Uncertainty in paleohydrologic reconstructions from molecular δD values

Compound-specific δD measurements can be used for quantitative estimation of source water δD values, a useful tracer for paleohydrologic changes. Such estimates have quantifiable levels of uncertainty that are often miscalculated, resulting in inaccurate error reporting in the scientific literature that can impact paleohydrologic interpretations. Here, we summarize the uncertainties inherent to molecular δD measurements and the quantification of source water δD values, and discuss the assumptions involved when omitting various sources of uncertainty. Using standard protocols from measurement science, we derive the equations necessary to quantify these various sources of uncertainty. We show that analytical uncertainty is usually improperly estimated and that after apparent fractionation between δD values of source water and molecule, normalization of data to the VSMOW scale introduces the largest amount of uncertainty. Lastly, to facilitate systematic error reporting we provide an Uncertainty Calculator spreadsheet to conveniently calculate uncertainty in δD measurements

Organic thermal maturity as a proxy for frictional fault heating: Experimental constraints on methylphenanthrene kinetics at earthquake timescales

Biomarker thermal maturity is widely used to study burial heating of sediments over millions of years. Heating over short timescales such as during earthquakes should also result in measurable increases in biomarker thermal maturity. However, the sensitivity of biomarker thermal maturity reactions to short, higher-temperature heating has not been established. We report on hydrous pyrolysis experiments that determine the kinetic parameters of methylphenanthrene maturation at timescales and temperatures relevant to earthquake heating. Samples of Woodford Shale were heated at temperatures up to 343 °C over 15–150 min. The thermal maturity of the samples as measured by the methylphenanthrene index-1 (MPI-1) increased with heating time and temperature. We find that MPI-1 increases with time and temperature consistent with a first-order kinetic model and Arrhenius temperature relationship. Over the timescales tested here, MPI-1 is strongly affected by maximum temperature and less sensitive to heating duration. Production of new phenanthrene isomers and expulsion of a liquid pyrolyzate also occurred. Differential expulsion of methylphenanthrene isomers affected the apparent maturity of the rock at lower temperatures and may need to be considered for organic-rich fault rocks. Our results demonstrate that the overall MPI-1 reaction extent in both the rock and pyrolyzate are a useful measure of thermal maturity and reflect temperature history during rapid heating

Constraints on the salinity–oxygen isotope relationship in the central tropical Pacific Ocean

Uncertainties surround the relationship between salinity and the stable isotopic composition of seawater, largely due to a dearth of modern seawater isotope data. Here we report 191 new, paired measurements of salinity and seawater oxygen isotopes (δ¹⁸O_sw) taken from the central tropical Pacific in May 2012, from the surface to 4600 m depth. We observe significant correlations between δ¹⁸O_sw and salinity across the study region, with slopes ranging from 0.23 to 0.31‰/psu for the mixed layer, and 0.35–0.42‰/psu for waters between the mixed layer and 500 m depth. When considering δ¹⁸O_sw–salinity across averages of individual water masses in the region, slopes range from 0.21 to 0.40‰/psu, albeit with appreciable scatter. Surface salinity and δ¹⁸O_sw data corresponding to the North Equatorial Countercurrent are significantly higher than previously observed, which we attribute to a weak westerly current and dry conditions in the region during the May 2012 cruise. Subsurface (80–500 m) salinity values from 2012 are significantly lower than corresponding values from pre-existing regional data, highlighting a different latitudinal sampling distribution, while subsurface δ¹⁸O_sw is not significantly different. Thus, in May 2012, δ¹⁸O_sw in this region could not be used to distinguish between subsurface water masses of different salinities. Unlike other regions where the surface ‘freshwater endmember’ is close to the δ¹⁸O value of regional precipitation, the freshwater endmember implied by our dataset (− 10.38‰) is consistent with a strong evaporative influence. Paired δ¹⁸O–δD values of precipitation and surface seawaters have similar slopes (5.0, 5.1), and relatively low intercepts (1.4, 0.8) indicating isotopic variability in both reservoirs is also partly controlled by evaporation

Proglacial lake sediment records reveal Holocene climate changes in the Venezuelan Andes

Lake sediment records from the Cordillera de Mérida in the northern Venezuelan Andes document the history of local glacial variability and climate changes during the Holocene (∼12 ka to the present). The valleys that contain these lakes have similar bedrock compositions and hypsometries, but have different headwall elevations and aspects, which makes them useful for investigating the magnitude of past glaciations. There was widespread glacial retreat in the Venezuelan Andes during the early Holocene, after which most watersheds remained ice free, and thus far only valleys with headwalls higher than ∼4400 m asl contain evidence of glaciation during the last ∼10 ka. There was a pronounced shift in sediment composition for the Montos (headwall: ∼4750 m asl) and Los Anteojos (headwall: ∼4400 m asl) records during the middle Holocene from ∼8.0 to 7.7 ka when conditions appear to have become ice free and drier. There is tentative evidence that the glacier in the Mucubají valley (headwall: ∼4609 m asl) advanced from ∼8.1 to 6.6 ka and then retreated during the latter stages of the middle Holocene. Clastic sediment accumulation in other nearby lake basins was either low or decreased throughout most of the middle Holocene as watersheds stabilized under warmer and/or drier conditions. In the Montos record, there was another major shift in sediment composition that occurred from ∼6.5 to 5.7 ka, similar to other regional records that suggest conditions were drier during this period. Overall, the late Holocene was a period of warmer and wetter conditions with ice extent at a minimum in the northern tropical Andes. There were also punctuated decadal to multi-centennial periods of higher clastic sediment accumulation during the last ∼4 ka, likely in response to periods of cooling and/or local precipitation changes. In watersheds with headwalls above 4600 m asl, there is evidence of glacial advances during the Little Ice Age (∼0.6–0.1 ka). The pattern of glacial variability is generally similar in both the northern and southern tropics during the Little Ice Age, suggesting that ice margins in both regions were responding to colder and wetter conditions during the latest Holocene. The observed pattern of Holocene climate variability in the Venezuelan Andes cannot be explained by insolation forcing alone, and tropical ocean influences were likely associated with the observed glacial and lake level changes

Biomarkers heat up during earthquakes: New evidence of seismic slip in the rock record

During earthquakes, faults heat up due to frictional work. However, evidence of heating from paleoearthquakes along exhumed faults remains scarce. Here we describe a method using thermal maturation of organic molecules in sedimentary rock to determine whether a fault has experienced differential heating compared to surrounding rocks. We demonstrate the utility of this method on an ancient, pseudotachylyte-hosting megathrust at Pasagshak Point, Alaska. Measurements of the ratio of thermally stable to thermally unstable compounds (diamondoids/n-alkanes) show that the melt-bearing rocks have higher thermal maturity than surrounding rocks. Furthermore, the mineralogy of the survivor grains and the presence of any organic molecules allow us to constrain the temperature rise during the ancient earthquakes to 840–1170 °C above ambient temperatures of ∼260 °C. From this temperature rise, we estimate that the frictional work of the earthquake was ∼105–228 MJ/m2. Using experimental friction measurements as a constraint, we estimate that the minimum slip necessary for heating was ∼1–8 m. This paper demonstrates that biomarkers will be a useful tool to identify seismic slip along faults without frictional melt

Constraints on the salinity–oxygen isotope relationship in the central tropical Pacific Ocean

Uncertainties surround the relationship between salinity and the stable isotopic composition of seawater, largely due to a dearth of modern seawater isotope data. Here we report 191 new, paired measurements of salinity and seawater oxygen isotopes (δ¹⁸O_sw) taken from the central tropical Pacific in May 2012, from the surface to 4600 m depth. We observe significant correlations between δ¹⁸O_sw and salinity across the study region, with slopes ranging from 0.23 to 0.31‰/psu for the mixed layer, and 0.35–0.42‰/psu for waters between the mixed layer and 500 m depth. When considering δ¹⁸O_sw–salinity across averages of individual water masses in the region, slopes range from 0.21 to 0.40‰/psu, albeit with appreciable scatter. Surface salinity and δ¹⁸O_sw data corresponding to the North Equatorial Countercurrent are significantly higher than previously observed, which we attribute to a weak westerly current and dry conditions in the region during the May 2012 cruise. Subsurface (80–500 m) salinity values from 2012 are significantly lower than corresponding values from pre-existing regional data, highlighting a different latitudinal sampling distribution, while subsurface δ¹⁸O_sw is not significantly different. Thus, in May 2012, δ¹⁸O_sw in this region could not be used to distinguish between subsurface water masses of different salinities. Unlike other regions where the surface ‘freshwater endmember’ is close to the δ¹⁸O value of regional precipitation, the freshwater endmember implied by our dataset (− 10.38‰) is consistent with a strong evaporative influence. Paired δ¹⁸O–δD values of precipitation and surface seawaters have similar slopes (5.0, 5.1), and relatively low intercepts (1.4, 0.8) indicating isotopic variability in both reservoirs is also partly controlled by evaporation

Synchronous Interhemispheric Holocene Climate Trends in the Tropical Andes

Holocene variations of tropical moisture balance have been ascribed to orbitally forced changes in solar insolation. If this model is correct, millennial-scale climate evolution should be antiphased between the northern and southern hemispheres, producing humid intervals in one hemisphere matched to aridity in the other. Here we show that Holocene climate trends were largely synchronous and in the same direction in the northern and southern hemisphere outer-tropical Andes, providing little support for the dominant role of insolation forcing in these regions. Today, sea-surface temperatures in the equatorial Pacific Ocean modulate rainfall variability in the outer tropical Andes of both hemispheres, and we suggest that this mechanism was pervasive throughout the Holocene. Our findings imply that oceanic forcing plays a larger role in regional South American climate than previously suspected, and that Pacific sea-surface temperatures have the capacity to induce abrupt and sustained shifts in Andean climate

Toward a Cenozoic history of atmospheric CO₂

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.</p

Toward a Cenozoic history of atmospheric CO₂

INTRODUCTIONAnthropogenic carbon dioxide (CO2) emissions have driven an increase in the global atmospheric CO2 concentration from 280 parts per million (ppm) before industrialization to an annual average of 419 ppm in 2022, corresponding to an increase in global mean surface temperature (GMST) of 1.1°C over the same period. If global CO2 emissions continue to rise, atmospheric CO2 could exceed 800 ppm by the year 2100. This begs the question of where our climate is headed. The geologic record is replete with both brief and extended intervals of CO2 concentration higher than today and thus provides opportunities to project the response of the future climate system to increasing CO2. For example, it has been estimated that global surface temperature 50 million years ago (Ma) was ~12°C higher than today, in tandem with atmospheric CO2 concentrations some 500 ppm higher (i.e., more than doubled) than present-day values. Consistent with these estimates, Antarctica and Greenland were free of ice at that time. However, reconstructing these values prior to direct instrumental measurements requires the use of paleoproxies—measurable properties of geological archives that are closely, but only indirectly, related to the parameter in question (e.g., temperature, CO2). To date, at least eight different proxies from both terrestrial and marine archives have been developed and applied to reconstruct paleo-CO2, but their underlying assumptions have been revised over time, and published reconstructions are not always consistent. This uncertainty complicates quantification of the climate responses to the ongoing rise of atmospheric CO2 concentrations.RATIONALEAlthough earlier studies have compiled published paleo-CO2 estimates, those studies typically applied only limited proxy vetting, included estimates that were made before the proxies were sufficiently validated, and/or focused on only a subset of available proxy data. The international consortium of the Cenozoic CO2 Proxy Integration Project (CenCO2PIP) has undertaken a 7-year effort to document, evaluate, and synthesize published paleo-CO2 records from all available archives, spanning the past 66 million years. The most reliable CO2 estimates were identified, some records were recalculated to conform with the latest proxy understanding, age models were updated where necessary and possible, and data were categorized according to the community’s level of confidence in each estimate. The highest-rated data were eventually combined into a reconstruction of the Cenozoic history of atmospheric CO2.RESULTSThe resulting reconstruction illustrates a more quantitatively robust relationship between CO2 and global surface temperature, yielding greater clarity and confidence than previous syntheses. The new record suggests that early Cenozoic “hothouse” CO2 concentrations peaked around 1600 ppm at ~51 Ma. Near 33.9 Ma, the onset of continent-wide Antarctic glaciation coincided with an atmospheric CO2 concentration of 720 ppm. By ~32 Ma, atmospheric CO2 had dropped to 550 ppm, and this value coincided with the onset of radiation in plants with carbon-concentrating mechanisms that populate grasslands and deserts today. CO2 remained below this threshold for the remainder of the Cenozoic and continued its long-term decrease toward the present. Along this trajectory, the middle Miocene (~16 Ma) marks the last time that CO2 concentrations were consistently higher than at present; Greenland was not yet glaciated at that time, and independent estimates suggest that sea level was some 50 m higher than today. Values eventually dropped below 270 ppm at the Plio-Pleistocene boundary (2.6 Ma), when Earth approached our current “icehouse” state of bipolar glaciation. This and other climatic implications of the revised CO2 curve, including the evolution of the cryosphere, flora, and fauna, along with the cross-disciplinary data assessment process, are detailed in the full online article.CONCLUSIONThis community-vetted CO2 synthesis represents the most reliable data available to date and a means to improve our understanding of past changes in global climate and carbon cycling as well as organismal evolution. However, this effort is still incomplete. Data remain sparse during the earlier part of the record and in some instances are dominated by estimates from a single proxy system. Generating a paleo-CO2 record with even greater confidence will require further research using multiple proxies to fill in data gaps and increase overall data resolution, resolve discrepancies between estimates from contemporaneous proxy analyses, reduce uncertainty of established methods, and develop new proxies.</div

Toward a Cenozoic history of atmospheric CO2

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution