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USGS2014

Automated determination of the stable carbon isotopic composition (δ 13 C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon (δ 13 C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO 2 ) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO 2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO 2 . This configuration provides a fully automated analysis of total carbon mass and δ 13 C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H 3 PO 4 ), which allows the carbonate and bicarbonate species in the sample to dissociate to CO 2 . The CO 2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO 2 through an infrared CO 2 detector and quantifies the CO 2 . The CO 2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na 2 S 2 O 8 ) is added, and the hydroxyl radicals oxidize the organics to CO 2 . Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

Techniques and Methods↗

USGS2023

Carbonate chemistry and carbon sequestration driven by inorganic carbon outwelling from mangroves and saltmarshes

Mangroves and saltmarshes are biogeochemical hotspots storing carbon in sediments and in the ocean following lateral carbon export (outwelling). Coastal seawater pH is modified by both uptake of anthropogenic carbon dioxide and natural biogeochemical processes, e.g., wetland inputs. Here, we investigate how mangroves and saltmarshes influence coastal carbonate chemistry and quantify the contribution of alkalinity and dissolved inorganic carbon (DIC) outwelling to blue carbon budgets. Observations from 45 mangroves and 16 saltmarshes worldwide revealed that >70% of intertidal wetlands export more DIC than alkalinity, potentially decreasing the pH of coastal waters. Porewater-derived DIC outwelling (81 ± 47 mmol m −2 d −1 in mangroves and 57 ± 104 mmol m −2 d −1 in saltmarshes) was the major term in blue carbon budgets. However, substantial amounts of fixed carbon remain unaccounted for. Concurrently, alkalinity outwelling was similar or higher than sediment carbon burial and is therefore a significant but often overlooked carbon sequestration mechanism.

Nature↗

USGS2018

Defining blue carbon: The emergence of a climate context for coastal carbon dynamics

Blue Carbon Ecosystems (BCEs) are defined as coastal wetland ecosystems with manageable and atmospherically significant carbon stocks and fluxes. Policy and management opportunities have promoted the emergence of blue carbon as a concept and spurred scientific interest to reduce uncertainties in coastal carbon budgets. The four major BCEs are generally classified by their plant communities: tidal marshes, tidal freshwater forests, mangroves, and seagrass meadows.

Book chapter↗

USGS2008

Record of the Late Devonian Hangenberg global positive carbon-isotope excursion in an epeiric sea setting: Carbonate production, organic-carbon burial and paleoceanography during the late Famennian

Latest Famennian marine carbonates from the mid-continent of North America were examined to investigate the Late Devonian (very late Famennian) Hangenberg positive carbon-isotope (??13 Ccarb) excursion. This global shift in the ?? 13C of marine waters began during the late Famennian Hangenberg Extinction Event that occurred during the Middle Siphonodella praesulcata conodont zone. The post-extinction recovery interval spans the Upper S. praesulcata Zone immediately below the Devonian-Carboniferous boundary. Positive excursions in ?? 13 Ccarb are often attributed to the widespread deposition of organic-rich black shales in epeiric sea settings. The Hangenberg ??13 Ccarb excursion documented in the Louisiana Limestone in this study shows the opposite trend, with peak ??13 Ccarb values corresponding to carbonate production in the U.S. mid-continent during the highstand phase of the very late Famennian post-glacial sea level rise. Our data indicate that the interval of widespread black shale deposition (Hangenberg Black Shale) predates the peak isotope values of the Hangenberg ??13 Ccarb excursion and that peak values of the Hangenberg excursion in Missouri are not coincident with and cannot be accounted for by high Corg burial in epeiric seas. We suggest instead that sequestration and burial of Corg in the deep oceans drove the peak interval of the ??13Ccarb excursion, as a result of a change in the site of deep water formation to low-latitude epeiric seas as the global climate shifted between cold and warm states.

Conference Paper↗

USGS2007

Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

The stable isotopic composition of dissolved inorganic carbon (??13C-DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed ?? 13C-DIC increased between 3-5??? from the stream source to the outlet weir approximately 0??5 km downstream, concomitant with increasing pH and decreasing PCO2. An increase in ??13C-DIC of 2.4 ?? 0??1??? per log unit decrease of excess PCO2 (stream PCO2 normalized to atmospheric PCO2) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO2 outgassing rather than exchange with atmospheric CO2 may be the primary cause of increased ?? 13C-DIC values downstream when PCO2 of surface freshwater exceeds twice the atmospheric CO2 concentration. Although CO2 outgassing caused a general increase in stream ??13C-DIC values, points of localized groundwater seepage into the stream were identified by decreases in ??13C-DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO2 during the early spring growing season. Thus, in spite of effects from CO2 outgassing, ??13C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright ?? 2007 John Wiley & Sons, Ltd.

Hydrological Processes↗

USGS2010

Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

Marine sediments contain about 500–10,000 Gt of methane carbon1, 2, 3, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined1, 4, but it releases relatively little methane to the ocean and atmosphere5. Sedimentary microbes convert most of the dissolved methane to carbon dioxide6, 7. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use Δ14C and δ13C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000–6,000 year age of dissolved organic carbon in the deep ocean8, and provide reduced organic matter and energy to deep-ocean microbial communities.

Nature Geoscience↗

USGS2021

Contribution of deep-sourced carbon from hydrocarbon seeps to sedimentary organic carbon: Evidence from radiocarbon and stable isotope geochemistry

Sulfate-driven anaerobic oxidation of methane (AOM) limits the release of methane from marine sediments and promotes the formation of carbonates close to the seafloor in seepage areas along continental margins. It has been established that hydrocarbon seeps are a source of methane, dissolved inorganic carbon, and dissolved organic carbon to marine environments. However, questions remain about the contribution of deep-sourced carbon from hydrocarbon seeps to the sedimentary organic carbon pool. In this study, we analyzed carbon quantity, radiocarbon content (as percent modern carbon, pMC), stable carbon isotopic compositions (as δ 13 C) of organic matter enclosed within seep carbonates from the Gulf of Mexico and the South China Sea to assess if sediment organic matter may be used as a proxy for methane seepage intensity. The δ 13 C values of organic matter (δ 13 C org ) exhibited a large range from −81.4‰ to −23.9‰. Radiocarbon contents of the carbonate-bound organic matter in seep carbonates ranged from 6% to 28% pMC, suggesting organic matter of the carbonates is a mixture of marine particulate organic matter (δ 13 C = −22‰ VPDB and 90% modern carbon) and biomass resulting from methane oxidation (assumed to have 0% modern carbon). Assuming constant productivity in the marine photic zone, it is proposed that seepage intensity and duration are the most important factors controlling the contribution of methane-derived carbon to the sedimentary column. This study reinforces the potential for using δ 13 C values of organic carbon to discern methane-rich environments in ancient sedimentary environments where authigenic carbonate is not present and to constrain the record of AOM through Earth history.

Chemical Geology↗

USGS1997

Equilibrium responses of global net primary production and carbon storage to doubled atmospheric carbon dioxide: Sensitivity to changes in vegetation nitrogen concentration

We ran the terrestrial ecosystem model (TEM) for the globe at 0.5° resolution for atmospheric CO 2 concentrations of 340 and 680 parts per million by volume (ppmv) to evaluate global and regional responses of net primary production (NPP) and carbon storage to elevated CO 2 for their sensitivity to changes in vegetation nitrogen concentration. At 340 ppmv, TEM estimated global NPP of 49.0 10 15 g (Pg) C yr −1 and global total carbon storage of 1701.8 Pg C; the estimate of total carbon storage does not include the carbon content of inert soil organic matter. For the reference simulation in which doubled atmospheric CO 2 was accompanied with no change in vegetation nitrogen concentration, global NPP increased 4.1 Pg C yr −1 (8.3%), and global total carbon storage increased 114.2 Pg C. To examine sensitivity in the global responses of NPP and carbon storage to decreases in the nitrogen concentration of vegetation, we compared doubled CO 2 responses of the reference TEM to simulations in which the vegetation nitrogen concentration was reduced without influencing decomposition dynamics (“lower N” simulations) and to simulations in which reductions in vegetation nitrogen concentration influence decomposition dynamics (“lower N+D” simulations). We conducted three lower N simulations and three lower N+D simulations in which we reduced the nitrogen concentration of vegetation by 7.5, 15.0, and 22.5%. In the lower N simulations, the response of global NPP to doubled atmospheric CO 2 increased approximately 2 Pg C yr −1 for each incremental 7.5% reduction in vegetation nitrogen concentration, and vegetation carbon increased approximately an additional 40 Pg C, and soil carbon increased an additional 30 Pg C, for a total carbon storage increase of approximately 70 Pg C. In the lower N+D simulations, the responses of NPP and vegetation carbon storage were relatively insensitive to differences in the reduction of nitrogen concentration, but soil carbon storage showed a large change. The insensitivity of NPP in the N+D simulations occurred because potential enhancements in NPP associated with reduced vegetation nitrogen concentration were approximately offset by lower nitrogen availability associated with the decomposition dynamics of reduced litter nitrogen concentration. For each 7.5% reduction in vegetation nitrogen concentration, soil carbon increased approximately an additional 60 Pg C, while vegetation carbon storage increased by only approximately 5 Pg C. As the reduction in vegetation nitrogen concentration gets greater in the lower N+D simulations, more of the additional carbon storage tends to become concentrated in the north temperate-boreal region in comparison to the tropics. Other studies with TEM show that elevated CO 2 more than offsets the effects of climate change to cause increased carbon storage. The results of this study indicate that carbon storage would be enhanced by the influence of changes in plant nitrogen concentration on carbon assimilation and decomposition rates. Thus changes in vegetation nitrogen concentration may have important implications for the ability of the terrestrial biosphere to mitigate increases in the atmospheric concentration of CO 2 and climate changes associated with the increases.

Global Biogeochemical Cycles↗

USGS1984

Carbonate and organic-carbon cycles and the history of upwelling at Deep Sea Drilling Project Site 532, Walvis Ridge, South Atlantic Ocean

Detailed carbonate and organic-carbon stratigraphies were constructed from samples collected every 20 cm in a 250-m hydraulic piston core recovered at DSDP Site 532 on Walvis Ridge. This sampling interval represents about one sample every 5000 yr., based on sediment accumulation rates calculated from nannofossil biostratigraphic zones. All samples were analyzed for percent CaCO 3 , resulting in a detailed carbonate stratigraphy for the past 5.0 m.y. The samples for the top 110 m of section were also analyzed for organic carbon in order to construct a detailed organiccarbon stratigraphy for the last 2.5 m.y. The recovered section has distinct dark-light color cycles with average periodicities of 55, 58, and 30 k.y. for the Quaternary, upper Pliocene, and lower Pliocene, respectively. Periodicities of carbonate cycles are similar to the color cycles; most carbonate minima correspond to the dark parts of color cycles. The average periodicity for carbonate cycles is about 36 k.y. Darker parts of color cycles usually contain higher concentrations of organic carbon, but the organic-carbon record does not follow the cyclicity of the color cycles in detail, at least for the last 2.5 m.y. Organic-carbon cycles have an average periodicity of about 34 k.y. for the Quaternary and upper Pliocene. The cycles of CaCO 3 and color have periodicities similar to those reported from carbonate stratigraphies from the northeast Atlantic, Caribbean, and eastern equatorial Pacific. The carbonate cycles at Site 532 are the result of external forcing, probably related to global climate, that affected fluctuations in both sediment supply from the African continental margin and productivity of siliceous organisms. The organic-carbon cycles have similar periodicities and similar changes in periodicities to those of the CaCO 3 cycles. Semiquantitative estimates of diatom abundance from smear slides and concentrations of biogenic SiO 2 calculated from chemical analyses suggest that upwelling at Site 532 was minor until about 3 m.y. ago. The Benguela-Current upwelling system either began at that time or, more likely, migrated into the area of Site 532, where it prevailed until some time between about 1.2 and 0.5 m.y. ago. The increase and decline of upwelling in the area of Site 532, however, did not disturb the trend of cyclicities of carbonate and organic carbon. The latest change in conditions at Site 532 was an increase in intensity of bottom currents during the past 0.5 m.y. that winnowed nannofossils, diatoms, and clay and left a lag deposit represented by a foraminifer-rich fades

Initial Reports of the D.S.D.P.↗

USGS2009

Modeling Carbon Dioxide, pH and Un-Ionized Ammonia Relationships in Serial Reuse Systems

In serial reuse systems, excretion of metabolic carbon dioxide has a significant impact on ambient pH, carbon dioxide, and un-ionized ammonia concentrations. This impact depends strongly on alkalinity, water flow rate, feeding rate, and loss of carbon dioxide to the atmosphere. A reduction in pH from metabolic carbon dioxide can significantly reduce the un-ionized ammonia concentration and increase the carbon dioxide concentrations compared to those parameters computed from influent pH. The ability to accurately predict pH in serial reuse systems is critical to their design and effective operation. A trial and error solution to the alkalinity–pH system was used to estimate important water quality parameters in serial reuse systems. Transfer of oxygen and carbon dioxide across the air–water interface, at overflow weirs, and impacts of substrate-attached algae and suspended bacteria were modeled. Gas transfer at the weirs was much greater than transfer across the air–water boundary. This simulation model can rapidly estimate influent and effluent concentrations of dissolved oxygen, carbon dioxide, and un-ionized ammonia as a function of water temperature, elevation, water flow, and weir type. The accuracy of the estimates strongly depends on assumed pollutional loading rates and gas transfer at the weirs. The current simulation model is based on mean daily loading rates; the impacts of daily variation loading rates are discussed. Copies of the source code and executable program are available free of charge.

Aquacultural Engineering↗

USGS2009

Rapid assessment of U.S. forest and soil organic carbon storage and forest biomass carbon sequestration capacity

This report provides results of a rapid assessment of biological carbon stocks and forest biomass carbon sequestration capacity in the conterminous United States. Maps available from the U.S. Department of Agriculture are used to calculate estimates of current organic carbon storage in soils (73 petagrams of carbon, or PgC) and forest biomass (17 PgC). Of these totals, 3.5 PgC of soil organic carbon and 0.8 PgC of forest biomass carbon occur on lands managed by the U.S. Department of the Interior (DOI). Maps of potential vegetation are used to estimate hypothetical forest biomass carbon sequestration capacities that are 3–7 PgC higher than current forest biomass carbon storage in the conterminous United States. Most of the estimated hypothetical additional forest biomass carbon sequestration capacity is accrued in areas currently occupied by agriculture and development. Hypothetical forest biomass carbon sequestration capacities calculated for existing forests and woodlands are within ±1 PgC of estimated current forest biomass carbon storage. Hypothetical forest biomass sequestration capacities on lands managed by the DOI in the conterminous United States are 0–0.4 PgC higher than existing forest biomass carbon storage. Implications for forest and other land management practices are not considered in this report. Uncertainties in the values reported here are large and difficult to quantify, particularly for hypothetical carbon sequestration capacities. Nevertheless, this rapid assessment helps to frame policy and management discussion by providing estimates that can be compared to amounts necessary to reduce predicted future atmospheric carbon dioxide levels.

Open-File Report↗

USGS2010

A method for assessing carbon stocks, carbon sequestration, and greenhouse-gas fluxes in ecosystems of the United States under present conditions and future scenarios

he Energy Independence and Security Act of 2007 (EISA), Section 712, mandates the U.S. Department of the Interior to develop a methodology and conduct an assessment of the Nation’s ecosystems, focusing on carbon stocks, carbon sequestration, and emissions of three greenhouse gases (GHGs): carbon dioxide, methane, and nitrous oxide. The major requirements include (1) an assessment of all ecosystems (terrestrial systems, such as forests, croplands, wetlands, grasslands/shrublands; and aquatic ecosystems, such as rivers, lakes, and estuaries); (2) an estimate of the annual potential capacities of ecosystems to increase carbon sequestration and reduce net GHG emissions in the context of mitigation strategies (including management and restoration activities); and (3) an evaluation of the effects of controlling processes, such as climate change, land-use and land-cover change, and disturbances such as wildfires. The concepts of ecosystems, carbon pools, and GHG fluxes follow conventional definitions in use by major national and international assessment or inventory efforts. In order to estimate current ecosystem carbon stocks and GHG fluxes and to understand the potential capacity and effects of mitigation strategies, the method will use two time periods for the assessment: 2001 through 2010, which establishes a current ecosystem carbon and GHG baseline and will be used to validate the models; and 2011 through 2050, which will be used to assess potential capacities based on a set of scenarios. The scenario framework will be constructed using storylines of the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emission Scenarios (SRES), along with both reference and enhanced land-use and land-cover (LULC) and land-management parameters. Additional LULC and land-management mitigation scenarios will be constructed for each storyline to increase carbon sequestration and reduce GHG fluxes in ecosystems. Input from regional experts and stakeholders will be solicited to construct these scenarios. The methods for mapping the current LULC and ecosystem disturbances will require the extensive use of both remote-sensing data and field-survey data (for example, forest inventories) to capture and characterize landscape-changing events. For potential LULC changes and ecosystem disturbances, key drivers such as socioeconomic and climate changes will be used in addition to the biophysical data. The result of these analyses will be a series of maps for each future year for each scenario. These annual maps will form the basis for estimating carbon storage and GHG emissions. For terrestrial ecosystems, carbon storage, carbon-sequestration capacities, and GHG emissions under the present conditions and future scenarios will be assessed using the LULC-change and ecosystem-disturbance estimates in map format with a spatially explicit biogeochemical ensemble modeling system that incorporates properties of management activities (such as tillage or harvesting) and properties of individual ecosystems (such as energy exchange, vegetation characteristics, hydrological cycling, and soil attributes). For aquatic ecosystems, carbon burial in sediments and fluxes of GHG are functions of the present and future potential stream flow and sediment transport and will be assessed using empirical hydrological modeling methods. Validation and uncertainty analysis methods described in the methodology will follow established guidelines to assess the quality of the assessment results. The U.S. Environmental Protection Agency’s Level II ecoregions map will be the practical instrument for developing and delivering assessment results. Consequently, the ecoregion (there are 22 modified ecoregions) will be the reporting unit of the assessment because the scenarios, assessment results, validation, and uncertainty analysis will be produced at that scale. The implementation of these methods will require collaborations among various Federal agencies, State agencies, nongovernmental organizations, and the science community. Using the method described in this document, the assessment can be completed in approximately 3 to 4 years. The primary deliverables will be assessment reports containing tables, charts, and maps that will present the estimated GHG parameters annually for 2001 through 2050 by ecosystem, pool, and scenario. The results will permit the evaluation of a range of policies, mitigation options, and research topics, such as the demographic, LULC-change, or climate-change effects on carbon stocks, carbon sequestration, and GHG fluxes in ecosystems.

Scientific Investigations Report↗

USGS2015

Using stable isotopes of carbon to investigate the seasonal variation of carbon transfer in a northwestern Arkansas cave

Stable-isotope analyses are valuable in karst settings, where characterizing biogeochemical cycling of carbon along groundwater flow paths is critical for understanding and protecting sensitive cave and karst water resources. This study quantified the seasonal changes in concentration and isotopic composition ( δ 13C) of aqueous and gaseous carbon species—dissolved inorganic carbon (DIC) and gaseous carbon dioxide (CO 2 )—to characterize sources and transfer of these species along a karst flow path, with emphasis on a cave environment. Gas and water samples were collected from the soil and a cave in northwestern Arkansas approximately once a month for one year to characterize carbon cycling along a conceptual groundwater flow path. In the soil, as the DIC concentration increased, the isotopic composition of the DIC became relatively lighter, indicating an organic carbon source for a component of the DIC and corroborating soil DIC as a proxy for soil respiration. In the cave, a positive correlation between DIC and surface temperature was due to increased soil respiration as the organic carbon signal from the soil was transferred to the cave environment via the aqueous phase. CO 2 concentration was lowest in the cave during colder months and increased exponentially with increasing surface temperature, presumably due to higher rates of soil respiration during warmer periods and changing ventilation patterns between the surface and cave atmosphere. Isotopic disequilibrium between CO 2 and DIC in the cave was greatest when CO 2 concentration was changing during November/ December and March/April, presumably due to the rapid addition or removal of gaseous CO 2 . The isotopic disequilibrium between DIC and CO 2 provided evidence that cave CO 2 was a mixture of carbon from several sources, which was mostly constrained by mixture between atmospheric CO 2 and soil CO 2 . The concentration and isotopic composition of gaseous and aqueous carbon species were controlled by month-to-month variations in temperature and precipitation and provided insight into the sources of carbon in the cave. Stable carbon isotope ratios provided an effective tool to explore carbon transfer from the soil zone and into the cave, identify carbon sources in the cave, and investigate how seasonality affected the transfer of carbon in a shallow karst system.

Journal of Cave and Karst Studies↗

USGS2011

Fish as major carbonate mud producers and missing components of the tropical carbonate factory

Carbonate mud is a major constituent of recent marine carbonate sediments and of ancient limestones, which contain unique records of changes in ocean chemistry and climate shifts in the geological past. However, the origin of carbonate mud is controversial and often problematic to resolve. Here we show that tropical marine fish produce and excrete various forms of precipitated (nonskeletal) calcium carbonate from their guts (“low” and “high” Mg-calcite and aragonite), but that very fine-grained (mostly < 2 μm) high Mg-calcite crystallites (i.e., MgCO 3 ) are their dominant excretory product. Crystallites from fish are morphologically diverse and species-specific, but all are unique relative to previously known biogenic and abiotic sources of carbonate within open marine systems. Using site specific fish biomass and carbonate excretion rate data we estimate that fish produce ∼6.1 × 10 6 kg CaCO 3 /year across the Bahamian archipelago, all as mud-grade (the < 63 μm fraction) carbonate and thus as a potential sediment constituent. Estimated contributions from fish to total carbonate mud production average ∼14% overall, and exceed 70% in specific habitats. Critically, we also document the widespread presence of these distinctive fish-derived carbonates in the finest sediment fractions from all habitat types in the Bahamas, demonstrating that these carbonates have direct relevance to contemporary carbonate sediment budgets. Fish thus represent a hitherto unrecognized but significant source of fine-grained carbonate sediment, the discovery of which has direct application to the conceptual ideas of how marine carbonate factories function both today and in the past.

Proceedings of the National Academy of Sciences of↗

USGS1982

Methodologies for extraction of dissolved inorganic carbon for stable carbon isotope studies: Evaluation and alternatives

The gas evolution and the strontium carbonate precipitation techniques to extract dissolved inorganic carbon (DIC) for stable carbon isotope analysis were investigated. Theoretical considerations, involving thermodynamic calculations and computer simulation pointed out several possible sources of error in delta carbon-13 measurements of the DIC and demonstrated the need for experimental evaluation of the magnitude of the error. An alternative analytical technique, equilibration with out-gassed vapor phase, is proposed. The experimental studies revealed that delta carbon-13 of the DIC extracted from a 0.01 molar NaHC03 solution by both techniques agreed within 0.1 per mil with the delta carbon-13 of the DIC extracted by the precipitation technique, and an increase of only 0.27 per mil in that extracted by the gas evolution technique. The efficiency of extraction of DIC decreased with sulfate concentration in the precipitation technique but was independent of sulfate concentration in the gas evolution technique. Both the precipitation and gas evolution technique were found to be satisfactory for extraction of DIC from different kinds of natural water for stable carbon isotope analysis, provided appropriate precautions are observed in handling the samples. For example, it was found that diffusion of atmospheric carbon dioxide does alter the delta carbon-13 of the samples contained in polyethylene bottles; filtration and drying in the air change the delta carbon-13 of the samples contained in polyethylene bottles; filtration and drying in the air change the delta carbon-13 of the precipitation technique; hot manganese dioxide purification changes the delta carbon-13 of carbon dioxide. (USGS)

Water-Resources Investigations Report↗

USGS2008

Carbonate precipitation by the thermophilic archaeon Archaeoglobus fulgidus: A model of carbon flow for an ancient microorganism

Microbial carbonate precipitation experiments were conducted using the archaeon bacteria Archaeoglobus fulgidus to determine chemical and isotopic fractionation of organic and inorganic carbon into mineral phases. Carbonate precipitation was induced in two different experiments using A. fulgidus to determine the relative abundance of organically derived carbon incorporated into carbonate minerals as well as to define any distinct phases or patterns that could be attributed to the precipitation process. One experiment used a medium containing 13C-depleted organic carbon and 13C-enriched inorganic carbon, and the other used a 14C-labeled organic carbon source. Results indicated that 0.9 - 24.8% organic carbon was incorporated into carbonates precipitated by A. fulgidus and that this process was mediated primarily by pH and CO2 emission from cells. Data showed that the carbon in the CO2 produced from this microorganism is incorporated into carbonates and that the rate at which precipitation occurs and the dynamics of the carbonate precipitation process are strongly mediated by the specific steps involved in the biochemical process for lactate oxidation by A. fulgidus.

Biogeosciences Discussions↗

USGS2024

Structure and morphology of chars and activated carbons obtained from thermal treatment of coal and biomass origin materials, including their wastes: Results from the ICCP Microscopy of Carbon Materials Working Group

This paper describes the evaluation of petrographic textures in char and activated carbon derived from coal, coal by-products and biomass, formed during carbonization and activation processes. This work represents the results of interlaboratory exercises from 2016 to 2022 of the Microscopy of Carbon Materials Working Group in Commission III of the International Committee for Coal and Organic Petrology. The interlaboratory exercises were run on photomicrograph samples. For textural characterization of carbon materials, the existing American Society for Testing and Materials (ASTM) classification system for metallurgical coke was applied. Morphological differences were evaluated in 29 carbon material types, including 22 char samples, and 7 activated carbon (AC) samples obtained experimentally using conventional direct/indirect and microwave heating technologies. This approach gives an extended view on the identification of microporous carbons, and how a certain heat treatment develops a certain optical texture and structure in a raw material. The requested evaluation of carbon materials was related to their porosity, origin, extent, and characteristics, which are particular to each carbon material type. Because carbon matrices can form a wide range of optical textures during heat treatment it is important to demonstrate which carbon occurrences will have a crucial role in industrial applications dominated by adsorption phenomena. The interlaboratory exercises included 17 participants from 14 laboratories. Four sets of digital black and white and colour photomicrographs were distributed, which in total comprised 184 fields of different types of carbon material. The results were evaluated based on four levels: (i) optical texture (isotropic/anisotropic), (ii) optical type and size (punctiform, mosaic, fiber, ribbon, domain), iii) morphology (porous, non-porous/massive), and (iv) particle origin (precursor type). The statistical method applied to evaluate the results was based on “raw agreement indices”. Comparative analyses of the average values of the level of overall agreement showed homogeneity in the results, the mean value was 89%, with a minimum value of 87% and a maximum value of 91% for those who participated in at least three out of four exercises.

International Journal of Coal Geology↗

USGS2012

Varve calibrated records of carbonate and organic carbon accumulation over the last 2000 years in the Black Sea

Sedimentologic and geochemical studies of box and gravity cores recovered from the Black Sea during the first leg of a multileg international Black Sea expedition in 1988 allow reconstruction of the basinwide Holocene environmental history of the Black Sea. In the deeper parts of the basin, box cores typically recovered a flocculent surface layer (“fluff”), laminated coccolith marls of Unit I (25–45 cm thick), and the upper 5–10 cm of finely laminated, dark‐colored sapropels of Unit II. Fine‐grained, homogeneous mud turbidites are interbedded with Units I and II over much of the basin, but the stratigraphie position of these turbidites differs, from site to site. The deposition of individual turbidites up to 15 cm thick does not appear to have significantly disturbed underlying laminae. Sediment trap deployments in the Black Sea suggest that light and dark laminae couplets represent annual increments of sedimentation (i.e., varves); we have therefore constructed a varve chronology for the sequence in order to correlate and date distinctive sedimentation and paleoenvironmental events. Distinctive groups of laminae in Unit I can be correlated across the entire deeper basin (a distance of more than 1000 km). This implies a remarkable homogeneity in production, accumulation, and preservation of biogenic material over much of the Black Sea during deposition of Unit I. The change from deposition of finely laminated, organic carbon‐rich sapropels (Unit II) to laminated, more calcareous, coccolith‐rich marls (Unit I) is thought to represent the crossing of a salinity threshold for Emiliania huxleyi. The varve chronology sets this change at about 1.63 ka (1633±100 yr B.P.), but the record of magnetic secular variation measured in several cores produces an age estimate of about 2.0 ka for the base of Unit I, or about 1.2 times the varve age. The average of six calibrated accelerator mass spectrometry radiocarbon ages for the base of Unit I is 2.7 ka, or about 1.7 times the varve age. Following the initial change to coccolith‐dominated sedimentation, deposition of sapropel resumed for at least one significant period, 1.56–1.25 ka. Since 1.25 ka, cycles of carbonate deposition with quasi‐decadal periodicities have produced characteristic darker and lighter assemblages of laminae. These cycles may have been climatically driven. Geochemical analyses coupled with the varve ages adopted herein indicate that accumulation rates of carbonate are nearly an order of magnitude higher in Unit I (averaging 35–45 g m −2 yr −1 ) than in sapropelic Unit II. which contains primarily detrital carbonate. The accumulation of lithogenic components in parts of Unit I is only 1.5 times the rate in Unit II. Deepwater organic carbon accumulation rates are somewhat higher in Unit I (3.5–4.5 g m −2 yr −1 ) than in the upper part of Unit II. Organic carbon accumulation rates in Unit I are somewhat antithetic to those of carbonate, and on the basis of this and additional constraints placed by pyrolysis and carbon isotopic analyses of organic material, it appears that terrestrial organic matter is an important component (perhaps >25%) of total organic carbon burial in the basin. Unit I in the western part of the Black Sea has a higher terrestrial organic component and higher accumulation rates of terrigenous clastic material than Unit I in the eastern part. This difference between eastern and western Black Sea is to be expected because of the major rivers that empty into the western Black Sea from eastern Europe, Ukraine, and Russia. Shallow slope sites, but still within euxinic bottom waters, have lower organic carbon accumulation rates and lower pyrolysis hydrogen indices than deepwater basinal sites, suggesting selective resuspension and oxidation of organic matter at basin margins and focusing of organic matter deposition toward the basin center. A comparison of the Black Sea data with those from several open ocean sites with similar water depths showed no significant difference between organic carbon accumulation rates under oxic and anoxic conditions. For a given bulk accumulation rate the organic carbon accumulation rates, normalized to primary productivity, are about the same in both settings.

Global Biogeochemical Cycles↗