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Development of the hydrosphere and atmosphere, with special reference to probable composition of the early atmosphere

A satisfactory hypothesis of the development of the hydrosphere and atmosphere depends upon evidence from many sciences and the solution of many other fundamental problems of earth history. But because it is so closely related to many other problems, any progress toward unravelling the history of the hydrosphere and atmosphere limits the range of permissible speculation about such distantly related questions as the origin of the solar system, continents, mountains, and living organisms. Several hypotheses of the source of the earth’s air and waters are examined for their consistency with established principles and observed geologic evidence, and special attention is given to the probable composition of the early atmosphere. Hypotheses of the origin of the atmosphere and hydrosphere fall into two chief categories: (1) that all air and water of the earth are residual from a dense primitive atmosphere that once enveloped a molten globe; or (2) that they have accumulated at the earth’s surface by leakage from the interior. The quantities of water, carbon dioxide, organic carbon, nitrogen, sulfur, etc., that have been or are now part of the earth’s atmosphere and hydrosphere may be estimated within reasonable limits of uncertainty and these “excess” volatiles afford a basis for testing chemical consequences of the alternative hypotheses. Several writers have suggested that the primitive atmosphere may have been composed largely of CH 4 and NH 3 . However, the equilibrium constants for reactions of these and other gases, combined with the evidence of the “excess” volatiles, indicate that CO 2 and N 2 are much more likely. The stabilities of methane and ammonia depend upon the presence of free hydrogen; and the escape rate of hydrogen from the earth is such that methane probably could have persisted in significant amounts in the early atmosphere no more than 10 6 to 10 8 years. For all but a relatively brief period at the very beginning of earth history, the atmosphere probably contained CO 2 and N 2 rather than CH 4 and NH 3 . When the consequences of a dense atmosphere of CO 2 and N 2 (but with almost no free O 2 or H 2 ) are examined, it is found that several chemical effects (such as the quantity of rocks that would have to be weathered, of sodium dissolved in sea water, and of CaCO 3 deposited on the sea floor very early in early history) are not borne out by the observed geologic record. From this and other lines of evidence it seems extremely improbable that the present atmosphere and hydrosphere are residual from any such dense primitive atmosphere. Instead, it seems likely that the atmosphere and hydrosphere have accumulated gradually during geologic time by the escape of water vapor, CO 2 , CO, N 2 , and other volatiles from intrusive and extrusive rocks that have risen more or less continuously from the deep interior of the earth. The amount of free oxygen in the early atmosphere is a separate problem that cannot be solved until the evidence of the earliest rocks has been appraised more fully. Current hypotheses of the origin of life appear to require a reducing atmosphere, yet it seems likely that oxygen has been accumulating from the photodissociation of water vapor ever since the earth was formed. The oxidation of ferrous iron and sulfides in the earliest sediments may have kept the oxygen content very low, and life may have begun in local reducing environments.

GSA Special Papers

Response of global soil consumption of atmospheric methane to changes in atmospheric climate and nitrogen deposition

Soil consumption of atmospheric methane plays an important secondary role in regulating the atmospheric CH 4 budget, next to the dominant loss mechanism involving reaction with the hydroxyl radical (OH). Here we used a process-based biogeochemistry model to quantify soil consumption during the 20th and 21st centuries. We estimated that global soils consumed 32–36 Tg CH 4 yr −1 during the 1990s. Natural ecosystems accounted for 84% of the total consumption, and agricultural ecosystems only consumed 5 Tg CH 4 yr −1 in our estimations. During the twentieth century, the consumption rates increased at 0.03–0.20 Tg CH 4 yr −2 with seasonal amplitudes increasing from 1.44 to 3.13 Tg CH 4 month −1 . Deserts, shrublands, and xeric woodlands were the largest sinks. Atmospheric CH 4 concentrations and soil moisture exerted significant effects on the soil consumption while nitrogen deposition had a moderate effect. During the 21st century, the consumption is predicted to increase at 0.05-1.0 Tg CH 4 yr −2 , and total consumption will reach 45–140 Tg CH 4 yr −1 at the end of the 2090s, varying under different future climate scenarios. Dry areas will persist as sinks, boreal ecosystems will become stronger sinks, mainly due to increasing soil temperatures. Nitrogen deposition will modestly reduce the future sink strength at the global scale. When we incorporated the estimated global soil consumption into our chemical transport model simulations, we found that nitrogen deposition suppressed the total methane sink by 26 Tg during the period 1998–2004, resulting in 6.6 ppb higher atmospheric CH 4 mixing ratios compared to without considering nitrogen deposition effects. On average, a cumulative increase of every 1 Tg soil CH 4 consumption decreased atmospheric CH 4 mixing ratios by 0.26 ppb during the period 1998–2004.

Global Biogeochemical Cycles

Comparison of mercury mass loading in streams to atmospheric deposition in watersheds of Western North America: Evidence for non-atmospheric mercury sources

Annual stream loads of mercury (Hg) and inputs of wet and dry atmospheric Hg deposition to the landscape were investigated in watersheds of the Western United States and the Canadian-Alaskan Arctic. Mercury concentration and discharge data from flow gauging stations were used to compute annual mass loads with regression models. Measured wet and modeled dry deposition were compared to annual stream loads to compute ratios of Hg stream load to total Hg atmospheric deposition. Watershed land uses or cover included mining, undeveloped, urbanized, and mixed. Of 27 watersheds that were investigated, 15 had some degree of mining, either of Hg or precious metals (gold or silver), where Hg was used in the amalgamation process. Stream loads in excess of annual Hg atmospheric deposition (ratio > 1) were observed in watersheds containing Hg mines and in relatively small and medium-sized watersheds with gold or silver mines, however, larger watersheds containing gold or silver mines, some of which also contain large dams that trap sediment, were sometimes associated with lower load ratios (< 0.2). In the non-Arctic regions, watersheds with natural vegetation tended to have low ratios of stream load to Hg deposition (< 0.1), whereas urbanized areas had higher ratios (0.34–1.0) because of impervious surfaces. This indicated that, in ecosystems with natural vegetation, Hg is retained in the soil and may be transported subsequently to streams as a result of erosion or in association with dissolved organic carbon. Arctic watersheds (Mackenzie and Yukon Rivers) had a relatively elevated ratio of stream load to atmospheric deposition (0.27 and 0.74), possibly because of melting glaciers or permafrost releasing previously stored Hg to the streams. Overall, our research highlights the important role of watershed characteristics in determining whether a landscape is a net source of Hg or a net sink of atmospheric Hg.

Science of the Total Environment

The precision of wet atmospheric deposition data from national atmospheric deposition program/national trends network sites determined with collocated samplers

A collocated, wet-deposition sampler program has been operated since October 1988 by the U.S. Geological Survey to estimate the overall sampling precision of wet atmospheric deposition data collected at selected sites in the National Atmospheric Deposition Program and National Trends Network (NADP/NTN). A duplicate set of wet-deposition sampling instruments was installed adjacent to existing sampling instruments at four different NADP/NTN sites for each year of the study. Wet-deposition samples from collocated sites were collected and analysed using standard NADP/NTN procedures. Laboratory analyses included determinations of pH, specific conductance, and concentrations of major cations and anions. The estimates of precision included all variability in the data-collection system, from the point of sample collection through storage in the NADP/NTN database. Sampling precision was determined from the absolute value of differences in the analytical results for the paired samples in terms of median relative and absolute difference. The median relative difference for Mg2+, Na+, K+ and NH4+ concentration and deposition was quite variable between sites and exceeded 10% at most sites. Relative error for analytes whose concentrations typically approached laboratory method detection limits were greater than for analytes that did not typically approach detection limits. The median relative difference for SO42- and NO3- concentration, specific conductance, and sample volume at all sites was less than 7%. Precision for H+ concentration and deposition ranged from less than 10% at sites with typically high levels of H+ concentration to greater than 30% at sites with low H+ concentration. Median difference for analyte concentration and deposition was typically 1.5-2-times greater for samples collected during the winter than during other seasons at two northern sites. Likewise, the median relative difference in sample volume for winter samples was more than double the annual median relative difference at the two northern sites. Bias accounted for less than 25% of the collocated variability in analyte concentration and deposition from weekly collocated precipitation samples at most sites.A collocated, wet-deposition sampler program has been operated since OCtober 1988 by the U.S Geological Survey to estimate the overall sampling precision of wet atmospheric deposition data collected at selected sites in the National Atmospheric Deposition Program and National Trends Network (NADP/NTN). A duplicate set of wet-deposition sampling instruments was installed adjacent to existing sampling instruments four different NADP/NTN sites for each year of the study. Wet-deposition samples from collocated sites were collected and analysed using standard NADP/NTN procedures. Laboratory analyses included determinations of pH, specific conductance, and concentrations of major cations and anions. The estimates of precision included all variability in the data-collection system, from the point of sample collection through storage in the NADP/NTN database.

Atmospheric Environment

Use of a regional atmospheric model to simulate lake-atmosphere feedbacks associated with Pleistocene Lakes Lahontan and Bonneville

A regional model of the atmosphere (version 4 of the NCAR mesoscale model, MM4) was used to assess whether lake-effect precipitation was a significant component of the late-Pleistocene hydrologic budgets of Lakes Lahontan and Bonneville. Control simulations for January and July of 1979 were made using MM4, and the Pleistocene highstand surface areas of the lakes were added to the model and the simulations repeated. In the January simulations, 18% of the moisture added to the modeled atmosphere by Lake Lahontan returned to the Lahontan basin as precipitation, while 32% of the water evaporated from Lake Bonneville fell as precipitation over the Bonneville basin. In the July simulations, 7% of the moisture added to the modeled atmosphere by Lake Lahontan returned to the Lahontan basin as precipitation, and 4% of the water evaporated from Lake Bonneville fell as precipitation over the Bonneville basin. An additonal January simulation was made with the lake surface areas set at onehalf their highstand extents (the average surface area 20 to 15 ka BP). Results from this simulation were similar to the simulation with the highstand lakes, indicating lake-effect precipitation could have been a significant component of the hyrologic budgets of the lakes before and during the highstand period. ?? 1992 Springer-Verlag.

Climate Dynamics

The effects of atmospheric nitrogen deposition in the Rocky Mountains of Colorado and southern Wyoming— A synthesis and critical assessment of published results

The Rocky Mountain region of Colorado and southern Wyoming receives as much as 7 kilograms per hectare per year ((kg/ha)/yr) of atmospheric nitrogen (N) deposition, an amount that may have caused changes in aquatic and terrestrial life in otherwise pristine ecosystems. The Rocky Mountain National Park, in its role of protecting air-quality related values under provisions of the Clean Air Act Amendments of 1977, has provided support for this synthesis and critical assessment of published literature on the effects of atmospheric N deposition. Results from published studies indicate a long-term increase in the rate of atmospheric N deposition during the 20th century, but no region-wide increase during the past 2 decades, although the rate of atmospheric N deposition has increased at three sites east of the Continental Divide in the Front Range region since the mid-1980s. Much of the increase in atmospheric N deposition at all three sites has resulted from an increase in the ammonium concentrations of wet deposition; this suggests an increase in contributions from agricultural areas or from vehicle traffic east of the Rocky Mountains. Lakes at two study sites in the Front Range (Loch Vale and Green Lakes Valley) had NO 3 - concentrations of 30 to 40 micromoles per liter (µmol/L) during early spring snowmelt and remained at 5 to 10 µmol/L during summer. Retention of N in atmospheric wet deposition in some sub-catchments of these lakes was less than 50 percent, which reflects an advanced stage of N saturation. Nitrate concentrations in surface waters west of the Continental Divide were lower—often less than 10 µmol/L during snowmelt and less than 2 µmol/L during summer -- than surface waters east of the Divide, except in areas such as the Mt. Zirkel Wilderness that receive elevated amounts of atmospheric N deposition of 4 to 5 (kg/ha)/yr. Atmospheric N deposition in the Front Range east of the Divide may have altered the composition of alpine tundra-plant communities and lake diatoms, but additional studies would be needed to definitively demonstrate the hypothesized cause-and-effect relations. Rates of N-mineralization and nitrification in soils of the Front Range have increased in response to increased atmospheric N deposition. Projected future population growth and energy use in Colorado and the west increase the likelihood that the subtle effects of atmospheric N deposition now evident in the Front Range will become more pronounced and widespread in the future. The likelihood of future increased N emissions along the Front Range warrants a continuation of existing long-term precipitation and surface-water chemistry monitoring programs, and an expansion of the networks into areas that receive large amounts of atmospheric N deposition, but currently lack adequate monitoring. Long-term study and expanded sampling are needed to address uncertainties about the effects of atmospheric N deposition on terrestrial plant communities, nutrient limitation in lake plankton, shifts of dominant species within diatom communities, and on amphibian response to episodic surface-water acidification.

Colorado, Wyoming

Atmospheric nitrogen deposition in the Chesapeake Bay watershed: A history of change

The Chesapeake Bay watershed has been the focus of pioneering studies of the role of atmospheric nitrogen (N) deposition as a nutrient source and driver of estuarine trophic status. Here, we review the history and evolution of scientific investigations of the role of atmospheric N deposition, examine trends from wet and dry deposition networks, and present century-long (1950–2050) atmospheric N deposition estimates. Early investigations demonstrated the importance of atmospheric deposition as an N source to the Bay, providing 25%–40% among all major N sources. These early studies led to the unprecedented inclusion of targeted decreases in atmospheric N deposition as part of the multi-stakeholder effort to reduce N loads to the Bay. Emissions of nitrogen oxides (NO x ) and deposition of wet nitrate, oxidized dry N, and dry ammonium (NH 4 + ) sharply and synchronously declined by 60%–73% during 1995–2019. These decreases largely resulted from implementation of Title IV of the 1990 Clean Air Act Amendments, which began in 1995. Wet NH 4 + deposition shows no significant trend during this period. The century-long atmospheric N deposition estimates indicate an increase in total atmospheric N deposition in the Chesapeake watershed from 1950 to a peak of ~15 kg N/ha/yr in 1979, trailed by a slight decline of <10% through the mid-1990s, and followed by a sharp decline of about 40% thereafter through 2019. An additional 21% decline in atmospheric N deposition is projected from 2015 to 2050. A comparison of the Potomac River and James River watersheds indicates higher atmospheric N deposition in the Potomac, likely resulting from greater emissions from higher proportions of agricultural and urban land in this basin. Atmospheric N deposition rose from 30% among all N sources to the Chesapeake Bay watershed in 1950 to a peak of 40% in 1973, and a decline to 28% by 2015. These data highlight the important role of atmospheric N deposition in the Chesapeake Bay watershed and present a potential opportunity for decreases in deposition to contribute to further reducing N loads and improving the trophic status of tidal waters.

New York, New Jersey, Delaware, Maryland, Pennsylv

Atmospheric nitrogen in the Mississippi River Basin: Amissions, deposition and transport

Atmospheric deposition of nitrogen has been cited as a major factor in the nitrogen saturation of forests in the north-eastern United States and as a contributor to the eutrophication of coastal waters, including the Gulf of Mexico near the mouth of the Mississippi River. Sources of nitrogen emissions and the resulting spatial patterns of nitrogen deposition within the Mississippi River Basin, however, have not been fully documented. An assessment of atmospheric nitrogen in the Mississippi River Basin was therefore conducted in 1998-1999 to: (1) evaluate the forms in which nitrogen is deposited from the atmosphere; (2) quantify the spatial distribution of atmospheric nitrogen deposition throughout the basin; and (3) relate locations of emission sources to spatial deposition patterns to evaluate atmospheric transport. Deposition data collected through the NADP/NTN (National Atmospheric Deposition Program/National Trends Network) and CASTNet (Clean Air Status and Trends Network) were used for this analysis. NO(x) Tier 1 emission data by county was obtained for 1992 from the US Environmental Protection Agency (Emissions Trends Viewer CD, 1985-1995, version 1.0, September 1996) and NH3 emissions data was derived from the 1992 Census of Agriculture (US Department of Commerce. Census of Agriculture, US Summary and County Level Data, US Department of Commerce, Bureau of the Census. Geographic Area series, 1995:1b) or the National Agricultural Statistics Service (US Department of Agriculture. National Agricultural Statistics Service Historical Data. Accessed 7/98 at URL, 1998. http://www.usda.gov/nass/pubs/hisdata.htm). The highest rates of wet deposition of NO3- were in the north-eastern part of the basin, downwind of electric utility plants and urban areas, whereas the highest rates of wet deposition of NH4+ were in Iowa, near the center of intensive agricultural activities in the Midwest. The lowest rates of atmospheric nitrogen deposition were on the western (windward) side of the basin, which suggests that most of the nitrogen deposited within the basin is derived from internal sources. Atmospheric transport eastward across the basin boundary is greater for NO3- than NH4+, but a significant amount of NH4+ is likely to be transported out of the basin through the formation of (NH4)2SO4 and NH4NO3 particles - a process that greatly increases the atmospheric residence time of NH4+. This process is also a likely factor in the atmospheric transport of nitrogen from the Midwest to upland forest regions in the North-East, such as the western Adirondack region of New York, where NH4+ constitutes 38% of the total wet deposition of N.

Science of Total Environment

Development of ion-exchange collectors for monitoring atmospheric deposition of inorganic pollutants in Alaska parklands

Between 2010 and 2014, the U.S. Geological Survey completed a series of laboratory and field experiments designed to develop methodology to support the National Park Service’s long-term atmospheric pollutant monitoring efforts in parklands of Arctic Alaska. The goals of this research were to develop passive sampling methods that could be used for long-term monitoring of inorganic pollutants in remote areas of arctic parklands and characterize relations between wet and dry deposition of atmospheric pollutants to that of concentrations accumulated by mosses, specifically the stair-step, splendid feather moss, Hylocomium splendens. Mosses and lichens have been used by National Park Service managers as atmospheric pollutant biomonitors since about 1990; however, additional research is needed to better characterize the dynamics of moss bioaccumulation for various classes of atmospheric pollutants. To meet these research goals, the U.S. Geological Survey investigated the use of passive ionexchange collectors (IECs) that were adapted from the design of Fenn and others (2004). Using a modified IEC configuration, mulitple experiments were completed that included the following: (a) preliminary laboratory and development testing of IECs, (b) pilot-scale validation field studies during 2012 with IECs at sites with instrumental monitoring stations, and (c) deployment of IECs in 2014 at sites in Alaska having known or suspected regional sources of atmospheric pollutants where samples of Hylocomium splendens moss also could be collected for comparison. The targeted substances primarily included ammonium, nitrate, and sulfate ions, and certain toxicologically important trace metals, including cadmium, cobalt, copper, nickel, lead, and zinc. Deposition of atmospheric pollutants is comparatively low throughout most of Alaska; consequently, modifications of the original IEC design were needed. The most notable modification was conversion from a single-stage mixed-bed column to a two-stage arrangement. With the modified IEC design, ammonium, nitrate, and sulfate ions were determined with a precision of between 5 and 10 percent relative standard deviation for the low loads that happen in remote areas of Alaska. Results from 2012 field studies demonstrated that the targeted ions were stable and fully retained on the IEC during field deployment and could be fully recovered by extraction in the laboratory. Importantly, measurements of annual loads determined by combining snowpack and IEC sampling at sites near National Atmospheric Deposition Program monitoring stations was comparable to results obtained by the National Atmospheric Deposition Program. Field studies completed in 2014 included snowpack and IEC samples to measure depositional loads; the results were compared to concentrations of similar substances in co-located moss samples. Analyses of constituents in snow and IECs included ammonium, nitrate, and sulfate ions; and a suite of trace metals. Constituent measurements in Hylocomium splendens moss included total nitrogen, phosphorous, and sulfur, and trace metals. To recover ammonium ions and metal ions from the upper cation-exchange column, a two-step extraction procedure was developed from laboratory spiking experiments. The 2014 studies determined that concentrations of certain metals, nitrogen, and sulfur in tissues of Hylocomium splendens moss reflected differences in presumptive deposition from local atmospheric sources. Moss tissues collected from two sites farthest from urban locales had the lowest levels of total nitrogen and sulfur, whereas tissues collected from three of the urban sites had the greatest concentrations of many of the trace metals. Moss tissue concentrations of three trace metals (cobalt, chromium, and nickel) were strongly (positively) Spearman’s rank correlated ( p <0.05) with annual depositional loads of those metals. In addition, moss sulfur concentrations were positively rank correlated with annual depositional loads of sulfate ( p <0.07). Exploratory models indicated linear uptake of the three metals by Hylocomium splendens moss and nonlinear uptake of sulfur from sulfate. Our results provided useful preliminary models for several of the targeted substances; however, our ability to characterize relations between concentrations in moss and loadings for many of the metals was precluded by several factors. The few test sites, small concentration gradients, and generally low concentrations hampered model developments. In addition, the weather was unusually warm throughout Alaska during the winter of 2013–14, which caused intermittent melting of the snowpack at some of the test sites; consequently, our measurements of overwinter loads based on snowpack samples (obtained in late March) probably underestimated the actual loads. Regardless of these potential limitations, these studies have established a foundation to support further studies that can improve our understanding of how mosses accumulate inorganic substances and ultimately how mosses might be used as biomonitors of atmospheric pollutants; moreover, the successful development and validation of the IECs during this research documents how the methodology can be used for future monitoring efforts in remote regions of Alaska and elsewhere.

Alaska

Controlling for anthropogenically induced atmospheric variation in stable carbon isotope studies

Increased use of stable isotope analysis to examine food-web dynamics, migration, transfer of nutrients, and behavior will likely result in expansion of stable isotope studies investigating human-induced global changes. Recent elevation of atmospheric CO2 concentration, related primarily to fossil fuel combustion, has reduced atmospheric CO2 ??13C (13C/12C), and this change in isotopic baseline has, in turn, reduced plant and animal tissue ??13C of terrestrial and aquatic organisms. Such depletion in CO2 ??13C and its effects on tissue ??13C may introduce bias into ??13C investigations, and if this variation is not controlled, may confound interpretation of results obtained from tissue samples collected over a temporal span. To control for this source of variation, we used a high-precision record of atmospheric CO2 ??13C from ice cores and direct atmospheric measurements to model modern change in CO2 ??13C. From this model, we estimated a correction factor that controls for atmospheric change; this correction reduces bias associated with changes in atmospheric isotopic baseline and facilitates comparison of tissue ??13C collected over multiple years. To exemplify the importance of accounting for atmospheric CO2 ??13C depletion, we applied the correction to a dataset of collagen ??13C obtained from mountain lion (Puma concolor) bone samples collected in California between 1893 and 1995. Before correction, in three of four ecoregions collagen ??13C decreased significantly concurrent with depletion of atmospheric CO2 ??13C (n ??? 32, P ??? 0.01). Application of the correction to collagen ??13C data removed trends from regions demonstrating significant declines, and measurement error associated with the correction did not add substantial variation to adjusted estimates. Controlling for long-term atmospheric variation and correcting tissue samples for changes in isotopic baseline facilitate analysis of samples that span a large temporal range. ?? Springer-Verlag 2005.

Oecologia

The utility of atmospheric analyses for the mitigation of artifacts in InSAR

The numerical weather models (NWMs) developed by the meteorological community are able to provide accurate analyses of the current state of the atmosphere in addition to the predictions of the future state. To date, most attempts to apply the NWMs to estimate the refractivity of the atmosphere at the time of satellite synthetic aperture radar (SAR) data acquisitions have relied on predictive models. We test the hypothesis that performing a final assimilative routine, ingesting all available meteorological observations for the times of SAR acquisitions, and generating customized analyses of the atmosphere at those times will better mitigate atmospheric artifacts in differential interferograms. We find that, for our study area around Mount St. Helens (Amboy, Washington, USA), this approach is unable to model the refractive changes and provides no mean benefit for interferogram analysis. The performance is improved slightly by ingesting atmospheric delay estimates derived from the limited local GPS network; however, the addition of water vapor products from the GOES satellites reduces the quality of the corrections. We interpret our results to indicate that, even with this advanced approach, NWMs are not a reliable mitigation technique for regions such as Mount St. Helens with highly variable moisture fields and complex topography and atmospheric dynamics. It is possible, however, that the addition of more spatially dense meteorological data to constrain the analyses might significantly improve the performance of weather modeling of atmospheric artifacts in satellite radar interferograms.

Journal of Geophysical Research B: Solid Earth

Sentinel-2 and WorldView-3 atmospheric correction and signal normalization based on ground-truth spectroradiometric measurements

Remote sensing satellite Earth Observing Systems (EOS) provide a variety of products for monitoring Earth surface processes at varying spatial and spectral resolutions. Combining information from high and medium spatial resolution images is valuable for monitoring ground cover and vegetation status in cropland, grassland, forests, and other natural settings. However, coupling information from different EOS requires compensating for atmospheric and view angle effects before integrating comparable surface reflectance (SR) values. The objectives of this study were i) to assess how different atmospheric constituents affect the atmospheric correction results in Sentinel-2 and WorldView-3 imagery, ii) to establish a relationship with field spectra measurements, and iii) to develop an empirical approach to ensure that SR values extracted from different EOS can be normalized for use in monitoring vegetation and land cover status. We compared surface reflectance values derived from Sentinel-2 images corrected with Sen2Cor, MODTRAN or FLAASH atmospheric correction approaches for the visible-to-near infrared regions. Additionally, this information was compared to SR values extracted from WorldView-3 imagery acquired from the same dates and location (Central Spain) and corrected with MODTRAN and FLAASH approaches. Assessment of the atmospheric correction was conducted by comparing satellite image SR with ground-truth spectra acquired with a FieldSpec hand-held spectroradiometer. The results emphasized the importance of using common atmospheric parameters collected from ancillary data sources (i.e. MODIS Atmosphere & Land products) to ensure a reliable SR comparison. When compared to field-collected spectral data, SR from corrected Sentinel-2 push-broom imagery showed a reliable match (<4% difference in the visible bands and <0.52% difference in the near infrared bands). However, SR imagery from the pointable WorldView-3 instrument showed significant deviation, likely resulting from the effects of steep off-nadir acquisition angles (24.6° to 39.1°) combined with surface anisotropy. The magnitude and sign of the deviation in SR differed depending on the vegetation type, wavelength and sun-surface-sensor geometry. Therefore, it was necessary to account for angular effects to ensure reliable comparisons of imagery from the different EOS. In this study, an empirical angular correction approach was developed based on calibrating each WorldView-3 band against the ground-truth spectra. This correction allowed for the accurate signal normalization of WorldView-3 and Sentinel-2 imagery SR in the visible-to-near infrared regions.

ISPRS Journal of Photogrammetry and Remote Sensing

Stable isotope evidence for an atmospheric origin of desert nitrate deposits in northern Chile and southern California, U.S.A.

Natural surficial accumulations of nitrate-rich salts in the Atacama Desert, northern Chile, and in the Death Valley region of the Mojave Desert, southern California, are well known, but despite many geologic and geochemical studies, the origins of the nitrates have remained controversial. N and O isotopes in nitrate, and S isotopes in coexisting soluble sulfate, were measured to determine if some proposed N sources could be supported or rejected, and to determine if the isotopic signature of these natural deposits could be used to distinguish them from various types of anthropogenic nitrate contamination that might be found in desert groundwaters. High-grade calich-a-type nitrate deposits from both localities have δ 15 N values that range from −5 to +5‰, but are mostly near 0‰. Values of δ 15 N near 0‰ are consistent with either bulk atmospheric N deposition or microbial N fixation as major sources of the N in the deposits. δ 18 O values of those desert nitrates with δ 15 N near 0‰ range from about +31 to +50‰ (V-SMOW), significantly higher than that of atmospheric O 2 (+23.5‰). Such high values of δ 18 O are considered unlikely to result entirely from nitrification of reduced N, but rather resemble those of modern atmospheric nitrate in precipitation from some other localities. Assuming that limited modern atmospheric isotope data are applicable to the deposits, and allowing for nitrification of co-deposited ammonium, it is estimated that the fraction of the nitrate in the deposits that could be, accounted for isotopically by atmospheric N deposition may be at least 20% and possibly as much as 100%. δ 34 S values are less diagnostic but could also be consistent with atmospheric components in some of the soluble sulfates associated with the deposits. The stable isotope data support the hypothesis that some high-grade caliche-type nitrate-rich salt deposits in some of the Earth's hyperarid deserts represent long-term accumulations of atmospheric deposition (possibly in the order of 104 yr for the Death Valley region, 10 7 yr for the Atacama Desert) in the relative absence of soil leaching or biologic cycling. The combined N and O isotope signature of the nitrate in these deposits is significantly different from those of many other natural and anthropogenic sources of nitrate.

Chemical Geology

Strong atmospheric chemistry feedback to climate warming from Arctic methane emissions

The magnitude and feedbacks of future methane release from the Arctic region are unknown. Despite limited documentation of potential future releases associated with thawing permafrost and degassing methane hydrates, the large potential for future methane releases calls for improved understanding of the interaction of a changing climate with processes in the Arctic and chemical feedbacks in the atmosphere. Here we apply a “state of the art” atmospheric chemistry transport model to show that large emissions of CH4 would likely have an unexpectedly large impact on the chemical composition of the atmosphere and on radiative forcing (RF). The indirect contribution to RF of additional methane emission is particularly important. It is shown that if global methane emissions were to increase by factors of 2.5 and 5.2 above current emissions, the indirect contributions to RF would be about 250% and 400%, respectively, of the RF that can be attributed to directly emitted methane alone. Assuming several hypothetical scenarios of CH4 release associated with permafrost thaw, shallow marine hydrate degassing, and submarine landslides, we find a strong positive feedback on RF through atmospheric chemistry. In particular, the impact of CH4 is enhanced through increase of its lifetime, and of atmospheric abundances of ozone, stratospheric water vapor, and CO2 as a result of atmospheric chemical processes. Despite uncertainties in emission scenarios, our results provide a better understanding of the feedbacks in the atmospheric chemistry that would amplify climate warming.

Global Biogeochemical Cycles

Response of the water level in a well to Earth tides and atmospheric loading under unconfined conditions

The response of the water level in a well to Earth tides and atmospheric loading under unconfined conditions can be explained if the water level is controlled by the aquifer response averaged over the saturated depth of the well. Because vertical averaging tends to diminish the influence of the water table, the response is qualitatively similar to the response of a well under partially confined conditions. When the influence of well bore storage can be ignored, the response to Earth tides is strongly governed by a dimensionless aquifer frequency Q ′ u . The response to atmospheric loading is strongly governed by two dimensionless vertical fluid flow parameters: a dimensionless unsaturated zone frequency, R , and a dimensionless aquifer frequency Q u . The differences between Q ′ u and Q u are generally small for aquifers which are highly sensitive to Earth tides. When Q ′ u and Q u are large, the response of the well to Earth tides and atmospheric loading approaches the static response of the aquifer under confined conditions. At small values of Q ′ u and Q u , well response to Earth tides and atmospheric loading is strongly influenced by water table drainage. When R is large relative to Q u , the response to atmospheric loading is strongly influenced by attenuation and phase shift of the pneumatic pressure signal in the unsaturated zone. The presence of partial penetration retards phase advance in well response to Earth tides and atmospheric loading. When the theoretical response of a phreatic well to Earth tides and atmospheric loading is fit to the well response inferred from cross-spectral estimation, it is possible to obtain estimates of the pneumatic diffusivity of the unsaturated zone and the vertical hydraulic conductivity of the aquifer.

Water Resources Research

Effects of the atmosphere on the detection of surface changes from Landsat multispectral scanner data

The atmospheric effects on radiometric data recorded in the Landsat multispectral scanner system (MSS) bands are compiled for cases of representative and ideal atmospheric conditions. The effects are expressed as a difference between the Earth's surface spectral reflectivity, a 0 , and the surface-atmosphere system spectral reflectivity, a s , derived from the satellite data, a s &minus;a 0 = &minus;a 0 [l+(l/&mu; 0 )](B+W) + 2a 2 0 B + g(&mu; 0 )B/2&mu; 0 where &mu; 0 is the cosine of the solar zenith angle, B and W are the backscattering and absorption optical thickness respectively, and the function g( &mu; 0 ) is the anisotropy of backscattering to the zenith from the direct beam. This formula is accurate only for an atmosphere of low optical thickness. Also, the equation applies only to large areas having a uniform reflectivity, because adjacency effects due to reflection from the terrain surrounding the object pixel and subsequent scattering by the atmosphere are not considered. It is concluded that in the quantitative monitoring of surface changes from satellites, scattering effects predominate in some applications (for example, bathy-metric mapping of coastal waters), whereas absorption effects predominate in other applications (for example, monitoring desert fringe areas). Different measurements are more appropriate for assessing the scattering effects than for assessing the absorption effects. These effects on the monitoring of surface changes by the use of Landsat MSS data are discussed in terms of departures of the actual atmosphere at the time of a satellite passage from a &lsquo;minima&rsquo; atmosphere having no aerosols and characterized by gaseous absorption corresponding to minimal water vapour amounts.

International Journal of Remote Sensing

An assessment of the carbon balance of arctic tundra: comparisons among observations, process models, and atmospheric inversions

Although arctic tundra has been estimated to cover only 8% of the global land surface, the large and potentially labile carbon pools currently stored in tundra soils have the potential for large emissions of carbon (C) under a warming climate. These emissions as radiatively active greenhouse gases in the form of both CO 2 and CH 4 could amplify global warming. Given the potential sensitivity of these ecosystems to climate change and the expectation that the Arctic will experience appreciable warming over the next century, it is important to assess whether responses of C exchange in tundra regions are likely to enhance or mitigate warming. In this study we compared analyses of C exchange of Arctic tundra between 1990&ndash;1999 and 2000&ndash;2006 among observations, regional and global applications of process-based terrestrial biosphere models, and atmospheric inversion models. Syntheses of the compilation of flux observations and of inversion model results indicate that the annual exchange of CO 2 between arctic tundra and the atmosphere has large uncertainties that cannot be distinguished from neutral balance. The mean estimate from an ensemble of process-based model simulations suggests that arctic tundra acted as a sink for atmospheric CO 2 in recent decades, but based on the uncertainty estimates it cannot be determined with confidence whether these ecosystems represent a weak or a strong sink. Tundra was 0.6 &deg;C warmer in the 2000s compared to the 1990s. The central estimates of the observations, process-based models, and inversion models each identify stronger sinks in the 2000s compared with the 1990s. Similarly, the observations and the applications of regional process-based models suggest that CH 4 emissions from arctic tundra have increased from the 1990s to 2000s. Based on our analyses of the estimates from observations, process-based models, and inversion models, we estimate that arctic tundra was a sink for atmospheric CO 2 of 110 Tg C yr -1 (uncertainty between a sink of 291 Tg C yr -1 and a source of 80 Tg C yr -1 ) and a source of CH 4 to the atmosphere of 19 Tg C yr -1 (uncertainty between sources of 8 and 29 Tg C yr -1 ). The suite of analyses conducted in this study indicate that it is clearly important to reduce uncertainties in the observations, process-based models, and inversions in order to better understand the degree to which Arctic tundra is influencing atmospheric CO 2 and CH 4 concentrations. The reduction of uncertainties can be accomplished through (1) the strategic placement of more CO 2 and CH 4 monitoring stations to reduce uncertainties in inversions, (2) improved observation networks of ground-based measurements of CO 2 and CH 4 exchange to understand exchange in response to disturbance and across gradients of hydrological variability, and (3) the effective transfer of information from enhanced observation networks into process-based models to improve the simulation of CO 2 and CH 4 exchange from arctic tundra to the atmosphere.

Biogeosciences