 and v v ni values above 0 8 recorded from the lower part of the hbs all point to anoxic euxinic conditions being present as do high total organic carbon contents toc above 10 and degree of pyritisation dop values around 0 75 however the presence of benthic fauna over the lower part of the hbs attests to opportunistic colonisation of the seafloor during oxic episodes evidence for similar episodes has also been recognised over the middle part of the hbs e g u th values below 1 25 ni co values below 4 v v ni values below 0 8 toc values of 3 to 5 5 and dop values of 0 4 to 0 75 plus the common occurrence of benthic fauna anoxic conditions returned during the deposition of the upper part of the hsb though they were not as well developed as when the lower part of the shale was laid down of interest is the presence of small pyrite framboids and isorenieratene biomarkers in all the analysed samples which suggest that euxinic conditions persisted in the photic zone of the water column a twenty centimetre thick layer of volcanogenic deposits tuffites is present in the middle part of the hbs the geochemical characteristics of which are typical of ocean floor basalts the occurrence of volcanogenic material below and within the hbs together with an absence of calcium carbonate over its upper part the presence of abundant tetrads just above the black shale and a drastic decrease in faunal frequency in the upper part of the hbs imply that volcanism may have caused oceanic acidification or hypercapnia that in turn potentially may have influenced the hangenberg mass extinction event

hydrographic conditions of the devono carboniferous north american seaway inferred from sedimentary mo toc relationships abstract deepwater anoxia developed widely within a series of silled intracratonic basins in north america during the middle devonian to early carboniferous but the hydrographic factors contributing to this development are virtually unknown the present study demonstrates that the degree of enrichment of strongly hydrogenous elements such as molybdenum mo in the organic rich shales that accumulated in these basins has the potential to provide information about paleohydrographic conditions most of the study units 49 of 55 exhibit significant positive covariation between elemental mo and toc concentrations yet there is substantial variation in the statistical parameters that define these relationships specifically the regression lines characterizing mo toc covariation have slopes m ranging from 2 to 65 10 4 although a majority of the study units yield m values between 10 and 25 10 4 the parameter m exhibits systematic stratigraphic variation within individual basins and geographic variation among basins suggesting that mo toc relationships were controlled by slowly evolving watermass characteristics of the devono carboniferous north american seaway a recent study of modern anoxic silled basins algeo t j lyons t w 2006 mo total organic carbon covariation in modern anoxic marine environments implications for analysis of paleoredox and paleohydrographic conditions paleoceanography 21 pa1016 doi 10 1029 2004pa001112 demonstrated that m is closely linked to the degree of restriction of the subpycnoclinal watermass as reflected in aqueous mo concentrations mo aq and deepwater renewal times dw these relationships reflect control of sedimentary mo enrichment by both the amount of sedimentary organic matter i e host phase availability and the concentration of aqueous mo i e source ion availability when applied to black shales of the devono carboniferous north american seaway these relationships permit both qualitative and quantitative inferences regarding the degree of restriction of deepwaters in cratonic basins and the evolution of hydrographic conditions through time black shales associated with early stages of sea level rise commonly exhibit low m values 1000 yr higher sea level stands resulted in more open marine conditions and enhanced deepwater renewal leading to deposition of black shales with m values up to 65 equivalent to mo aq 70 of the normal seawater concentration and dw

cold seeps and authigenic carbonate formation in monterey bay california abstract authigenic carbonate associated with modern cold seep biological communities and their extinct analogues exhibit a broad range in stable isotope and mineral composition within the limited geographic area of monterey bay although such variations in ancient samples have been used to infer differing tectonic settings these carbonates all formed within a faulted continental margin environment and chemical variations reflect local differences in the sources and flux of carbon to sediment pore fluids the slow seepage of fluid and with it dissolved carbon along the transform faulted continental margin results in discrete areas of enhanced microbial sulfate reduction oxidation of methane from both biogenic and thermogenic origins as well as the active precipitation of both high mg calcite hmc and dolomite the authigenic carbonates include semicontinuous pavements of shallow cemented sediments surrounding benthic communities circular or pipe like chimneys interpreted as cemented conduits formed as a result of methane gas expulsion centimeter to meter scale rings doughnuts or slabs winnowed from variable depths within sediments and carbonate veins ankerite or calcite or cements in faulted basement rocks draped with bacterial mat abundant pyrite framboids preferentially filling the tests of the benthic foraminifer uvigerina peregrina and characteristic of the hmc bearing samples are products of a zone of shallow microbial sulfate reduction a process fundamental to the nourishment of the chemosynthetic cold seep communities sites on a sedimented ridge west of the san gregorio fault zone have carbon isotopic values between 35 and 56 that are strongly influenced by carbon derived from methane the higher values of 18 o more enriched in 18 o are found closer to the active fault zone carbonates from sites within the san gregorio fault zone or from monterey canyon floor exposures of miocene sediments have carbon isotope values between 7 and 26 that are mixtures of sedimentary organic carbon and microbially oxidized hydrocarbons from organic rich petroleum source rocks dolomite bearing samples are more enriched in both 18 o and 13 c bulk carbonate samples with heavier 18 o 18 o 3 5 result from the abundance of authigenic dolomite and low temperatures of formation local destabilization of clathrates might also create pore fluids that are more enriched in both 13 c and 18 o

was phanerozoic reef history controlled by the distribution of non enzymatically secreted reef carbonates microbial carbonate and biologically induced cement throughout most of the phanerozoic reef rigidity resulted as much or more from early lithification by microbial carbonates and biologically induced cements non enzymatic carbonates than from biological encrustation of or by large enzymatically secreted metazoan skeletons reef framework is divided into four categories 1 skeletal metazoan 2 non skeletal microbialite stromatolite and thrombolite 3 calcimicrobe and 4 biocementstone in which small or delicate organisms serve as scaffolds for rigid cement crusts the last three categories are dominated by non enzymatic carbonates skeletal framework and non skeletal microbialite framework were the most abundant framework types through the phanerozoic the composition and abundance of skeletal framework was controlled largely by mass extinction events but most reefs consisted of both microbialite and skeletal organisms in a mutually beneficial relationship microbialite framework was abundant throughout the palaeozoic and early mesozoic but declined after the jurassic calcimicrobe framework was important during the cambrian early ordovician and devonian and biocementstone framework was important from the late mississippian to the late triassic the phanerozoic history of reefs does not correlate well with the stratigraphic distribution of large skeletal reef builders or with a variety of physicochemical parameters including sea level history wilson cycle or global climate cycles because non enzymatic carbonates result from induction by non obligate calcifiers and not enzymatic precipitation by obligate calcifiers the distribution of these carbonates was controlled to a larger extent by temporal changes in physicochemical parameters affecting the saturation state of sea water with respect to carbonate minerals changes in pco ca mg ratios cation concentrations and temperature may have affected the abundance of non enzymatic carbonates and hence reefs independently from the effects of these same parameters and mass extinction events on skeletal reef biota the decline in abundance of reefal microbialite and absence of calcimicrobe and biocementstone reef framework after the jurassic may be a result of relatively low saturation states of sea water owing to increased removal and sequestration of finite marine carbonate resources by calcareous plankton since the jurassic reef history is difficult to correlate with temporal changes in specific global parameters because these parameters affect skeletal biota and biologically induced carbonate precipitation independently hence reef history was regulated not just by skeletal reef biota but by parameters governing non enzymatic carbonates

secular variation in abiotic marine carbonates constraints on phanerozoic atmospheric carbon dioxide contents and oceanic mg ca ratios abiotic marine carbonates have been precipitated as ooids and synsedimentary cement within shallow marine carbonate sequences throughout the phanerozoic these components exhibit variable abundances and compositions that temporally correlate with estimates of global eustasy with rising sea level aragonite and acicular magnesium calcite precipitation gave way to the formation of equant calcite and possibly dolomite similarly the abundance of ooids was limited by positions of global sea level and associated changes in ocean chemistry modern abiotic marine carbonates also exhibit variable abundances and compositions as a function of changing fluid chemistry with latitude and depth chemical data on ambient marine waters suggest that carbonate ion concentrations and rates of precipitation presently control the nature of marine cement and ooids using data from modern oceans to calculate the requisite atmospheric pco 2 levels necessary to form this range of phases in ancient seas suggests that atmos

growth mechanisms and geochemistry of carbonate concretions from the cambrian wheeler formation utah usa carbonate concretions provide unique records of ancient biogeochemical processes in marine sediments typically they form in organic rich mudstones where a significant fraction of the bicarbonate required for carbonate precipitation is supplied from the decomposition of organic matter in the sediments as a result carbonates that comprise concretions are usually characterized by broad ranges in 13c and include values that are significantly depleted relative to seawater this article reports results from a physical petrographic and geochemical analysis of 238 concretions from the wheeler formation cambrian series 3 utah usa which are unusual in several respects most prominently they formed in organic poor mudstones total organic carbon 0 1 to 0 5 and are characterized by a narrow range of 13c that onlaps the range of contemporaneous seawater values subtle centre to edge trends in 13c demonstrate that concretion precipitation was initiated by local chemical gradients set up by microbial activity in the sediments but was sustained during growth by a large pool of inorganic bicarbonate probably derived from alkaline bottom waters the large inorganic pool appears to have been important in facilitating rapid precipitation of the concretion matrix which occurred via both displacive and replacive carbonate precipitation during early diagenesis stable isotope data from cogenetic pyrite 34s and silica 18o phases provide insight into the evolution of biogeochemical processes during concretion growth and suggest that concretions were formed almost entirely during sulphate reduction with only minor modification thereafter concretions of the wheeler formation appear to represent an end member system of concretion formation in which rapid growth was promoted by ions supplied from sea water as such they offer insight into the spectrum of processes that may influence the growth of carbonate concretions in marine sediments

environmental analysis of paleoceanographic systems based on molybdenum uranium covariation abstract modern low oxygen marine systems exhibit patterns of molybdenum uranium covariation that can be linked to specific attributes and processes of the depositional system including 1 variation in benthic redox conditions 2 the operation of particulate shuttles within the water column and 3 the evolution of watermass chemistry the importance of these factors in each depositional system can be assessed both from the degree of enrichment of authigenic molybdenum mo auth and uranium u auth and from the mo u auth ratio of the sediment relative to the seawater mo u molar ratio of 7 5 7 9 in open ocean systems with suboxic bottomwaters u auth enrichment tends to exceed that of mo auth owing to onset of u auth accumulation at the fe ii fe iii redox boundary resulting in sediment mo u auth ratios less than that of seawater as bottomwaters become increasingly reducing and at least occasionally sulfidic the rate of accumulation of mo auth increases relative to that of u auth and sediment mo u auth ratios equal or exceed that of seawater in restricted marine systems with permanently sulfidic deepwaters the relative enrichment of mo auth and u auth depends on additional factors in the cariaco basin which has an aqueous mo u ratio similar to that of seawater the operation of a particulate mn fe oxyhydroxide shuttle serves to accelerate the transfer of mo to the seafloor leading to strong enrichments in mo auth relative to u auth in the black sea the chemistry of the deep watermass has evolved to the point where its aqueous mo u ratio is only 0 04 that of seawater as a consequence of which sediments deposited under deepwater influence are depleted in mo auth relative to u auth these mo u covariation patterns can be used to gain a better understanding of the watermass attributes and processes of ancient low oxygen marine systems analysis of anoxic facies from two north american paleomarine systems the late pennsylvanian midcontinent sea lpms and the late devonian seaway lds reveals authigenic mo u relationships similar to those of the modern marine environments above implying similar redox and hydrographic controls the observed patterns are consistent with laterally unconfined circulation and strong watermass exchange within the lpms and with markedly restricted deepwater circulation in silled basins of the lds patterns of authigenic mo u covariation may prove useful in analysis of other paleoceanographic systems to reveal aspects of watermass composition and environmental dynamics

reconstructing the palaeoecosystem and palaeodepositional environment within the upper devonian lower mississippian bakken formation a biomarker approach abstract biomarkers have been used extensively to correlate oil families oil source rock relationships and source inputs and to help identify the palaeodepositional environment for a given geological sedimentary unit despite their application in characterising the bakken formation shales a number of biomarkers still appear unable to provide us a consistent understanding regarding heterogeneity in source organic matter and palaeoenvironment here we infer the palaeodepositional environment within the bakken formation shales using a biomarker suite and biomarker depth profiles we also use the occurrence and abundance of biomarkers to define organic facies and to make inferences regarding biotic interactions drawn from modern analogues the variations and co occurrence of biomarkers is explained by the existence of a proposed complex algal bacterium bacteriovore palaeoecosystem this approach not only helps explain the depth variation in occurrence and concentration of biomarkers and the molecular composition of associated organic matter but also advances the use of biomarker analysis and biomarker associations to determine a complex environment sensitive palaeoecosystem

palaeoceanographic controls on geochemical characteristics of organic rich exshaw mudrocks role of enhanced primary production organic rich source rocks have generally been attributed to enhanced preservation of organic matter under anoxic bottom waters here geochemical analysis of kerogen and whole rock samples of organic rich lithofacies b1 and organic lean lithofacies b2 laminated mudrocks of the devonian carboniferous exshaw formation alberta highlight the importance of primary production in governing the quantity and quality of organic matter lower si al k al ti al and quartz clay ratios in lithofacies b2 similar maceral types and the laminated fabric of the two lithofacies indicate that the quality and quantity of organic matter are not related to grain size redox or organic matter source changes high total organic carbon toc and hydrogen index hi low oxidation index ox i ratio of oxygen functional groups to aliphatic groups derived by ftir lighter 15ntot and heavier 13corg isotopes indicate that kerogen of lithofacies b1 accumulated during periods of high organic carbon production and delivery of relatively fresh labile well preserved organic matter to the sea floor in contrast low toc hi high ox i heavier 15ntot and lighter 13corg isotopes indicate low primary productivity and delivery high recycling and poor preservation of organic matter during accumulation of lithofacies b2

oxygen isotope microanalysis by secondary ion mass spectrometry suggests continuous 300 million year history of calcite cementation and dolomitization in the devonian bakken formation calcite cementation and dolomitization are key diagenetic processes in many sedimentary systems unravelling detailed histories and timescales of cementation and replacement is however often compromised by the limited spatial resolution of many analytical techniques in some cases multiple grains are co analyzed so that diagenetic histories are blurred and reaction periods are difficult to establish in this study we have used 10 micrometer resolution in situ secondary ion mass spectrometry to determine the oxygen isotope composition of 197 individual 10 50 micrometer size crystals of dolomite and calcite from six samples in a single core of upper devonian middle bakken member siltstones and sandstones the major tight oil formation of the williston basin usa this amount of data places important constraints on the range of temperatures and times that carbonate cementation and replacement occurred petrographic data show that microcrystalline calcite cement is an early phase and combined with mineralogical data suggest that much of the dolomite replaces calcite over spatial scales of less than a centimeter analyses of individual calcite crystals have a range of 5 for 18o in the group of crystals and for the group of individual dolomite crystals 10 these sub centimeter ranges are as great as those observed in previous studies of carbonate cements sampled over many meters and remind us that previous low resolution studies may have inadvertently analyzed mixed phases there is no relationship between dolomite texture and isotopic composition at this spatial scale microscale backscattered electron imagery and scanning electron microscopy cathodoluminescence zoning is seen but cannot be resolved with a 10 micrometer spot size assuming since it is an early cement that calcite precipitated from seawater 18o 1 5 it formed at ca 15 40 c mainly at the lower temperatures present day formation waters in devonian rocks in this region have oxygen isotope compositions of 7 8 vsmow using these values as a likely dolomitizing fluid we suggest that dolomitization occurred continuously between 40 and 140 c over 150 200 million years most likely in a fluid with a high mg ca ratio resulting from gypsum formation in local evaporites we suggest that this exceptionally low rate of dolomitization was controlled by the low rate of supply of mg in a very sluggish flow regime dolomitization is incomplete because of a limited supply of mg

marine carbon reservoir corg ccarb coupling and the evolution of the proterozoic carbon cycle the post 2 0 ga proterozoic c isotope record reveals two distinct yet interrelated trends a stepwise increase in average 13c from 0 calculated with respect to the peedee belemnite isotope standard prior to ca 1 3 ga to 5 in the neoproterozoic and a concomitant increase in the magnitude of isotopic excursions steady state and non steady state models suggest that these fundamental changes are best explained by a combination of evolving burial fluxes and a secular decrease in the size of the marine dissolved inorganic carbon dic reservoir the dic reservoir size affects the sensitivity of the isotopic system to biogeochemical perturbation major rearrangements of carbon cycling during the proterozoic in part related to the evolving marine carbon reservoir permit elevated 13c values to be sustained for geologically long time spans recognition of this dependence on dic reservoir size provides for the first time a direct link between changing carbonate precipitation styles and the marine c isotope record and may help constrain estimates of proterozoic p co2

revised interpretations of stable c and o patterns in carbonate rocks resulting from meteoric diagenesis abstract a positive correlation between the 13c and 18o values of carbonate rocks is a screening tool widely used to identify the overprint of meteoric diagenesis on the original isotopic composition of a sample in particular it has been suggested that systematic change from negative to positive 13c and 18o values with increasing depth in the core is an indicator of alteration within the zone of mixing between meteoric and marine waters in this paper we propose that such covariance is not generated within the traditionally defined mixing zone and that positive correlations between 13c and 18o values in marine carbonates are not necessarily indicators of meteoric alteration this new interpretation is based on data collected from the shallow sub surface of the bahamas a region unequivocally influenced by meteoric waters to depths of at least 200 m below the current sediment water interface the classic interpretation of the diagenetic environments based on changes in the 13c and 18o values would suggest the maximum penetration of freshwater occurs between 65 and 100 m below seafloor below these depths a strong positive covariation between the 13c and 18o values exists and would traditionally be defined as the mixing zone however based upon known changes in sea level the penetration of the freshwater lens extends significantly below this limit we contend that the zone showing covariance of 13c and 18o values is actually altered within the freshwater lens and not the mixing zone as previously proposed the co varying trend in 13c and 18o values is the result of diagenetic processes occurring at the interface between vadose and phreatic zones significantly greater rates of recrystallization and neomorphism are driven by the increased rates of oxidation of organic matter at this transition with progressively less alteration occurring with increasing depth as sea level oscillates the position of this interface moves through the deposit causing cumulative alteration throughout the section hence we propose that the covariation between 13c and 18o values is a consequence of varying degrees of alteration rather than the result of diagenesis occurring within the zone where marine and freshwater fluids mix furthermore within the pervasively altered vadose zone there is little correlation between 13c and 18o values and therefore covariation between 13c and 18o values is not an unequivocal indicator of meteoric diagenesis

marine redox conditions in the middle proterozoic ocean and isotopic constraints on authigenic carbonate formation insights from the chuanlinggou formation yanshan basin north china abstract to improve our understanding of ocean chemistry and biogeochemical cycling following the termination of large scale paleoproterozoic iron formation if deposition 1 85 billion years ago ga we conducted a fe s c mo geochemical study of the 1 65 ga chuanlinggou formation yanshan basin north china despite the cessation of if deposition our results suggest the presence of anoxic but non euxinic ferruginous conditions persisted below the surface mixed layer for the deepest portion of the continental rifting basin and that this pattern is apparently independent of the local organic carbon content however our paired s isotope data of carbonate associated sulfate and pyrite suggest presence of sulfate in pore fluids which is not consistent with insufficient sulfate for bacterial sulfate reduction in the water column despite evidence for deposition under anoxic conditions sedimentary molybdenum mo concentrations are mostly not enriched relative to average continental crust this relationship is consistent with the notion that sulfide dominated conditions in the water column and or the sediments are required for mo enrichment and validates past assertions that mo enrichment patterns in ancient shales track both the local presence and global distribution of euxinia specifically in addition we identified extensive diagenetic carbonate precipitation in the upper chuanlinggou formation with only moderately negative 13 c values 3 4 1 4 we propose with support from a numerical model that these diagenetic carbon isotope values were most likely derived from precipitation of carbonates dominantly in the methanic zone within the sediments diagenetic carbonate precipitation in the methanic zone is likely to have been more extensive in the proterozoic than the phanerozoic due to porewater oxidant limitation

anachronistic facies from a drowned lower triassic carbonate platform lower member of the alwa formation ba id exotic oman mountains abstract the lower member of the alwa formation lower olenekian found within the ba id exotic in the oman mountains sultanate of oman consists of ammonoid bearing pelagic limestones that were deposited on an isolated drowned carbonate platform on the neotethyan gondwana margin the strata contain a variety of unusual carbonate textures and features including thrombolites frutexites bearing microbialites that contain synsedimentary cements matrix free breccias surrounded by isopachous calcite cement and fissures and cavities filled with large botryoidal cements thrombolites are found throughout the study interval and occur as 0 5 1 0 m thick lenses or beds that contain laterally laterally linked stromatactis cavities the frutexites bearing microbialites occur less frequently and also form lenses or beds up to 30 cm thick the microbialites may be laminated and often developed on hardgrounds in addition the frutexites bearing microbialites also contain synsedimentary calcite cement crusts and botryoids typically frutexites bearing microbialites low level of calcium carbonate supersaturation associated with anoxic conditions and deposition below a stable chemocline formed the results of this study point to continued environmental stress in the region during the early triassic that likely contributed to the uneven recovery from the permian triassic mass extinction

a weathering hypothesis for glaciation at high atmospheric pco2 during the late ordovician new paired carbonate and organic carbon isotope analyses from nevada usa together with a consideration of the effects of mountain building and ice sheet coverage of the continents on atmospheric pco2 lead to a new hypothesis for the cause of the late ordovician glaciation we suggest that the taconic orogeny which commenced in the late middle ordovician caused a long term decline in atmospheric pco2 through increased weatherability of silicate rocks ice sheet growth was triggered when pco2 decreased to a threshold of 10 present atmospheric level and proceeded by positive ice albedo feedback in the midst of glaciation atmospheric pco2 began to rise as continental silicate weathering rates declined in response to coverage of weathering terrains by ice sheets at first this enhanced greenhouse effect was overcompensated for by ice albedo effects ultimately however atmospheric pco2 reached a level which overwhelmed the cooling effects of ice albedo and the glaciation ended the isotope results can be interpreted to indicate that atmospheric pco2 rose during the glaciation consistent with other proxy information although alternative interpretations are possible the large positive carbonate isotope excursion observed in late ordovician rocks around the world is explained as the expected response to increased carbonate platform weathering during glacioeustatic sea level lowstand rather than as a response to increased organic carbon burial

a model for atmospheric co 2 over phanerozoic time a new model has been constructed for calculating the level of atmospheric co sub 2 over phanerozoic time which is much simpler mathematically than the blag model but more complex geologically and biologically results suggest that there has been a notable pattern of varying atmospheric co sub 2 level over the past 570 my with high levels during the mesozoic and early paleozoic and low levels during the permo carboniferous and late cenozoic sensitivity analysis shows that within reasonable limits of the principal governing parameters this qualitative trend of varying co sub 2 is relatively insensitive to the actual values chosen for these parameters causes of the co sub 2 variation are multiple and no single geological or biological process can be called upon to explain all co sub 2 variation for all time the calculated trend of co sub 2 over time agrees well with independent estimations of paleoclimates thus the greenhouse theory of paleoclimate on a long geological time scale is supported by the results of the present study

isotopic evidence for massive oxidation of organic matter following the great oxidation event the stable isotope record of marine carbon indicates that the proterozoic eon began and ended with extreme fluctuations in the carbon cycle in both the paleoproterozoic 2500 to 1600 million years ago ma and neoproterozoic 1000 to 542 ma extended intervals of anomalously high carbon isotope ratios 13c indicate high rates of organic matter burial and release of oxygen to the atmosphere in the neoproterozoic the high 13c interval was punctuated by abrupt swings to low 13c indicating massive oxidation of organic matter we report a paleoproterozoic negative 13c excursion that is similar in magnitude and apparent duration to the neoproterozoic anomaly this shunga francevillian anomaly may reflect intense oxidative weathering of rocks as the result of the initial establishment of an oxygen rich atmosphere

microbial carbonate abundance compared with fluctuations in metazoan diversity over geological time abstract secular variation in microbial carbonate abundance may be reflected by stromatolite morphotype diversity and reefal microbial carbonate abundance these datasets reveal long term changes over the past 3000 myr that include a peak of abundance 1250 myr ago late proterozoic decline cambrian resurgence and fluctuating decline during the remainder of the phanerozoic it is conceivable that proterozoic metazoan diversification coincided with inception of stromatolite decline 1250 myr ago but microbial carbonate increase during cambrian metazoan radiation together with failure of microbial carbonates to increase in the aftermaths of the end ordovician end triassic and end cretaceous mass extinctions suggest that factors in addition to metazoan competition significantly influenced long term changes in microbial carbonate abundance

joining forces combined biological and geochemical proxies reveal a complex but refined high resolution palaeo oxygen history in devonian epeiric seas abstract two devonian black shale intervals were analysed using a carefully integrated palaeontological geochemical approach to interpret relative bottom water oxygen levels at a resolution and sensitivity possible only through the combined approach biological data presented as both trace and body fossil abundance and size suggest generally low bottom water oxygen conditions the frequently laminated sediments would be viewed traditionally as recording appreciable intervals of anoxic and or euxinic anoxic and h 2 s containing bottom waters the inclusion of parallel geochemical results however refines this perspective well established iron proxies for depositional redox tell us that anoxic and euxinic conditions were intermittent and short lived if present at all manganese and molybdenum data point to conditions with a likelihood of very low oxygen in bottom waters during intervals with high pore water concentrations of hydrogen sulphide near the sediment water interface these elevated sulphide concentrations under iron limited diagenetic conditions varied with organic content and may have further inhibited benthic colonization and an active infaunal community more specifically the combined palaeontological and geochemical data sets point to depleted bottom water oxygen contents with evidence for hydrogen sulphide limited dominantly or exclusively to the pore waters anoxia and euxinia if present occurred only intermittently and lasted only briefly perhaps on seasonal time scales tied to primary productivity cycles or climatically induced variation in water column stratification the time scales and mechanisms of rapid redox variation remain to be studied the details of such transitional and dynamic settings are best viewed from a multi proxy biogeochemical and palaeoecological perspective as an important byproduct geochemical methods refined in multi proxy studies of phanerozoic shales can then be extended with greater utility to precambrian strata without trace and body fossils

late devonian and early mississippian bakken and exshaw black shale source rocks western canada sedimentary basin a sequence stratigraphic interpretation the late devonian and early mississippian bakken and exshaw formations are a continuum of regionally correlated organic rich up to 35 total organic carbon black shale source rocks covering much of the western canada sedimentary basin the bakken formation is composed of 1 a black mudstone lower member 2 a gray mudstone sandstone middle member and 3 a black mudstone upper member the exshaw formation beneath the alberta plains and in exposures in the foothills and front ranges of the rocky mountains is composed of 1 a lower black shale member and 2 an upper siltstone member the basal black shale unit of the lower mississippian banff formation overlying the exshaw formation is a second organic rich interval these black shales are regionally significant hydrocarbon source rocks and local reservoirs the middle bakken member is a locally important reservoir rock with substantial economic potential the bakken and exshaw formations and the basal banff black shale are divisible into three systems tracts 1 a transgressive systems tract 2 a lowstand systems tract and 3 a second transgressive systems tract lodgepole and banff formation carbonates overlying the bakken and exshaw formations are part of a highstand systems tract a sequence boundary occurs between the lower and middle bakken members the conformable equivalent of this sequence boundary is within the exshaw black shale member variations in the internal composition of these systems tracts imply that two depocenters 1 the williston basin and 2 the prophet trough and the western margin of the north american craton were affected differently by relative sea level rise and fall during bakken and exshaw deposition because of differences in water depth and sediment accommodation spatial and temporal changes in black shale and gray mudstone sandstone as highlighted by this sequence stratigraphic interpretation may have significant impacts on source rock potential and hydrocarbon reservoir size location and quality

interpreting carbon isotope excursions carbonates and organic matter abstract variations in the carbon isotopic compositions of marine carbonate and organic carbon provide a record of changes in the fraction of organic carbon buried through time and may provide clues to changes in rates of weathering and sources of organic carbon paired carbonate and organic carbon isotope determinations provide a possibility of interpreting not only changes in the global carbon cycle through time but changes in atmospheric pco2 as well interpretations of these types of data are typically rather qualitative a quantitative basis is required to develop a better understanding of changes in the carbon cycle for this purpose we employ a simple model of the global carbon cycle which is subjected to a number of different perturbations each lasting 500 ky i e much longer than the residence times of carbon and phosphorus in the ocean atmosphere system in addition to standard considerations of carbon mass and isotopic fluxes to the ocean atmosphere system from weathering and volcanism and fluxes of organic carbon and carbonate carbon to sediments the model incorporates sensitivity of the photosynthetic carbon isotope effect to changes in pco2 the inclusion of this parameter leads to unexpected carbon isotope responses to forcing that causes increased rates of organic carbon burial a series of simple to more complex simulations illustrates the significant effects of varying differences between the carbon isotopic composition of sedimented carbonate and organic carbon b with constant b a 50 increase in organic carbon burial produces a parallel increase in carbonate and organic carbon isotopic compositions however the same simulation with b responsive to pco2 changes produces an initial parallel 13 c increase but this is followed by an even greater 13 c enrichment in organic carbon because pco2 falls in response to increased organic carbon burial the counterintuitive overall result of the enhanced organic carbon burial event is that the carbonate carbon isotopic composition actually decreases because of the more substantial increase in 13 c org in addition we illustrate the effects on carbon isotopic compositions of the oceanic inorganic carbon reservoir and buried organic matter of a 50 increase in volcanic co2 outgassing a 50 increase in weathering rate with coupled phosphate and riverine carbon flux responses a 50 decrease in shale associated organic carbon weathering a 50 decrease in silicate weathering rate and the possible effects of the rise in abundance of c4 plants in the late miocene to recent we compare the model simulated carbon isotopic responses for some of these experiments to paired carbonate and organic carbon records to illustrate how these records might be interpreted in light of the model response

chlorobiaceae in palaeozoic seas revealed by biological markers isotopes and geology biomarker hydrocarbons in oils and sediments have considerable potential for assessing the nature of biological processes in the past but only a few can be uniquely related to particular organisms reef hosted oils in the silurian of the michigan basin canada and the devonian of western canada have high abundances of 1 alkyl 2 3 6 trimethylbenzenes their precise structures suggest that they are diagenetic products of aromatic carotenoids of the green sulphur bacteria individual components are enriched in 13c by 7 8 relative to the saturated hydrocarbons of the same oil an isotopic anomaly of this magnitude and direction correlates with a component of photosynthetic carbon assimilation by the reductive tricarboxylic acid cycle these results together with data on palaeoenvironments provide compelling evidence for the existence in ancient restricted seas of microbial communities containing chlorobiaceae organisms with distinctive biochemistry which leave morphologically identifiable remains

ichnology of a late devonian early carboniferous low energy seaway the bakken formation of subsurface saskatchewan canada assessing paleoenvironmental controls and biotic responses abstract in spite of the high interest on the late devonian early carboniferous bakken formation as one of the most important oil plays in north america and the numerous studies carried out in this unit no ichnologic analysis has been presented yet based on conventional sedimentologic data previous studies of the bakken interpreted the unit as formed entirely under open marine conditions however integration of ichnology has been key to the identification of not only open marine but also brackish water marginal marine conditions based on the geometry of the sedimentary bodies and the sequence stratigraphic framework the brackish water interval is interpreted as an embayment with limited or intermittent connection to the open sea salinity oxygen content and storms are regarded as the most important environmental parameters that controlled the distribution and nature of the trace fossils in the bakken formation sparse bioturbation relatively low ichnodiversity and the impoverished cruziana ichnofacies characterize the marginal marine deposits suggesting stressful brackish water conditions marine deposits from the middle member in contrast are highly bioturbated with a moderate ichnodiversity and the distal cruziana ichnofacies that flourished during fully marine well oxygenated conditions there is only a slight difference between the total ichnodiversity of the open marine interval ten ichnogenera and that of the brackish water interval seven ichnogenera ichnodiversity should not be considered at face value and isolated from other aspects when evaluating stress levels in order to detect a brackish water signal lack of bioturbation in the black shale of the lower and upper members resulted from anoxic conditions the passage from anoxic lower member to well oxygenated conditions middle member was gradational as is revealed by the occurrence of oxygen deficient trace fossils at the top of the lower member finally the contrasting styles in tempestite preservation in upper offshore deposits from the lower and upper open marine intervals is attributed to variations in the intensity and frequency of storm during deposition of the highstand and transgressive deposits

production and preservation of organic matter during deposition of the bakken formation late devonian and early mississippian williston basin abstract the organic rich up to 35 toc lower and upper black mudstone members of the bakken formation late devonian and early mississippian accumulated in response to both increased productivity and enhanced preservation that resulted from unique palaeogeographic palaeoceanographic and palaeoclimatic conditions during bakken deposition the semi isolated williston basin was located close to the equator 5 to 10 n in a zone of prevailing east to west winds a pattern of estuarine like marine circulation between the williston basin and open ocean conditions at the western craton edge of north america is proposed surface water discharged from the basin was replaced by nutrient rich deeper water sourced from the equatorial undercurrent in the pacific basin undercurrent flow into the williston basin upwelled providing a potentially sustainable source of nutrients to enhance productivity in the surface photic zone during black mudstone deposition in response to increased productivity that led to a high rate of organic sedimentation and quiescent deep water conditions due primarily to the geographic isolation of the basin and the restriction of estuarine like circulation to the upper water column anoxic bottom water developed on the basin floor as sea level rose during lower and upper black mudstone deposition anoxic bottom water expanded across the basin enhancing organic matter preservation conditions in the williston basin demonstrate that both increased productivity and improved preservation can be essential and complementary factors affecting organic rich mud deposition these results have potentially important implications for the accumulation of similarly organic rich deposits across the north american interior during late devonian and early mississippian time

traces in the dark sedimentary processes and facies gradients in the upper devonian lower mississippian upper shale member of the bakken formation williston basin north dakota u s a discussion i would like to comment on a recent paper by egenhoff and fishman 2013 that discusses observations made on cores of the bakken shale and presents a methodology to examine and describe these cores in this contribution i would like to discuss some of their observations and conclusions related to perceived bioturbation features the authors very eloquently came up with an attractive title for their paper traces in the dark and it is this darkness that i would like to shine some light on some of the burrows that are shown like the burrow tubes with contrasting fill in their figure 4 are rather clear and there is no disagreement others like those in their figure 5 may just as well be cross sections of pellets and probably a thin section parallel to bedding would be required to sort out their actual origin e g macquaker et al 2010 the aspects that i found the most troubling are shown in their figure 6 a and b where a laminated black shale is shown on which the authors drew white lines to highlight what they interpret to be burrows that penetrate this laminated shale and there is the rub without these white lines i would never have been able to see these burrows and i have seen plenty of subtle bioturbation in shales before e g schieber 2003 having worked on devonian black shales for two decades i actually have hundreds of thin sections like this one in my collection the silt laminae in sections from my collection especially if only a few grains thick show gaps and discontinuities in the ten to hundred micron range quite commonly but i personally would not interpret these gaps in terms

isotope signatures associated with early meteoric diagenesis the environments in which carbonate diagenesis proceeds have been documented in previous studies of holocene and late pleistocene sediments and limestones on barbados west indies variations in the carbon and oxygen isotopic composition of limestones produced during early freshwater diagenesis have been observed in this study to occur in specific patterns six potentially useful patterns emerge when one views stable isotope data within a stratigraphic framework 1 the subaerial exposure surface is characterized by strongly 12c enriched limestones 13c compositions of underlying limestones grow progressively heavier with increasing depth 2 the subaerial exposure surface may also be marked by slight 18o enrichment 3 an abrupt shift in 18o values may differentiate sediments above the exposure surface from those below 4 sediments altered in the marine meteoric mixing zone may be characterized by positive covariance between their 18o and 13c compositions 5 the vadose phreatic boundary may be marked by a sharp increase in 13c values in the seaward portions of a fresh groundwater system and 6 samples contemporaneously altered in a single fresh groundwater system within an areally restricted region should display a narrow range of 18o and a wide range of 13c compositions analysis of samples from five palaeozoic and mesozoic formations which contained petrographic evidence of early freshwater diagenesis showed that isotope patterns similar to those observed in barbados limestones have been preserved in rocks as old as mississippian these isotope patterns could prove to be useful for identifying diagenetically induced porosity trends in carbonate rocks they might be used to identify limestones diagenetically altered in meteoric environments to identify mixing zone cements and dolomites and to trace the regional and vertical distributions of early meteoric groundwater systems in ancient carbonate formations

aryl isoprenoids and diaromatic carotenoids in paleozoic source rocks and oils from the western canada and williston basins abstract aryl isoprenoids in the range c13 c31 have been identified in source rock bitumens and oils from several paleozoic age petroleum systems in the western canada and williston basins the principal compounds possess the 2 alkyl 1 3 4 trimethyl substitution pattern characteristic of diaromatic carotenoids found in the chlorobiaceae family of photosynthetic sulfur bacteria two c40 perhydrodiaromatic carotenoids which are structurally related to the presumed precursors of the aryl isoprenoids have also been identified in oils and source rock bitumens of the duvernay late devonian petroleum system pyrolysis gas chromatograms of kerogens isolated from several paleozoic source rocks show an unusual abundance of 1 2 3 4 tetramethylbenzene it is proposed that this compound arises from cleavage of diaromatic carotenoid moieties which have been incorporated into the kerogen structure with increasing maturation concentrations of the aryl isoprenoids in duvernay source rock bitumens increase to a point whereas the c40 perhydrodiaromatic carotenoids decrease steadily previous studies have suggested that aryl isoprenoids may be indicators of enhanced salinity environments this is not supported by the present work which shows high concentrations in source rocks associated with presumed normal marine salinities there is however a general association with intervals of condensed clastic or mixed clastic carbonate sedimentation within carbonate depositional systems from the association found and from parallels to modern habitats of photosynthetic bacteria it can be inferred that these biomarkers indicate prolific bacterial growth in a stratified water column at and below the oxic anoxic boundary layer in sub tropical to tropical marine environments

methane derived carbonates and authigenic pyrite from the northwestern black sea abstract methane seeps in the northwestern black sea are accompanied by carbonate and pyrite precipitates sediments were sampled at locations on the romanian 120 m depth and ukrainian 180 200 m depth shelf and slope layered carbonate crusts are formed of i carbonate cemented siliciclastic sediment containing dreissenoid bivalves ii microcrystalline high mg calcite or aragonite and iii aragonitic cement the dreissena sediment is subrecent and was deposited during the freshwater phase of the black sea it has been affected by seepage of methane rich fluids which induced intergranular precipitation of authigenic carbonates the microcrystalline carbonates exhibit an intense autofluorescence high mg calcite contains 11 14 mol mgco3 the aragonitic cement 8300 9500 ppm sr forms either isopachous layers or botryoids microbial filaments about 10 20 m in diameter and up to 900 m in length are preserved within and on carbonate crusts the carbonates are depleted in 13c microcrystalline carbonate ranges from 27 to 41 pdb and botryoidal aragonite ranges from 26 to 38 pdb the 13c depletion indicates that the carbonates predominantly derive from the microbial oxidation of methane carbonate deposits do not project up into the oxic water column they are restricted to the anoxic water column and to anoxic sediments revealing the crucial role of anaerobic methane oxidation for carbonate precipitation 14c contents give apparent radiocarbon ages of 20 640 180 a bp for a sample of botryoidal aragonite and 19 110 180 a bp for a sample of microcrystalline carbonate compatible with minimum ages of carbon derived from a fossil hydrocarbon source the 18o values of methane derived carbonates show a narrow range from 1 2 to 0 2 pdb 87sr 86sr ratios of microcrystalline carbonate mean 0 70927 and aragonitic cement mean 0 70918 are indistinguishable from ambient seawater mean 0 70917 and thus indicate a shallow sr source higher 87sr 86sr ratios of the dreissena sediment mean 0 71005 are probably caused by sr derived from detrital mica carbonates are accompanied by blocks and crusts composed of pyrite the framboidal sulphide exhibits a palisade like fabric with framboids arranged to parallel pillars sulphur isotopic ratios 34s ranging from 16 8 to 19 7 cdt indicate that the sulphur derives not from the 34s depleted h2s of the water column or the uppermost sediment layers most likely pyrite formed in the lacustrine sediments after the first incursion of mediterranean seawater

the lost devonian sequence sequence stratigraphy of the middle bakken member and the importance of clastic dykes in the lower bakken member shale north dakota usa abstract the late devonian to early mississippian bakken formation in the williston basin of north dakota usa shows a tri partite subdivision a middle mixed carbonate siliciclastic member is sandwiched in between two black siliciclastic mudstones the lower and upper bakken member shales however the transition from the lower shale member to the middle member does not represent a gradual coarsening but contains in places several millimeter to centimeter thick siliciclastic mudstones and carbonates that consist of three facies 1 a glauconitic carbonate rich siliciclastic mudstone 2 a carbonate mud to wackestone and 3 an echinoderm wacke to packstone with shell fragments these three facies are present in many all of the cores close and directly in the basin center in mountrail county north dakota at least one of these three facies is present in all 23 cores included in this study this thin carbonate unit at the transition between the lower and the middle bakken members is interpreted as representing the remnants of the transgressive systems tract it is assumed that relative sea level fell before deposition of the middle bakken member establishing a proximal coarse grained to distal fine grained depositional transect that successively migrated into the basin during the subsequent transgression the siliciclastic input was low to absent and the entire sedimentary system switched to depositing carbonates the proximal to distal transect during this time showed coarse grained packstones and grainstones close to the shoreline and a fining outwards towards the distal parts of the basin this transgression also eroded what remained of the regressive and most of the subsequent transgressive sediments leaving only the thin carbonate layer behind evidence for the regression even though no sediment is directly preserved along the lower to middle bakken member contact comes from the fill of clastic dykes that cut through the lower bakken member shale the fill of the clastic dykes is partly siliciclastic and partly carbonate and not similar to any of the surrounding sediment this indicates that these dykes must have originated before the middle bakken member was deposited yet the overlying sediment must have been carbonate at some point and siliciclastic another time as it is not present anymore this sediment must have been entirely removed by erosion the here presented model suggests that the bakken formation reflects two entire sea level oscillations the first encompasses the lower bakken member shale and the siliciclastic regressive portion of the lowstand only preserved as infill of the clastic dykes the subsequent transgression deposited the carbonates now blanketing the lower to middle bakken member transition and the highstand and subsequent regression plus lowstand are represented by the middle bakken member the transgressive surface and therewith the onset of the topmost bakken transgression is marked by the transition from the middle to the upper bakken shale member

a global marine sedimentary response to the end permian mass extinction examples from southern turkey and the western united states the end permian mass extinction greatly diminished marine diversity and brought about a whole scale restructuring of marine ecosystems these ecosystem changes also profoundly affected the sedimentary record data presented here attained through facies analyses of strata deposited during the immediate aftermath of the end permian mass extinction southern turkey and at the close of the early triassic southwestern united states in combination with a literature review show that sedimentary systems were profoundly affected by 1 a reduction in biotic diversity and abundance and 2 long term environmental fluctuations that resulted from the end permian crisis lower triassic strata display widespread microbialite and carbonate seafloor fan development and contain indicators of suppressed infaunal bioturbation such as flat pebble conglomerates and wrinkle structures facies considered unusual in post cambrian subtidal deposits our observations suggest that depositional systems too respond to biotic crises and that certain facies may act as barometers of ecologic and environmental change independent of fossil assemblage analyses close investigation of facies changes during other critical times in earth history may serve as an important tool in interpreting the ecology of metazoans and their environment

episodic cenozoic tectonism and the development of the nw european passive continental margin the north atlantic margins are archetypally passive yet they have experienced post rift vertical movements of up to kilometre scale the cenozoic history of such movements along the nw european margin from ireland to mid norway is examined by integrating published analyses of uplift and subsidence with higher resolution tectono stratigraphic indicators of relative movements including results from the stratagem project three episodes of epeirogenic movement are identified in the early mid and late cenozoic distinct from at least one phase of compressive tectonism two forms of epeirogenic movement are recognised referred to as tilting coeval subsidence and uplift rotations 1 over distances of 100s of kilometres and sagging strongly differential subsidence rotations up to 4 over distances 100 km each epeirogenic episode involved relatively rapid 10 ma km scale tectonic movements that drove major changes in patterns of sedimentation to find expression in regional unconformity bounded stratigraphic units early cenozoic tilting late paleocene to early eocene c 60 50 ma caused the basinward progradation of shelf slope wedges from elongate uplifts along the inner continental margin and from offshore highs mid cenozoic sagging late eocene to early oligocene c 35 25 ma ended wedge progradation and caused the onset of contourite deposition in deep water basins late cenozoic tilting early pliocene to present 4 0 5 ma again caused the basinward progradation of shelf slope wedges from uplifts along the inner margin including broad dome like features and from offshore highs the early mid and late cenozoic epeirogenic episodes coincided with atlantic plate reorganisations but the observed km scale tectonic movements are too large to be accounted for as flexural deflections due to intra plate stress variations mantle lithosphere interactions are implied but the succession of epeirogenic episodes of differing form are difficult to reconcile with the various syn to post rift mechanisms of permanent and or transient movements proposed in the hypothetical context of a plume beneath iceland the epeirogenic movements can be explained as dynamic topographic responses to changing forms of small scale convective flow in the upper mantle tilting as coeval upwelling and downwelling above an edge driven convection cell sagging as a loss of dynamic support above a former upwelling the inferred cenozoic succession of epeirogenic tilting sagging and tilting is proposed to record the episodic evolution of upper mantle convection during ocean opening a process that may also be the underlying cause of plate reorganisations the postulated episodes of flow reorganisation in the ne atlantic region have testable implications for epeirogenic movements along the adjacent oceanic spreading ridge and conjugate continental margin as well as on other atlantic type passive margins

geobiology of microbial carbonates metazoan and seawater saturation state influences on secular trends during the phanerozoic abstract microbial carbonates are long ranging essentially bacterial aquatic sediments their calcification is dependent on ambient water chemistry and their growth is influenced by competition with other organisms such as metazoans in this paper these relationships are examined by comparing the geological record of microbial carbonates with metazoan history and secular variations in caco3 saturation state of seawater marine abundance data show that microbial carbonates episodically declined during the phanerozoic eon past 545 myr from a peak 500 myr ago this abundance trend is generally inverse to that of marine metazoan taxonomic diversity supporting the view that metazoan competition has progressively limited the formation of microbial carbonates lack of empirical values concerning variables such as seawater ionic composition atmospheric partial pressure of co2 and ph currently restricts calculation of caco3 saturation state for the phanerozoic as a whole to the use of modeled values these data together with palaeotemperature data from oxygen isotope analyses allow calculation of seawater caco3 saturation trends microbial carbonate abundance shows broad positive correspondence with calculated seawater saturation state for caco3 minerals during the interval 150 545 myr ago consistent with the likelihood that seawater chemistry has influenced the calcification and therefore accretion and preservation of microbial carbonates these comparisons suggest that both metazoan influence and seawater saturation state have combined to determine the broad pattern of marine microbial carbonate abundance throughout much of the phanerozoic in contrast for the major part of the precambrian it would seem reasonable to expect that seawater saturation state together with microbial evolution was the principal factor determining microbial carbonate development interrelationships such as these with feedbacks influencing organisms sediments and the environment are central to geobiology

relationship between inferred redox potential of the depositional environment and geochemistry of the upper pennsylvanian missourian stark shale member of the dennis limestone wabaunsee county kansas u s a analyses of 21 samples collected from a core of the 52 8 cm thick stark shale member of the dennis limestone in wabaunsee county kansas demonstrate four cycles with two orders of magnitude variations in contents of cd mo p v and zn and order of magnitude variations in contents of organic carbon cr ni se and u the observed variability in amounts and or ratios of many metals and amounts and compositions of the organic matter appear related to the cause and degree of water column stratification and the resulting absence presence of dissolved o2 or h2s high cd mo u v zn and s contents a high degree of pyritization dop 0 75 0 88 and high high v v ni 0 84 0 89 indicate the presence of h2s in a strongly stratified water column intermediate contents of metals and s intermediate dop 0 67 0 75 and intermediate v v ni 054 0 82 indicate a less strongly stratified anoxic water column whereas low metal contents and low v v ni 0 46 0 60 indicate a weakly stratified dysoxic water column high p contents at the top of the organic matter rich intervals within the stark shale member indicate that phosphate precipitation was enhanced near the boundary between anoxic and dysoxic water compositions relatively abundant terrestrial organic matter in intervals deposited from the more strongly stratified h2s bearing water column indicates a combined halocline thermocline with the fresher near surface water the transport mode for the terrestrial organic matter the predominance of algal organic matter in intervals deposited from a less strongly stratified water column indicates the absence of the halocline and the presence of the more generally established thermocline relatively low amounts of degraded hydrogen poor organic matter characterize intervals deposited in a weakly stratified dysoxic water column the inferred variability in chemistry of the depositional environments may be related to climate variations and or minor changes in sea level during the general phase of deeper water deposition responsible for this widespread shale member

authigenic carbonate formation rates in marine sediments and implications for the marine δ13c record abstract carbon isotope 13 c variations measured in carbonates have been attributed to large scale phenomena throughout earth history such as changes in atmospheric oxygen or global glaciations these interpretations follow from a model wherein the 13 c of marine dissolved inorganic carbon dic is controlled by the relative sedimentary burial rates of biogenic carbonate bc and organic carbon oc a new model proposes authigenic carbonate ac as a third major sedimentary c pool implying that 13 c anomalies are not necessarily indicative of extreme changes in the global carbon cycle and or atmospheric oxygen two conditions are required for ac formation to significantly alter bulk carbonate 13 c the ac isotopic composition must be at least 3 different from that of bc and the ac bc ratio must be 0 1 we use pore fluid ca and sr concentrations to estimate rates of ac formation in late cenozoic marine sediments then calculate relative fractions of ac oc and bc today ac is not expected to constitute a significant fraction of total sedimentary carbon ac oc bc globally however there are modern sites where local conditions promote elevated ac bc and anaerobic metabolisms can alter the 13 c of pore fluids we investigate these sites to determine what conditions might enable ac to alter 13 c of marine dic we find there is very little net addition of ac relative to bc but large quantities of ac form today across many settings via recrystallization in settings where remineralization of organic matter causes recrystallized carbonate to form with modified 13 c ac bc is generally too low for this recrystallization to significantly shift the 13 c of the bulk carbonate however exceptions are found in sites with very low bc and extensive methane oxidation suggesting that this environment type would need to be globally extensive in the past in order for ac formation to change the 13 c of marine dic

significance of stable carbon isotope trends in carbonate concretions formed in association with anaerobic oxidation of methane aom middle and upper devonian shale succession western new york state usa abstract carbonate concretions are concentrated along discrete stratigraphic horizons within middle and upper devonian carbonaceous black and organic deficient gray shale of western new york state textural characteristics preserved throughout studied concretions including a clay grain microfabric typical of flocculated clay and spherical algal cysts are consistent with a model entailing the formation of low density compaction resistant calcium carbonate masses at shallow burial depth within the zone of bacterial sulfate reduction burial of nascent concretions to the sulfate methane transition zone smtz was accompanied by the nearly complete infilling of porosity the diagenetic consequence of the anaerobic oxidation of methane aom each concretionary horizon then defines the position of the smtz stabilized during an episode of reduced sedimentation rate most analyzed concretions 75 of the middle devonian marcellus formation into the upper devonian gowanda formation display center to edge profiles of increasing bulk 13c far fewer concretions are characterized by radial profiles of decreasing 13c the common radial profiles of increasing 13c can be attributed to aom related kinetic carbon isotope fractionation under diagenetic conditions of limited methane which favors the production of dissolved inorganic carbon of increasing 13c less common concretions displaying center to edge profiles of diminishing 13c may record the anaerobic oxidation of more strongly 13c depleted methane produced by carbon dioxide reduction methanogenesis related to the degradation of organic matter within and near the smtz or aom back flux an enzyme mediated equilibrium isotope effect these processes are favored by sulfate limited diagenetic conditions more typical of the lower smtz and immediately underlying upper methanogenic zone mez contradictory isotope profiles of texturally similar concretions can be accounted for by diagenesis associated with an extended smtz esmtz comprising the methane limited smtz and the underlying sulfate deficient upper mez vertical shifts of the diagenetic horizons of the esmtz induced by variable methane flux would have juxtaposed concretions displaying seemingly incompatible isotopic histories