Assessing risk to fresh water resources from long term CO2 injection- laboratory and field studies

In developing a site for geologic sequestration, one must assess potential consequences of failure to adequately contain injected carbon dioxide (CO2). Upward migration of CO2 or displacement of saline water because of increased pressure might impact protected water resources 100s to 1000s of meters above a sequestration interval. Questions posed are: (1) Can changes in chemistry of fresh water aquifers provide evidence of CO2 leakage from deep injection/sequestration reservoirs containing brine and or hydrocarbons? (2) What parameters can we use to assess potential impacts to water quality? (3) If CO2 leakage to freshwater aquifers occurs, will groundwater quality be degraded and if so, over what time period? Modeling and reaction experiments plus known occurrences of naturally CO2-charged potable water show that the common chemical reaction products from dissolution of CO2 into freshwater include rapid buffering of acidity by dissolution of calcite and slower equilibrium by reaction with clays and feldspars. Results from a series of laboratory batch reactions of CO2 with diverse aquifer rocks show geochemical response within hours to days after introduction of CO2. Results included decreased pH and increased concentrations of cations in CO2 experimental runs relative to control runs using argon (Ar). Some cation (Ba, Ca, Fe, Mg, Mn, and Sr) concentrations increased over and an order of magnitude during CO2 runs. Results are aquifer dependant in that experimental vessels containing different aquifer rocks showed different magnitudes of increase in cation concentrations. Field studies designed to improve understanding of risk to fresh water are underway in the vicinity of (1) SACROC oilfield in Scurry County, Texas, USA where CO2 has been injected for enhanced oil recovery (EOR) since 1972 and (2) the Cranfield unit in Adams County, Mississippi, USA where CO2 EOR is currently underway. Both field studies are funded by the U.S. Department of Energy (DOE) regional carbon sequestration partnership programs and industrial sponsors. Preliminary results of groundwater monitoring are currently available for the SACROC field study where researchers investigated 68 water wells and one spring during five field excursions between June 2006 and July 2008. Results to date show no trend of preferential degradation below drinking water standards in areas of CO2 injection (inside SACROC) as compared to areas outside of the SACROC oil field.Bureau of Economic Geolog

Extended Cave Drip Water Time Series Captures the 2015–2016 El Niño in Northern Borneo

Time series of cave drip water oxygen isotopes (δ18O) provide site‐specific assessments of the contributions of climate and karst processes to stalagmite δ18O records employed for hydroclimate reconstructions. We present ~12‐year‐long time series of biweekly cave drip water δ18O variations from three sites as well as a daily resolved local rainfall δ18O record from Gunung Mulu National Park in northern Borneo. Drip water δ18O variations closely match rainfall δ18O variations averaged over the preceding 3–18 months. We observe coherent interannual drip water δ18O variability of ~3‰ to 5‰ related to the El Niño–Southern Oscillation (ENSO), with sustained positive rainfall and drip water δ18O anomalies observed during the 2015/2016 El Niño. Evidence of nonlinear behavior at one of three drip water monitoring sites implies a time‐varying contribution from a longer‐term reservoir. Our results suggest that well‐replicated, high‐resolution stalagmite δ18O reconstructions from Mulu could characterize past ENSO‐related variability in regional hydroclimate.Plain Language SummaryCave stalagmites allow for the reconstruction of past regional rainfall variability over the last hundreds of thousands of years with robust age control. Such reconstructions rely on the fact that differences in the isotopic composition of rainwater set by regional rainfall patterns is preserved as the rainwater travels through cave bedrock to feed the cave drip waters forming stalagmites. Long‐term monitoring of rainwater and cave drip water isotopes ground truth the climate to stalagmite relationship across modern‐day changes in regional rainfall. Twelve years of monitoring data presented in this study identify individual El Niño–Southern Oscillation events in rainfall and cave drip water isotopic composition, providing a strong foundation for stalagmite‐based climate reconstructions from this site.Key PointsThree 12‐year‐long cave drip water δ18O time series capture El Niño and La Niña events in northern BorneoEstimates of karst residence times range from 3 to 18 months, with a secondary contribution from a longer‐term reservoir at one drip siteDrip water nonstationarity implies multiple stalagmites are required to reconstruct El Niño–Southern Oscillation variability over timePeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/154266/1/grl60264-sup-0002-2019GL086363-SI.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154266/2/grl60264_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154266/3/grl60264.pd

Trace metal and carbon isotopic variations in cave dripwater and stalagmite geochemistry from northern Borneo

We investigate stalagmite trace metal ratios and carbon isotopic composition (δ^(13)C) as potential paleoclimate proxies by comparing cave dripwaters, stalagmites, and bedrock composition from Gunung Mulu and Gunung Buda National Parks in northern Borneo, a tropical rainforest karst site. Three year long, biweekly time series of dripwater Mg/Ca, Sr/Ca, and δ^(13)C from several drips at our site are not correlated with rainfall variability, indicative of a relatively weak relationship between hydroclimate and dripwater geochemistry at our site. However, combining all of the dripwater geochemical data gathered over four field trips to our site (N > 300 samples), we find that drips with highly variable Mg[Sr]/Ca have relatively invariable δ^(18)O values close to the mean. We hypothesize that increased residence times translate into reduced variance in dripwater δ^(18)O through mixing in the epikarst as well as increased Mg[Sr]/Ca values through increased calcite precipitation in the epikarst. Mg/Ca, Sr/Ca, and δ^(13)C time series from three overlapping stalagmites that grew over the last 27 kyrs are characterized by strong centennial-scale variations, and bear little resemblance to previously published, well-reproduced δ^(18)O time series from the same stalagmites. The only shared signal among the three stalagmites' geochemical time series is a relative decrease of 1‰ in δ^(13)C from the Last Glacial Maximum to the Holocene, consistent with a transition from savannah (C4) to rainforest (C3) conditions documented in nearby records. Taken together, our study indicates that stalagmite Mg[Sr]/Ca ratios are poor indicators of hydroclimate conditions at our site, while stalagmite δ^(13)C exhibits some reproducible signals on glacial-interglacial timescales

Northern Borneo stalagmite records reveal West Pacific hydroclimate across MIS 5 and 6

Over the past decades, tropical stalagmite δ^(18)O records have provided valuable insight on glacial and interglacial hydrological variability and its relationship to a variety of natural climate forcings. The transition out of the penultimate glaciation (MIS 6) represents an important target for tropical hydroclimate reconstructions, yet relatively few such reconstructions resolve this transition. Particularly, comparisons between Termination 1 and 2 provide critical insight on the extent and influence of proposed climate mechanisms determined from paleorecords and model experiments spanning the recent deglaciation. Here we present a new compilation of western tropical Pacific hydrology spanning 0–160 ky BP, constructed from eleven different U/Th-dated stalagmite δ^(18)O records from Gunung Mulu National Park in northern Borneo. The reconstruction exhibits significant precessional power in phase with boreal fall insolation strength over the 0–160 ky BP period, identifying precessional insolation forcing as the dominant driver of hydroclimate variability in northern Borneo on orbital timescales. A comparison with a network of paleoclimate records from the circum-Pacific suggests the insolation sensitivity may arise from changes in the Walker circulation system. Distinct millennial-scale increases in stalagmite δ^(18)O, indicative of reduced regional convection, occur within glacial terminations and may reflect a response to shifts in inter-hemispheric temperature gradients. Our results imply that hydroclimate in this region is sensitive to external forcing, with a response dominated by large-scale temperature gradients

Transformation of ENSO-related rainwater to dripwater δ^(18)O variability by vadose water mixing

Speleothem oxygen isotopes (δ^(18)O) are often used to reconstruct past rainfall δ^(18)O variability, and thereby hydroclimate changes, in many regions of the world. However, poor constraints on the karst hydrological processes that transform rainfall signals into cave dripwater add significant uncertainty to interpretations of speleothem-based reconstructions. Here we present several 6.5 year, biweekly dripwater δ^(18)O time series from northern Borneo and compare them to local rainfall δ^(18)O variability. We demonstrate that vadose water mixing is the primary rainfall-to-dripwater transformation process at our site, where dripwater δ^(18)O reflects amount-weighted rainfall δ^(18)O integrated over the previous 3–10 months. We document large interannual dripwater δ^(18)O variability related to the El Niño–Southern Oscillation (ENSO), with amplitudes inversely correlated to dripwater residence times. According to a simple stalagmite forward model, asymmetrical ENSO extremes produce significant offsets in stalagmite δ^(18)O time series given different dripwater residence times. Our study highlights the utility of generating multiyear, paired time series of rainfall and dripwater δ^(18)O to aid interpretations of stalagmite δ^(18)O reconstructions

Rainfall variations in central Indo-Pacific over the past 2,700 y

Tropical rainfall variability is closely linked to meridional shifts of the Intertropical Convergence Zone (ITCZ) and zonal movements of the Walker circulation. The characteristics and mechanisms of tropical rainfall variations on centennial to decadal scales are, however, still unclear. Here, we reconstruct a replicated stalagmite-based 2,700-y-long, continuous record of rainfall for the deeply convective northern central Indo-Pacific (NCIP) region. Our record reveals decreasing rainfall in the NCIP over the past 2,700 y, similar to other records from the northern tropics. Notable centennial- to decadal-scale dry climate episodes occurred in both the NCIP and the southern central Indo-Pacific (SCIP) during the 20th century [Current Warm Period (CWP)] and the Medieval Warm Period (MWP), resembling enhanced El Niño-like conditions. Further, we developed a 2,000-y-long ITCZ shift index record that supports an overall southward ITCZ shift in the central Indo-Pacific and indicates southward mean ITCZ positions during the early MWP and the CWP. As a result, the drying trend since the 20th century in the northern tropics is similar to that observed during the past warm period, suggesting that a possible anthropogenic forcing of rainfall remains indistinguishable from natural variability

Northern Borneo stalagmite records reveal West Pacific hydroclimate across MIS 5 and 6

Over the past decades, tropical stalagmite δ18Orecords have provided valuable insight on glacial and interglacial hydrological variability and its relationship to a variety of natural climate forcings. The transition out of the penultimate glaciation (MIS 6) represents an important target for tropical hydroclimate reconstructions, yet relatively few such reconstructions resolve this transition. Particularly, comparisons between Termination1 and 2 provide critical insight on the extent and influence of proposed climate mechanisms determined from paleorecords and model experiments spanning the recent deglaciation. Here we present a new compilation of western tropical Pacific hydrology spanning 0–160kyBP, constructed from eleven different U/Th-dated stalagmite δ18Orecords from Gunung Mulu National Park in northern Borneo. The reconstruction exhibits significant precessional power in phase with boreal fall insolation strength over the 0–160kyBP period, identifying precessional insolation forcing as the dominant driver of hydroclimate variability in northern Borneo on orbital timescales. A comparison with a network of paleoclimate records from the circum-Pacific suggests the insolation sensitivity may arise from changes in the Walker circulation system. Distinct millennial-scale increases in stalagmite δ18O, indicative of reduced regional convection, occur within glacial terminations and may reflect a response to shifts in inter-hemispheric temperature gradients. Our results imply that hydroclimate in this region is sensitive to external forcing, with a response dominated by large-scale temperature gradients. . , , , , , , , , , ,

Transformation of ENSO‐related rainwater to dripwater δ18O variability by vadose water mixing

Speleothem oxygen isotopes (δ18O) are often used to reconstruct past rainfall δ18O variability, and thereby hydroclimate changes, in many regions of the world. However, poor constraints on the karst hydrological processes that transform rainfall signals into cave dripwater add significant uncertainty to interpretations of speleothem-based reconstructions. Here we present several 6.5 year, biweekly dripwater δ18O time series from northern Borneo and compare them to local rainfall δ18O variability. We demonstrate that vadose water mixing is the primary rainfall-to-dripwater transformation process at our site, where dripwater δ18O reflects amount-weighted rainfall δ18O integrated over the previous 3–10 months. We document large interannual dripwater δ18O variability related to the El Niño–Southern Oscillation (ENSO), with amplitudes inversely correlated to dripwater residence times. According to a simple stalagmite forward model, asymmetrical ENSO extremes produce significant offsets in stalagmite δ18O time series given different dripwater residence times. Our study highlights the utility of generating multiyear, paired time series of rainfall and dripwater δ18O to aid interpretations of stalagmite δ18O reconstructions

The Iso2k Database: A global compilation of paleo-δ18O and δ2H records to aid understanding of Common Era climate

Reconstructions of global hydroclimate during the Common Era (CE; the past ~ 2000 years) are important for providing context for current and future global environmental change. Stable isotope ratios in water are quantitative indicators of hydroclimate on regional to global scales, and these signals are encoded in a wide range of natural geologic archives. Here we present the Iso2k database, a global compilation of previously published datasets from a variety of natural archives that record the stable oxygen (δ18O) or hydrogen (δ2H) isotopic composition of environmental waters, which reflect hydroclimate changes over the CE. The Iso2k database contains 756 isotope records from the terrestrial and marine realms, including: glacier and ground ice (205); speleothems (68); corals, sclerosponges, and mollusks (145); wood (81); lake sediments and other terrestrial sediments (e.g., loess) (158); and marine sediments (99). Individual datasets have temporal resolutions ranging from sub-annual to centennial, and include chronological data where available. A fundamental feature of the database is its comprehensive metadata, which will assist both experts and non-experts in the interpretation of each record and in data synthesis. Key metadata fields have standardized vocabularies to facilitate comparisons across diverse archives and with climate model simulated fields. This is the first global-scale collection of water isotope proxy records from multiple types of geological and biological archives. It is suitable for evaluating hydroclimate processes through time and space using large-scale synthesis, model-data intercomparison and (paleo)data assimilation. The Iso2k database is available for download at: https://doi.org/10.6084/m9.figshare.11553162 (McKay and Konecky, 2020)