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USGS2011

Applying monitoring, verification, and accounting techniques to a real-world, enhanced oil recovery operational CO2 leak

The use of carbon dioxide (CO 2 ) for enhanced oil recovery (EOR) is being tested for oil fields in the Illinois Basin, USA. While this technology has shown promise for improving oil production, it has raised some issues about the safety of CO 2 injection and storage. The Midwest Geological Sequestration Consortium (MGSC) organized a Monitoring, Verification, and Accounting (MVA) team to develop and deploy monitoring programs at three EOR sites in Illinois, Indiana, and Kentucky, USA. MVA goals include establishing baseline conditions to evaluate potential impacts from CO 2 injection, demonstrating that project activities are protective of human health and the environment, and providing an accurate accounting of stored CO 2 . This paper focuses on the use of MVA techniques in monitoring a small CO 2 leak from a supply line at an EOR facility under real-world conditions. The ability of shallow monitoring techniques to detect and quantify a CO 2 leak under real-world conditions has been largely unproven. In July of 2009, a leak in the pipe supplying pressurized CO 2 to an injection well was observed at an MGSC EOR site located in west-central Kentucky. Carbon dioxide was escaping from the supply pipe located approximately 1 m underground. The leak was discovered visually by site personnel and injection was halted immediately. At its largest extent, the hole created by the leak was approximately 1.9 m long by 1.7 m wide and 0.7 m deep in the land surface. This circumstance provided an excellent opportunity to evaluate the performance of several monitoring techniques including soil CO 2 flux measurements, portable infrared gas analysis, thermal infrared imagery, and aerial hyperspectral imagery. Valuable experience was gained during this effort. Lessons learned included determining (1) hyperspectral imagery was not effective in detecting this relatively small, short-term CO 2 leak, (2) even though injection was halted, the leak remained dynamic and presented a safety risk concern during monitoring activities and, (3) the atmospheric and soil monitoring techniques used were relatively cost-effective, easily and rapidly deployable, and required minimal manpower to set up and maintain for short-term assessments. However, characterization of CO 2 distribution near the land surface resulting from a dynamic leak with widely variable concentrations and fluxes was challenging.

Illinois, Indiana, and Kentucky↗

USGS2026

VegET evapotranspiration for Africa: Continental-scale simulation, multi-product evaluation, and drought assessment

Study region Continental Africa, encompassing diverse climatic zones—tropical, arid, and temperate—and spanning major transboundary river basins such as the Nile, Niger, Congo, Volta, and Zambezi River Basins. The region exhibits pronounced hydroclimatic gradients and heterogeneous land use systems ranging from rainfed croplands and rangelands to dense tropical forests and irrigated schemes. Study focus Actual evapotranspiration (ETa) is a central component of the terrestrial water balance, governing the redistribution of water and energy between the land surface and the atmosphere. Accurate estimation of ETa at continental scale is critical for hydrological monitoring, water resource management, and climate adaptation, as well as for quantifying water, energy, and carbon fluxes that underpin sustainable development. In this study, we applied the agro-hydrologic VegET v2 model to simulate a new, high-resolution, continental-scale ETa dataset for Africa (2000–2021). The model results were benchmarked against four widely used remote sensing-based products—MODIS16 v6.1, SSEBop v6.1, WaPOR v3, and GLEAM v4.1a—across major climate zones, land use types, and River Basins, providing a comprehensive multi-product evaluation of evapotranspiration dynamics across the continent. New hydrological insights for the region Validation against eddy covariance flux tower observations at eight representative sites confirmed that VegET v2 accurately reproduces the seasonal dynamics of observed ETa, achieving a correlation (r) of 0.8 and an RMSE of 25 mm month⁻¹ —accuracy that is comparable to or higher than accuracies of satellite-based products MODIS16, SSEBop, and GLEAM. This study represents one of the first Africa-wide hydrological simulations of ETa, extending the VegET model beyond basin-scale applications. Intercomparisons reveal that VegET aligns closely with MODIS16, SSEBop, and GLEAM in humid and tropical regions (r = 0.80–0.90; RMSE < 20 mm month⁻¹), while greater discrepancies appear in arid and semi-arid zones, where WaPOR tends to overestimate ETa (RMSE ≥ 28 mm month⁻¹). Despite these differences, VegET effectively captures spatial and temporal ETa variability across rainfed croplands, forests, and savannas, supporting its utility in regional water balance assessments, water accounting, and drought monitoring. A key application of VegET v2 is the Evapotranspiration Deficit Index (ETDI), derived by integrating VegET-based ETa with potential evapotranspiration (PET) to quantify water stress. ETDI successfully captured major drought episodes across Africa, including persistent Sahelian and southern African dry spells, the 2020–2021 winter drought in the Maghreb, and the 2018–2019 austral summer drought in southern Africa, while identifying positive anomalies over central Africa indicative of recurrent wetness. These results underscore VegET’s capability as a hydrologically consistent, operational tool for continental ETa monitoring and drought assessment, offering support for basin-scale water balance studies, food security planning, and climate resilience across Africa’s diverse hydrological environments.

Journal of Hydrology: Regional Studies↗

USGS2005

Seasonal exposures to triazine and other pesticides in surface waters in the western Highveld corn-production region in South Africa

The objective of this study was to characterize concentrations of atrazine, terbuthylazine, and other pesticides in amphibian habitats in surface waters of a corn-production area of the western Highveld region (North-West Province) of South Africa. The study was conducted from November 2001 to June 2002, coinciding with the corn-production season. Pesticide residues were measured at regular intervals in surface water from eight ponds, three in a non-corn-growing area (NCGA) and five within the corn-growing area (CGA). Measured atrazine concentrations differed significantly among sites and between samples. In the five CGA sites, the maximum atrazine concentrations measured during the study ranged from 1.2 to 9.3 ??g/L. Although no atrazine was recorded as being applied in the catchment of the three NCGA sites, maximum concentrations from 0.39 to 0.84 ??g/L were measured during the study, possibly as a result of atmospheric transport. Maximum measured concentrations of terbuthylazine ranged from 1.22 to 2.1 ??g/L in the NCGA sites and from 1.04 to 4.1 ??g/L in the CGA sites. The source of terbuthylazine in the NCGA sites may have been in use other than in corn. The triazine degradation products, deisopropylatrazine (DIA) and deethylatrazine (DEA) and diaminochlorotriazine (DACT) were also found in water from both the CGA and NCGA sites. Concentrations of DIA were ??? 1 ??g/L throughout the season, while DEA concentrations were mostly <0.5 ??g/L before planting but increased after planting and application of herbicides to concentrations > 2 ??g/L in some locations. Concentrations of DACT were highly variable (LOD to 8 ??g/L) both before and after planting and application, suggesting that they resulted from historical use of triazines in the area. Other herbicides such as simazine and acetochlor were only detected infrequently and pesticides such as S-metolachlor, cypermethrin, monocrotophos, and terbuphos, known to be used in the CGA, were not detected in any of the samples. Because of dilution by higher than normal rainfall in the study period, these concentrations may not be predictive of those in years of normal rainfall. ?? 2004 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

USGS2008

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region

Environmental Pollution↗

USGS2011

Changes in the chemistry of acidified Adirondack streams from the early 1980s to 2008

Lakes in the Adirondack region of New York have partially recovered in response to declining deposition, but information on stream recovery is limited. Here we report results of Adirondack stream monitoring from the early 1980s to 2008. Despite a 50% reduction in atmospheric deposition of sulfur, overall increases in pH of only 0.28 and ANC of 13 μeq L −1 were observed in 12 streams over 23 years, although greater changes did occur in streams with lower initial ANC, as expected. In the North Tributary of Buck Creek with high dissolved organic carbon (DOC) concentrations, SO 4 2 − "> SO42− concentrations decreased from 1999 to 2008 at a rate of 2.0 μmol L −1 y −1 , whereas in the neighboring South Tributary with low DOC concentrations, the decrease was only 0.73 μmol L −1 y −1 . Ca 2+ leaching decreased in the North Tributary due to the SO 4 2 − "> SO42− decrease, but this was partially offset by an increase in Ca 2+ leaching from increased DOC concentrations.

New York↗

USGS2014

Spatial distribution of mercury in southeastern Alaskan streams influenced by glaciers, wetlands, and salmon

Southeastern Alaska is a remote coastal-maritime ecosystem that is experiencing increased deposition of mercury (Hg) as well as rapid glacier loss. Here we present the results of the first reported survey of total and methyl Hg (MeHg) concentrations in regional streams and biota. Overall, streams draining large wetland areas had higher Hg concentrations in water, mayflies, and juvenile salmon than those from glacially-influenced or recently deglaciated watersheds. Filtered MeHg was positively correlated with wetland abundance. Aqueous Hg occurred predominantly in the particulate fraction of glacier streams but in the filtered fraction of wetland-rich streams. Colonization by anadromous salmon in both glacier and wetland-rich streams may be contributing additional marine-derived Hg. The spatial distribution of Hg in the range of streams presented here shows that watersheds are variably, yet fairly predictably, sensitive to atmospheric and marine inputs of Hg.

Alaska↗

USGS2014

Effects of urbanization on mercury deposition and accumulation in New England

We compare total mercury (HgT) loading and methylmercury (MeHg) accumulation in streams and lakes from an urbanized area (Boston, Massachusetts) to rural regions of southern New Hampshire and Maine. The maximum HgT loading, as indicated by HgT atmospheric deposition, HgT emissions, and sediment HgT concentrations, did not coincide with maximum MeHg concentrations in fish. Urbanized ecosystems were areas of high HgT loading but had low MeHg concentrations in fish. Controls on MeHg production and accumulation appeared to be related primarily to HgT loading in undeveloped areas, while ecosystem sensitivity to MeHg formation appeared to be more important in regulating accumulation of MeHg in the urban area.

Connecticut, Maine, Massachusetts, New Hampshire, ↗

USGS2016

Conifer density within lake catchments predicts fish mercury concentrations in remote subalpine lakes

Remote high-elevation lakes represent unique environments for evaluating the bioaccumulation of atmospherically deposited mercury through freshwater food webs, as well as for evaluating the relative importance of mercury loading versus landscape influences on mercury bioaccumulation. The increase in mercury deposition to these systems over the past century, coupled with their limited exposure to direct anthropogenic disturbance make them useful indicators for estimating how changes in mercury emissions may propagate to changes in Hg bioaccumulation and ecological risk. We evaluated mercury concentrations in resident fish from 28 high-elevation, sub-alpine lakes in the Pacific Northwest region of the United States. Fish total mercury (THg) concentrations ranged from 4 to 438 ng/g wet weight, with a geometric mean concentration (±standard error) of 43 ± 2 ng/g ww. Fish THg concentrations were negatively correlated with relative condition factor, indicating that faster growing fish that are in better condition have lower THg concentrations. Across the 28 study lakes, mean THg concentrations of resident salmonid fishes varied as much as 18-fold among lakes. We used a hierarchal statistical approach to evaluate the relative importance of physiological, limnological, and catchment drivers of fish Hg concentrations. Our top statistical model explained 87% of the variability in fish THg concentrations among lakes with four key landscape and limnological variables: catchment conifer density (basal area of conifers within a lake's catchment), lake surface area, aqueous dissolved sulfate, and dissolved organic carbon. Conifer density within a lake's catchment was the most important variable explaining fish THg concentrations across lakes, with THg concentrations differing by more than 400 percent across the forest density spectrum. These results illustrate the importance of landscape characteristics in controlling mercury bioaccumulation in fish.

Environmental Pollution↗

USGS2020

Low O2 level enhances CH4-derived carbon flow into microbial communities in landfill cover soils

CH 4 oxidation in landfill cover soils plays a significant role in mitigating CH 4 release to the atmosphere. Oxygen availability and the presence of co-contaminants are potentially important factors affecting CH 4 oxidation rate and the fate of CH 4 -derived carbon. In this study, microbial populations that oxidize CH 4 and the subsequent conversion of CH 4 -derived carbon into CO 2 , soil organic C and biomass C were investigated in landfill cover soils at two O 2 tensions, i.e., O 2 concentrations of 21% (“sufficient”) and 2.5% (“limited”) with and without toluene. CH 4 -derived carbon was primarily converted into CO 2 and soil organic C in the landfill cover soils, accounting for more than 80% of CH 4 oxidized. Under the O 2 -sufficient condition, 52.9%–59.6% of CH 4 -derived carbon was converted into CO 2 (CE CO2-C ), and 29.1%–39.3% was converted into soil organic C (CE organic-C ). A higher CE organic-C and lower CE CO2-C occurred in the O 2 -limited environment, relative to the O 2 -sufficient condition. With the addition of toluene, the carbon conversion efficiency of CH 4 into biomass C and organic C increased slightly, especially in the O 2 -limited environment. A more complex microbial network was involved in CH 4 assimilation in the O 2 -limited environment than under the O 2 -sufficient condition. DNA-based stable isotope probing of the community with 13 CH 4 revealed that Methylocaldum and Methylosarcina had a higher relative growth rate than other type I methanotrophs in the landfill cover soils, especially at the low O 2 concentration, while Methylosinus was more abundant in the treatment with both the high O 2 concentration and toluene. These results indicated that O 2 -limited environments could prompt more CH 4 -derived carbon to be deposited into soils in the form of biomass C and organic C, thereby enhancing the contribution of CH 4 -derived carbon to soil community biomass and functionality of landfill cover soils (i.e. reduction of CO 2 emission).

Environmental Pollution↗

USGS2021

Surface-air mercury fluxes and a watershed mass balance in forested and harvested catchments

Forest soils are among the world’s largest repositories for long-term accumulation of atmospherically deposited mercury (Hg), and understanding the potential for remobilization through gaseous emissions, aqueous dissolution and runoff, or erosive particulate transport to down-gradient aquatic ecosystems is critically important for projecting ecosystem recovery. Forestry operations, especially clear-cut logging where most of the vegetaiton is removed, can influence Hg mobility/fluxes, foodweb dynamics, and bioaccumulation processes. This paper measured surface-air Hg fluxes from catchments in the Pacific Northwest, USA, to determine if there is a difference between forested and logged catchments. These measurements were conducted as part of a larger project on the impact of forestry operations on Hg cycling which include measurements of water fluxes as well as impacts on biota. Surface-air Hg fluxes were measured using a commonly applied dynamic flux chamber (DFC) method that incorporated diel and seasonal variability in elemental Hg (Hg 0 ) fluxes at multiple forested and harvested catchments. The results showed that the forested ecosystem had depositional Hg 0 fluxes throughout most of the year (annual mean: −0.26 ng/m 2 /h). In contrast, the harvested catchments showed mostly emission of Hg 0 (annual mean: 0.63 ng/m 2 /h). Differences in solar radiation reaching the soil was the primary driver resulting in a shift from net deposition to emission in harvested catchments. The surface-air Hg fluxes were larger than the fluxes to water as runoff and accounted for 97% of the differences in Hg sequestered in forested versus harvested catchments.

Oregon↗

USGS2006

Cosmogenic 3He production rates revisited from evidences of grain size dependent release of matrix-sited helium

Measurements of the cosmogenic 3 He ( 3 He c ) content of various size aliquots of exposed olivines show that the fine fraction (<140 μm) has 3 He c concentrations between 14 and 100% lower than that of the coarse fractions (0.14–1 mm). Such differences attest to a grain size dependent partial release of 3 He c from the phenocrysts matrix during the preliminary in vacuo crushing. This result might have important implications since most 3 He c measurements have used for ∼20 yr a standard routine based on the fusion of bulk powdered phenocrysts, whatever their grain size. A suite of new data obtained from coarse olivine grains yielded a mean Sea Level High Latitude 3 He c production rate (SLHL P 3 ) of 128±5 and 136±6 at. g −1 yr −1 , depending on the scaling factors used. This new value, which is ∼15% higher than previously published rates, is obtained from 5 ropy flow surfaces of Mt Etna (38°N) and Hawaiian (19°N) volcanoes, at elevations between sea level and 870 m and ranging in age from 1.47±0.05 to 149±23 ka according to independent 14 C or K/Ar dating. 3 He loss during the crushing step might account for the discrepancy between the standard reference value of 110–115 at. g −1 y −1 and the higher SLHL P 3 proposed here. More generally, removal of the powdered fraction before fusion is an important point to consider in further studies in order to avoid any 3 He c systematic underestimates. An altitudinal section has also been sampled on the ropy surface of a ∼1500 yr single flow of Mauna Loa (19°N) which allowed a new empirical atmospheric attenuation length of 149±22 g cm −2 to be documented for 3 He c in olivines between 2400 and 4000 m elevations.

Earth and Planetary Science Letters↗

USGS2008

Isotope geochemistry of mercury in source rocks, mineral deposits and spring deposits of the California Coast Ranges, USA

We present here the first study of the isotopic composition of mercury in rocks, ore deposits, and active spring deposits from the California Coast Ranges, a part of Earth's crust with unusually extensive evidence of mercury mobility and enrichment. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of mercury deposits, hot-spring deposits that form at shallow depths (< 300??m) and silica-carbonate deposits that extend to depths of 1000??m. Active springs and geothermal areas continue to precipitate Hg and Au and are modern analogues to the fossil hydrothermal systems preserved in the ore deposits. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of mercury than volcanic rocks of the Clear Lake Volcanic Field. Mean mercury isotopic compositions (??202Hg) for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate mercury deposits have similar average mercury isotopic compositions that are indistinguishable from averages for the three rock units, although ??202Hg values for the mercury deposits have a greater variance than the country rocks. Precipitates from spring and geothermal waters in the area have similarly large variance and a mean ??202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate that there is little or no isotopic fractionation (< ?? 0.5???) during release of mercury from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of mercury in deposits, however, especially in their uppermost parts. Boiling of hydrothermal fluids, separation of a mercury-bearing CO2 vapor or reduction and volatilization of Hg(0) in the near-surface environment are likely the most important processes causing the observed Hg isotope fractionation. This should result in the release of mercury with low ??202Hg values into the atmosphere from the top of these hydrothermal systems. Estimates of mass balance suggest that residual Hg reservoirs are not measurably enriched in heavy Hg isotopes as a result of this process because only a small amount of Hg (< 4%) leaves actively ore-forming systems. ?? 2008 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS2009

Environmental influences on speleothem growth in southwestern Oregon during the last 380, 000 years

The growth of carbonate formations in caves (speleothems) is sensitive to changes in environmental conditions at the surface (temperature, precipitation and vegetation) and can provide useful paleoclimatic and paleoenvironmental information. We use 73 230 Th dates from speleothems collected from a cave in southwestern Oregon (USA) to constrain speleothem growth for the past 380 000 years. Most speleothem growth occurred during interglacial periods, whereas little growth occurred during glacial intervals. To evaluate potential environmental controls on speleothem growth we use two new modeling approaches: i) a one-dimensional thermal advection–diffusion model to estimate cave temperatures during the last glacial cycle, and ii) a regional climate model simulation for the Last Glacial Maximum (21 000 years before present) that assesses a range of potential controls on speleothem growth under peak glacial conditions. The two models are mutually consistent in indicating that permafrost formation did not influence speleothem growth during glacial periods. Instead, the regional climate model simulation combined with proxy data suggest that the influence of the Laurentide and Cordilleran ice sheets on atmospheric circulation induced substantial changes in water balance in the Pacific Northwest and affected speleothem growth at our location. The overall drier conditions during glacial intervals and associated periods of frozen topsoil at times of maximum surface runoff likely induced drastic changes in cave recharge and limited speleothem growth. This mechanism could have affected speleothem growth in other mid-latitude caves without requiring the presence of permafrost.

Oregon↗

USGS2010

On the nature of the dirty ice at the bottom of the GISP2 ice core

We present data on the triple Ar isotope composition in trapped gas from clean, stratigraphically disturbed ice between 2800 and 3040m depth in the GISP2 ice core, and from basal dirty ice from 3040 to 3053m depth. We also present data for the abundance and isotopic composition of O 2 and N 2 , and abundance of Ar, in the basal dirty ice. The Ar/N 2 ratio of dirty basal ice, the heavy isotope enrichment (reflecting gravitational fractionation), and the total gas content all indicate that the gases in basal dirty ice originate from the assimilation of clean ice of the overlying glacier, which comprises most of the ice in the dirty bottom layer. O 2 is partly to completely depleted in basal ice, reflecting active metabolism. The gravitationally corrected ratio of 40 Ar/ 38 Ar, which decreases with age in the global atmosphere, is compatible with an age of 100-250ka for clean disturbed ice. In basal ice, 40 Ar is present in excess due to injection of radiogenic 40Ar produced in the underlying continental crust. The weak depth gradient of 40 Ar in the dirty basal ice, and the distribution of dirt, indicate mixing within the basal ice, while various published lines of evidence indicate mixing within the overlying clean, disturbed ice. Excess CH 4 , which reaches thousands of ppm in basal dirty ice at GRIP, is virtually absent in overlying clean disturbed ice, demonstrating that mixing of dirty basal ice into the overlying clean ice, if it occurs at all, is very slow. Order-of-magnitude estimates indicate that the mixing rate of clean ice into dirty ice is sufficient to maintain a steady thickness of dirty ice against thinning from the mean ice flow. The dirty ice appears to consist of two or more basal components in addition to clean glacial ice. A small amount of soil or permafrost, plus preglacial snow, lake or ground ice could explain the observations.

Earth and Planetary Science Letters↗

USGS2012

On the causes of mid-Pliocene warmth and polar amplification

The mid-Pliocene (~ 3 to 3.3 Ma ago), is a period of sustained global warmth in comparison to the late Quaternary (0 to ~ 1 Ma ago), and has potential to inform predictions of long-term future climate change. However, given that several processes potentially contributed, relatively little is understood about the reasons for the observed warmth, or the associated polar amplification. Here, using a modelling approach and a novel factorisation method, we assess the relative contributions to mid-Pliocene warmth from: elevated CO 2 , lowered orography, and vegetation and ice sheet changes. The results show that on a global scale, the largest contributor to mid-Pliocene warmth is elevated CO 2 . However, in terms of polar amplification, changes to ice sheets contribute significantly in the Southern Hemisphere, and orographic changes contribute significantly in the Northern Hemisphere. We also carry out an energy balance analysis which indicates that that on a global scale, surface albedo and atmospheric emmissivity changes dominate over cloud changes. We investigate the sensitivity of our results to uncertainties in the prescribed CO 2 and orographic changes, to derive uncertainty ranges for the various contributing processes.

Earth and Planetary Science Letters↗

USGS2014

Crustal migration of CO2-rich magmatic fluids recorded by tree-ring radiocarbon and seismicity at Mammoth Mountain, CA, USA

Unrest at Mammoth Mountain over the past several decades, manifest by seismicity, ground deformation, diffuse CO 2 emissions, and elevated 3 He/ 4 He ratios in fumarolic gases has been driven by the release of CO 2 -rich fluids from basaltic intrusions in the middle to lower crust. Recent unrest included the occurrence of three lower-crustal (32–19 km depth) seismic swarms beneath Mammoth Mountain in 2006, 2008 and 2009 that were consistently followed by peaks in the occurrence rate of shallow (≤10 km depth) earthquakes. We measured 14 C in the growth rings (1998–2012) of a tree growing in the largest (∼0.3 km 2 ) area of diffuse CO 2 emissions on Mammoth Mountain (the Horseshoe Lake tree kill; HLTK) and applied atmospheric CO 2 concentration source area modeling to confirm that the tree was a reliable integrator of magmatic CO 2 emissions over most of this area. The tree-ring 14 C record implied that magmatic CO 2 emissions from the HLTK were relatively stable from 1998 to 2009, nearly doubled from 2009 to 2011, and then declined by the 2012 growing season. The initial increase in CO 2 emissions was detected during the growing season that immediately followed the largest (February 2010) peak in the occurrence rate of shallow earthquakes. Migration of CO 2 -rich magmatic fluids may have driven observed patterns of elevated deep, then shallow seismicity, while the relationship between pore fluid pressures within a shallow (upper 3 km of crust) fluid reservoir and permeability structure of the reservoir cap rock may have controlled the temporal pattern of surface CO 2 emissions.

California↗

USGS2018

Sulfur cycle in the Valles Caldera volcanic complex, New Mexico – Letter 1: Sulfate sources in aqueous system, and implications for S isotope record in Gale Crater on Mars

Initial in situ sulfur (S) isotope measurements of the Martian bedrock in Gale Crater have revealed an unexpectedly wide range of δ 34 S values (−47 to +28%). Generally, it is unclear what processes could have contributed to these large isotope fractionations. Therefore, we studied S sources and aqueous SO 2− 4 cycling in the Valles Caldera volcanic complex, New Mexico to better understand S isotope fractionations related to S degassing, hydrothermal activity, and low-temperature processes in aqueous environment. Overall, our study demonstrates that volcanic systems show large spatial heterogeneity in δ 34 S. Magmatic S sources are obvious in steam-dominated H 2 S degassing and precipitation of secondary minerals from hydrothermal fluids with low δ 34 S values of +0.9 ±3%. Locally, however, hydrothermal processes have resulted in more negative δ 34 S values in sulfide minerals (−18 to −4%) and more positive δ 34 S values in sulfate minerals (−1 to +3%). Major aqueous SO 2− 4 sources are oxidation of H 2 S from modern hydrothermal gas emission, and oxidation and dissolution of sulfide and sulfate minerals present in the hydrothermally altered bedrock and crater-lake sediments. The δ 34 S of aqueous SO 2− 4 in surface water and groundwater varies widely (−8 to +5%) and is similar to major S endmembers that undergo oxidation and/or dissolution by active hydrological system. Minor SO 2− 4 contributions with more positive δ 34 S values (+9 to +14%) come from deeply circulating geothermal fluids and negligible amounts from atmospheric deposition (+5 to +7% in snow). Elevated SO 2− 4 contents are mainly associated with modern and past H 2 S emissions and oxidations near the surface. On regional scale, however, most of the intracaldera bedrock is S-depleted, thus the SO 2− 4 contents are usually low in the surface aquatic system and younger sedimentary lake deposits formed at times of negligible near surface hydrothermal activity. In general, magmatic-hydrothermal processes apparently cause the largest δ 34 S variation in S-bearing minerals on volcanic terrains. Therefore, we infer that the measured wide range of δ 34 S values in the Gale sediments by the Curiosity rover on Mars can be explained by S isotope composition of magmatic-hydrothermal sulfide and sulfate minerals that were present in the initial igneous/volcanic rocks prior to crater formation. Later aqueous processes involved oxidation and dissolution of S minerals initially present in these rocks and led to subsequent formation of diagenetic fluids and alteration products enriched in SO 2− 4 with relatively large δ 34 S variation. Additionally, physical erosion, transport and deposition of detrital hydrothermal S minerals from igneous/volcanic rocks might be in part responsible for the measured wide range of δ 34 S in Gale Crater. These unique S isotope results, measured in situ on another planet for the first time, imply the importance of magmatic-hydrothermal fluids in S transport on early Mars and their subsequent alteration in low-temperature aqueous environments.

New Mexico↗

USGS2023

Deep root activity overprints weathering of petrogenic organic carbon in shale

The oxidation of organic carbon in sedimentary bedrock (petrogenic OC, OC p e t r o "> petro ) is increasingly recognized as a potential source of CO 2 to the atmosphere. Recent studies provide evidence for the mobilization and oxidation of OC p e t r o "> petro in sedimentary bedrock during rock weathering. However, the mechanisms and rates remain uncertain, particularly where overlying soils and vegetation drive contemporaneous oxidation of recently fixed organic carbon. Here, we quantify OC p e t r o "> petro weathering across a 16 m shale depth profile in a steep, rapidly eroding forested hillslope in the Northern California Coast Ranges. We report solid and gas phase radiocarbon and stable isotope analyses of samples extracted from specialized in-situ samplers, and a supporting laboratory incubation experiment of the shale regolith. OC p e t r o "> petro is removed from the weathered bedrock at a rate of approximately 0.12 gC/m 3 yr, which is orders of magnitude lower than the rate of OC p e t r o "> petro oxidation we achieved in the laboratory with crushed samples (557.1 gC/m 3 /yr). This disparity occurs despite high O 2 ( g ) "> 2(g) content across the depth profile, indicating that physical accessibility of OC p e t r o "> petro can regulate oxidative weathering. There is no direct radiocarbon evidence of OC p e t r o "> petro oxidation in CO 2 ( g ) "> 2(g) across the upper 13 m of the weathering profile during both wet and dry seasons. Instead, vadose zone CO 2 ( g ) "> 2(g) production at the site is dominated by respiration of recently fixed carbon associated with deep rooting. OC p e t r o "> petro is clearly mobilized across the vadose zone during weathering in this rapidly eroding, oxygen-rich, biologically dynamic hillslope, but at rates far below what can be measured given the contribution of root-derived CO 2 ( g ) "> 2(g) .

California↗

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