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USGS2023

Equilibrated gas and carbonate standard-derived dual (Δ47 and Δ48) clumped isotope values

Carbonate clumped isotope geochemistry has primarily focused on mass spectrometric determination of m/z 47 CO 2 for geothermometry, but theoretical calculations and recent experiments indicate paired analysis of the m/z 47 ( 13 C 18 O 16 O) and m/z 48 ( 12 C 18 O 18 O) isotopologues (referred to as Δ 47 and Δ 48 ) can be used to study non-equilibrium isotope fractionations and refine temperature estimates. We utilize 5,448 Δ 47 and 3,400 Δ 48 replicate measurements of carbonate samples and standards, and 183 Δ 47 and 195 Δ 48 replicate measurements of gas standards from 2015 to 2021 from a multi-year and multi-instrument data set to constrain Δ 47 and Δ 48 values for 27 samples and standards, including Devils Hole cave calcite, and study equilibrium Δ 47 -Δ 48 , Δ 47 -temperature, and Δ 48 -temperature relationships. We compare results to previously published findings and calculate equilibrium regressions based on data from multiple laboratories. We report acid digestion fractionation factors, Δ* 63-47 and Δ* 64-48 , and account for their dependence on the initial clumped isotope values of the mineral.

Geochemistry, Geophysics, Geosystems↗

USGS2024

Spatial, seasonal, and diel controls of nitrogen-carbon-oxygen cycling during lake-water infiltration to an aquifer

Many freshwater lakes are groundwater flow-through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake-bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O 2 ), and dissolved organic carbon (DOC) during lake-water recharge from a groundwater flow-through lake. Lake-water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O 2 and DOC concentrations decreased with depth while nitrate (NO 3 − ) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO 3 − production and transport was seasonally dependent. In winter, NO 3 − and O 2 were exported beyond 100-cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO 3 − reduction zones, and diel patterns of O 2 and NO 3 − penetration depths were observed. Microbial community compositions and stable isotope profiles (δ 15 N[NO 3 − ], δ 18 O[NO 3 − ], δ 18 O[O 2 ]) were consistent with apparent C–N–O reaction stoichiometries indicating O 2 reduction and nitrification in shallower porewater, followed by varying NO 3 − reduction at depth. Maximum porewater NO 3 − concentrations (∼10–20 μM) were limited by infiltrating O 2 concentrations and C/N ratios of reacting organic matter. Lake-water level variations caused changes in shoreline position and porewater velocities, while variations in lake-water temperature, DOC, and O 2 contributed to changes in reaction rates and depth of O 2 and NO 3 − penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Journal of Geophysical Research: Biogeosciences↗

USGS2025

The North American greenhouse gas budget: Emissions, removals, and integration for CO2, CH4, and N2O (2010–2019): Results From the Second REgional Carbon Cycle Assessment and Processes Study (RECCAP2)

Accurate accounting of greenhouse-gas (GHG) emissions and removals is central to tracking progress toward climate mitigation and for monitoring potential climate-change feedbacks. GHG budgeting and reporting can follow either the Intergovernmental Panel on Climate Change methodologies for National Greenhouse Gas Inventory (NGHGI) reporting or use atmospheric-based “top-down” (TD) inversions or process-based “bottom-up” (BU) approaches. To help understand and reconcile these approaches, the Second REgional Carbon Cycle Assessment and Processes study (RECCAP2) was established to quantify GHG emissions and removals for carbon dioxide (CO 2 ), methane (CH 4 ) and nitrous oxide (N 2 O), for ten-land and five-ocean regions for 2010–2019. Here, we present the results for the North American land region (Canada, the United States, Mexico, Central America and the Caribbean). For 2010–2019, the NGHGI reported total net-GHG emissions of 7,270 TgCO 2 -eq yr −1 compared to TD estimates of 6,132 ± 1,846 TgCO 2 -eq yr −1 and BU estimates of 9,060 ± 898 TgCO 2 -eq yr −1 . Reconciling differences between the NGHGI, TD and BU approaches depended on (a) accounting for lateral fluxes of CO 2 along the land-ocean-aquatic continuum (LOAC) and trade, (b) correcting land-use CO 2 emissions for the loss-of-additional-sink capacity (LASC), (c) avoiding double counting of inland water CH 4 emissions, and (d) adjusting area estimates to match the NGHGI definition of the managed-land proxy. Uncertainties remain from inland-water CO 2 evasion, the conversion of nitrogen fertilizers to N 2 O, and from less-frequent NGHGI reporting from non-Annex-1 countries. The RECCAP2 framework plays a key role in reconciling independent GHG-reporting methodologies to support policy commitments while providing insights into biogeochemical processes and responses to climate change.

Global Biogeochemical Cycles↗

USGS2013

Variations in the global carbon cycle during the Cretaceous related to climate, volcanism, and changes in atmospheric CO2

The stratigraphic record from both deep-sea and shallow-water depositional environments indicates that during late Aptian through Cenomanian time (1) global climates were considerably warmer than at present; (2) latitudinal gradients of atmospheric and oceanic temperatures were considerably less than at present; (3) rates of accumulation of organic matter of both marine and terrestrial origin were as high as or higher than during any other interval in the Mesozoic or Cenozoic; (4) the rate and volume of accumulation of CaCO 3 in the deep sea were reduced in response to a marked shoaling of the carbonate compensation depth; (5) seafloor spreading rates were somewhat more rapid than at any other time in the Cretaceous or Cenozoic; (6) off-ridge volcanism was intense and widespread, particularly in the ancestral Pacific Ocean basin; and (7) sea level was relatively high, forming widespread areas of shallow shelf seas. A marked increase in the rate of CO 2 outgassing due to volcanic activity between about 110 and 70 m.y. ago may have resulted in a buildup of atmospheric CO 2. A significant fraction of this atmospheric CO 2 may have been reduced by an increase in the production and burial of terrestrial organic carbon. Some excess CO 2may have been consumed by marine algal photosynthesis, but marine productivity apparently was low during the Aptian-Albian relative to terrestrial productivity. Terrestrial productivity also may have been stimulated by increased rainfall that resulted 504 from a warm global climate and increased marine transgression as well as by the higher CO 2.

Book chapter↗

USGS2012

Tectonic relations of carbon dioxide discharges and earthquakes

CO 2 ‐rich springs occur worldwide along major zones of seismicity. They are mostly in young orogenic belts, but some are in areas of rifting continental platforms. Analyses of 13 C content indicate that much of the CO 2 is derived from the mantle and that other important sources are the metamorphism of marine carbonate‐bearing sedimentary rocks and the degradation of organic material. The presence of calc‐silicate minerals, such as pumpellyite in metagraywacke, is evidence of former conversion of carbonate‐bearing rocks into calc‐silicate minerals and release of CO 2 . The CO 2 pressure in fractured rocks of a fault zone reduces the effective normal stress and, if it is sufficiently great, allows the fault to slip. If the pressure were maintained at a sufficiently high level, the fault behavior might be characterized by frequent small earthquakes and aseismic creep such as occur along active segments of the San Andreas system. The presence of CO 2 ‐rich springs may indicate a potentially hazardous seismic region. Monitoring of CO 2 discharges could be useful in earthquake prediction.

Journal of Geophysical Research B: Solid Earth↗

USGS1981

Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

Previous interest in light hydrocarbons from geothermal systems has focused principally on the origin of the methane1 and the estimation of subsurface temperatures from the carbon isotopic content of coexisting methane and carbon dioxide1-3. Higher molecular weight hydrocarbons were first reported in gases from Yellowstone National Park4, and have since been found to occur commonly in geothermal emanations in the western United States5. Isotopic measurements of individual geothermal hydrocarbons are now reported which help to explain the origin of these hydrocarbons. The thermal decomposition of sedimentary or groundwater organic matter is a principal source of hydrocarbons in four geothermal areas in western North America. ?? 1981 Nature Publishing Group.

Nature↗

USGS1985

Anomalous 13C enrichment in modern marine organic carbon

Marine organic carbon is heavier isotopically (13C enriched) than most land-plant or terrestrial organic C1. Accordingly, ??13C values of organic C in modern marine sediments are routinely interpreted in terms of the relative proportions of marine and terrestrial sources of the preserved organic matter2,3. When independent geochemical techniques are used to evaluate the source of organic matter in Cretaceous or older rocks, those rocks containing mostly marine organic C are found typically to have lighter (more-negative) ??13C values than rocks containing mostly terrestrial organic C. Here we conclude that marine photosynthesis in mid-Cretaceous and earlier oceans generally resulted in a greater fractionation of C isotopes and produced organic C having lighter ??13C values. Modern marine photosynthesis may be occurring under unusual geological conditions (higher oceanic primary production rates, lower PCO2) that limit dissolved CO2 availability and minimize carbon isotope fractionation4. ?? 1985 Nature Publishing Group.

Nature↗

USGS1992

Revised budget for the oceanic uptake of anthropogenic carbon dioxide

Tracer-calibrated models of the total uptake of anthropogenic CO 2 by the world's oceans give estimates of about 2 gigatonnes carbon per year 1 , significantly larger than a recent estimate 2 of 0.3-0.8 Gt C yr -1 for the synoptic air-to-sea CO 2 influx. Although both estimates require that the global CO 2 budget must be balanced by a large unknown terrestrial sink, the latter estimate implies a much larger terrestrial sink, and challenges the ocean model calculations on which previous CO 2 budgets were based. The discrepancy is due in part to the net flux of carbon to the ocean by rivers and rain, which must be added to the synoptic air-to-sea CO 2 flux to obtain the total oceanic uptake of anthropogenic CO 2 . Here we estimate the magnitude of this correction and of several other recently proposed adjustments to the synoptic air-sea CO 2 exchange. These combined adjustments minimize the apparent inconsistency, and restore estimates of the terrestrial sink to values implied by the modelled oceanic uptake.

Nature↗

USGS2017

Organic carbon burial in global lakes and reservoirs

Burial in sediments removes organic carbon (OC) from the short-term biosphere-atmosphere carbon (C) cycle, and therefore prevents greenhouse gas production in natural systems. Although OC burial in lakes and reservoirs is faster than in the ocean, the magnitude of inland water OC burial is not well constrained. Here we generate the first global-scale and regionally resolved estimate of modern OC burial in lakes and reservoirs, deriving from a comprehensive compilation of literature data. We coupled statistical models to inland water area inventories to estimate a yearly OC burial of 0.15 (range, 0.06–0.25) Pg C, of which ~40% is stored in reservoirs. Relatively higher OC burial rates are predicted for warm and dry regions. While we report lower burial than previously estimated, lake and reservoir OC burial corresponded to ~20% of their C emissions, making them an important C sink that is likely to increase with eutrophication and river damming.

Nature Communications↗

USGS2023

Boreal conifers maintain carbon uptake with warming despite failure to track optimal temperatures

Warming shifts the thermal optimum of net photosynthesis ( T optA ) to higher temperatures. However, our knowledge of this shift is mainly derived from seedlings grown in greenhouses under ambient atmospheric carbon dioxide (CO 2 ) conditions. It is unclear whether shifts in T optA of field-grown trees will keep pace with the temperatures predicted for the 21 st century under elevated atmospheric CO 2 concentrations. Here, using a whole-ecosystem warming controlled experiment under either ambient or elevated CO 2 levels, we show that T optA of mature boreal conifers increased with warming. However, shifts in T optA did not keep pace with warming as T optA only increased by 0.26–0.35 °C per 1 °C of warming. Net photosynthetic rates estimated at the mean growth temperature increased with warming in elevated CO 2 spruce, while remaining constant in ambient CO 2 spruce and in both ambient CO 2 and elevated CO 2 tamarack with warming. Although shifts in T optA of these two species are insufficient to keep pace with warming, these boreal conifers can thermally acclimate photosynthesis to maintain carbon uptake in future air temperatures.

Nature Communciations↗

USGS2017

Restoring tides to reduce methane emissions in impounded wetlands: A new and potent Blue Carbon climate change intervention

Coastal wetlands are sites of rapid carbon (C) sequestration and contain large soil C stocks. Thus, there is increasing interest in those ecosystems as sites for anthropogenic greenhouse gas emission offset projects (sometimes referred to as “Blue Carbon”), through preservation of existing C stocks or creation of new wetlands to increase future sequestration. Here we show that in the globally-widespread occurrence of diked, impounded, drained and tidally-restricted salt marshes, substantial methane (CH 4 ) and CO 2 emission reductions can be achieved through restoration of disconnected saline tidal flows. Modeled climatic forcing indicates that tidal restoration to reduce emissions has a much greater impact per unit area than wetland creation or conservation to enhance sequestration. Given that GHG emissions in tidally-restricted, degraded wetlands are caused by human activity, they are anthropogenic emissions, and reducing them will have an effect on climate that is equivalent to reduced emission of an equal quantity of fossil fuel GHG. Thus, as a landuse-based climate change intervention, reducing CH 4 emissions is an entirely distinct concept from biological C sequestration projects to enhance C storage in forest or wetland biomass or soil, and will not suffer from the non-permanence risk that stored C will be returned to the atmosphere.

Scientific Reports↗

USGS2013

Forest cutting and impacts on carbon in the eastern United States

Forest cutting is a major anthropogenic disturbance that affects forest carbon (C) storage and fluxes. Yet its characteristics and impacts on C cycling are poorly understood over large areas. Using recent annualized forest inventory data, we estimated cutting-related loss of live biomass in the eastern United States was 168 Tg C yr −1 from 2002 to 2010 (with C loss per unit forest area of 1.07 Mg ha −1 yr −1 ), which is equivalent to 70% of the total U.S. forest C sink or 11% of the national annual CO 2 emissions from fossil-fuel combustion over the same period. We further revealed that specific cutting-related C loss varied with cutting intensities, forest types, stand ages, and geographic locations. Our results provide new insights to the characteristics of forest harvesting activities in the eastern United States and highlight the significance of partial cutting to regional and national carbon budgets.

Scientific Reports↗

USGS2019

Radium accumulation in carbonate river sediments at oil and gas produced water discharges: Implications for beneficial use as disposal management

In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering. Here we investigate six permitted discharges on three neighboring tributary systems in Wyoming. During 2013-16, we evaluated radium activities of the permitted discharges and the potential for radium accumulation in associated stream sediments. Radium activities of the sediments at the points of discharge ranged from approximately 200-3600 Bq/kg with elevated activities above the background of 74 Bq/kg over 30 km downstream of one permitted discharge. Sediment as deep as 30 cm near the point of discharge had radium activities elevated above background. X-ray diffraction and targeted sequential extraction of radium in sediments indicate that radium is likely coprecipitated with carbonate, and to a lesser extent sulfate minerals. PHREEQC modeling predicts radium coprecipitation with aragonite and barite, but over-estimates the latter compared to observations of downstream sediment, where carbonate predominates. Mass-balance calculations indicate over 3 billion Bq of radium activity (226Ra+228Ra) is discharged each year from five of the discharges, combined, with only 5 percent of the annual load retained in stream sediments within 100m of the effluent discharges; the remaining 95 percent of the radium is transported farther downstream as sediment-associated and aqueous species

Environmental Science↗

USGS2015

Ecosystem carbon stocks and sequestration potential of federal lands across the conterminous United States

Federal lands across the conterminous United States (CONUS) account for 23.5% of the CONUS terrestrial area but have received no systematic studies on their ecosystem carbon (C) dynamics and contribution to the national C budgets. The methodology for US Congress-mandated national biological C sequestration potential assessment was used to evaluate ecosystem C dynamics in CONUS federal lands at present and in the future under three Intergovernmental Panel on Climate Change Special Report on Emission Scenarios (IPCC SRES) A1B, A2, and B1. The total ecosystem C stock was estimated as 11,613 Tg C in 2005 and projected to be 13,965 Tg C in 2050, an average increase of 19.4% from the baseline. The projected annual C sequestration rate (in kilograms of carbon per hectare per year) from 2006 to 2050 would be sinks of 620 and 228 for forests and grasslands, respectively, and C sources of 13 for shrublands. The federal lands’ contribution to the national ecosystem C budget could decrease from 23.3% in 2005 to 20.8% in 2050. The C sequestration potential in the future depends not only on the footprint of individual ecosystems but also on each federal agency’s land use and management. The results presented here update our current knowledge about the baseline ecosystem C stock and sequestration potential of federal lands, which would be useful for federal agencies to decide management practices to achieve the national greenhouse gas (GHG) mitigation goal.

PNAS↗

USGS2020

Large stocks of peatland carbon and nitrogen are vulnerable to permafrost thaw

Over many millennia, northern peatlands have accumulated large amounts of carbon and nitrogen, thus cooling the global climate. Over shorter timescales, peatland disturbances can trigger losses of peat and release of greenhouses gases. Despite their importance to the global climate, peatlands remain poorly mapped, and the vulnerability of permafrost peatlands to warming is uncertain. This study compiles over 7,000 field observations to present a data-driven map of northern peatlands and their carbon and nitrogen stocks. We use these maps to model the impact of permafrost thaw on peatlands and find that warming will likely shift the greenhouse gas balance of northern peatlands. At present, peatlands cool the climate, but anthropogenic warming can shift them into a net source of warming.

Proceedings of the National Academy of Sciences↗

USGS2016

Multi-decadal increases in dissolved organic carbon and alkalinity flux from the Mackenzie drainage basin to the Arctic Ocean

Riverine exports of organic and inorganic carbon (OC, IC) to oceans are intricately linked to processes occurring on land. Across high latitudes, thawing permafrost, alteration of hydrologic flow paths, and changes in vegetation may all affect this flux, with subsequent implications for regional and global carbon (C) budgets. Using a unique, multi-decadal dataset of continuous discharge coupled with water chemistry measurements for the Mackenzie River, we show major increases in dissolved OC (DOC) and IC (as alkalinity) fluxes since the early 1970s, for a watershed that covers 1.8 M km 2 of northwestern Canada, and provides substantial inputs of freshwater and biogeochemical constituents to the Arctic Ocean. Over a 39-year period of record, DOC flux at the Mackenzie mouth increased by 39.3% (44.5 ± 22.6 Gmol), while alkalinity flux increased by 12.5% (61.5 ± 60.1 Gmol). Isotopic analyses and substantial increases in sulfate flux indicate that increases in alkalinity are driven by accelerating sulfide oxidation, a process that liberates IC from rock and soils in the absence of CO 2 consumption. Seasonal and sub-catchment trends suggest that permafrost thaw plays an important role in the observed increases in DOC and alkalinity: sub-catchment increases for all constituents are confined to northern, permafrost-affected regions, while observed increases in autumn to winter are consistent with documented landscape-scale changes that have resulted from changing thaw dynamics. This increase in DOC and sulfide-derived alkalinity represents a substantial intensification of land-to-ocean C mobilization, at a level that is significant within the regional C budget. The change we observe, for example, is similar to current and projected future rates of CO 2 consumption by weathering in the Mackenzie basin.

Environmental Research Letters↗

USGS2018

Dissolved organic carbon and nitrogen release from boreal Holocene permafrost and seasonally frozen soils of Alaska

Permafrost (perennially frozen) soils store vast amounts of organic carbon (C) and nitrogen (N) that are vulnerable to mobilization as dissolved organic carbon (DOC) and dissolved organic and inorganic nitrogen (DON, DIN) upon thaw. Such releases will affect the biogeochemistry of permafrost regions, yet little is known about the chemical composition and source variability of active-layer (seasonally frozen) and permafrost soil DOC, DON and DIN. We quantified DOC, total dissolved N (TDN), DON, and DIN leachate yields from deep active-layer and near-surface boreal Holocene permafrost soils in interior Alaska varying in soil C and N content and radiocarbon age to determine potential release upon thaw. Soil cores were collected at three sites distributed across the Alaska boreal region in late winter, cut in 15 cm thick sections, and deep active-layer and shallow permafrost sections were thawed and leached. Leachates were analyzed for DOC, TDN, nitrate (NO 3 − ), and ammonium (NH 4 + ) concentrations, dissolved organic matter optical properties, and DOC biodegradability. Soils were analyzed for C, N, and radiocarbon ( 14 C) content. Soil DOC, TDN, DON, and DIN yields increased linearly with soil C and N content, and decreased with increasing radiocarbon age. These relationships were significantly different for active-layer and permafrost soils such that for a given soil C or N content, or radiocarbon age, permafrost soils released more DOC and TDN (mostly as DON) per gram soil than active-layer soils. Permafrost soil DOC biodegradability was significantly correlated with soil Δ 14 C and DOM optical properties. Our results demonstrate that near-surface Holocene permafrost soils preserve greater relative potential DOC and TDN yields than overlying seasonally frozen soils that are exposed to annual leaching and decomposition. While many factors control the fate of DOC and TDN, the greater relative yields from newly thawed Holocene permafrost soils will have the largest potential impact in areas dominated by organic-rich soils.

Alaska↗

USGS2025

Carbon and nitrogen isotopes of different native fish tissues from the Santa Ana River, California

Objective Stable isotopes are commonly used to understand the role of fishes in aquatic food webs. However, variability in species- and tissue-specific isotopic values can affect the inference that is drawn from a stable isotope study. We evaluated differences in stable isotopes of carbon (δ 13 C) and nitrogen (δ 15 N) among three tissue types (white muscle, caudal fin rays, and eye lenses) for Santa Ana Sucker Pantosteus santaanae and Arroyo Chub Gila orcuttii to inform the design of a stable isotope study in the Santa Ana River, an urban river that is located in southern California. Methods We used multivariate analyses to test for differences in the stable isotopes of carbon (δ 13 C) and nitrogen (δ 15 N) among the three tissue types that were collected from Santa Ana Sucker and Arroyo Chub. We also summarized the variability in isotopic values that was recorded over time in fish eye lenses and interpreted this variability in reference to the spatial patterns in isotopic values that have been previously reported throughout the Santa Ana River. Results We found that fin ray tissue and white muscle tissue were not significantly different for either isotope or fish species. Fish eye lenses were significantly higher in δ 13 C than muscle tissue, and eye lenses were significantly higher in δ 15 N than fin ray tissue for both fishes. We also found a greater range in δ 13 C and δ 15 N across eye lens layers for Santa Ana Sucker (δ 13 C = 2.01 ± 0.96‰, δ 15 N = 4.93 ± 4.18‰) than for Arroyo Chub (δ 13 C = 0.96 ± 0.65‰, δ 15 N = 4.63 ± 1.45‰). Conclusion Our results indicate that fin rays may be a viable nonlethal alternative to white muscle tissue for use in a stable isotope study of native fish of the Santa Ana River. Additionally, eye lenses could provide a chemical history of fishes within the river, but species-specific correction factors may be needed if stable isotope values for eye lenses are to be compared with more conventional tissue types (e.g., white muscle).

California↗