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CO2 cycle

This chapter discusses the use of models, observations, and laboratory experiments to understand the cycling of CO2 between the atmosphere and seasonal Martian polar caps. This cycle is primarily controlled by the polar heat budget, and thus the emphasis here is on its components, including solar and infrared radiation, the effect of clouds (water- and CO2-ice), atmospheric transport, and subsurface heat conduction. There is a discussion about cap properties including growth and regression rates, albedos and emissivities, grain sizes and dust and/or water-ice contamination, and curious features like cold gas jets and araneiform (spider-shaped) terrain. The nature of the residual south polar cap is discussed as well as its long-term stability and ability to buffer atmospheric pressures. There is also a discussion of the consequences of the CO2 cycle as revealed by the non-condensable gas enrichment observed by Odyssey and modeled by various groups.

Book chapter↗

Tracking nonpoint source nitrogen pollution in human-impacted watersheds

Nonpoint source nitrogen (N) pollution is a leading contributor to U.S. water quality impairments. We combined watershed N mass balances and stable isotopes to investigate fate and transport of nonpoint N in forest, agricultural, and urbanized watersheds at the Baltimore Long-Term Ecological Research site. Annual N retention was 55%, 68%, and 82% for agricultural, suburban, and forest watersheds, respectively. Analysis of δ 15 N-NO 3 – , and δ 18 O-NO 3 – indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between δ 15 N-NO 3 – and δ 18 O-NO 3 – in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed ∼50% at peak storm N loads). Positive correlations between δ 15 N-NO 3 – and δ 18 O-NO 3 – in watersheds suggested denitrification was removing septic system and agriculturally derived N, but N from belowground leaking sewers was less susceptible to denitrification. N transformations were also observed in a storm drain (no natural drainage network) potentially due to organic carbon inputs. Overall, nonpoint sources such as atmospheric deposition, wastewater, and fertilizer showed different susceptibility to watershed N export. There were large changes in nitrate sources as a function of runoff, and anticipating source changes in response to climate and storms will be critical for managing nonpoint N pollution.

Environmental Science & Technology↗

Marine bacterial degradation of brominated methanes

Brominated methanes are ozone-depleting compounds whose natural sources include marine algae such as kelp. Brominated methane degradation by bacteria was investigated to address whether bacterial processes might effect net emission of these compounds to the atmosphere. Bacteria in seawater collected from California kelp beds degraded CH2Br2 but not CHBr3. Specific inhibitors showed that methanotrophs and nitrifiers did not significantly contribute to CH2Br2 removal. A seawater enrichment culture oxidized 14CH2Br2 to 14CO2 as well as 14CH3Br to 14CO2. The rates of CH2Br2 degradation in laboratory experiments suggest that bacterial degradation of CH2Br2 in a kelp bed accounts for <1% of the CH2Br2 produced by the kelp. However, the half-life of CH2Br2 due to bacterial removal appears faster than hydrolysis and within an order of magnitude of volatilization to the atmosphere.Brominated methanes are ozone-depleting compounds whose natural sources include marine algae such as kelp. Brominated methane degradation by bacteria was investigated to address whether bacterial processes might effect net emission of these compounds to the atmosphere. Bacteria in seawater collected from California kelp beds degraded CH2Br2 but not CHBr3. Specific inhibitors showed that methanotrophs and nitrifiers did not significantly contribute to CH2Br2 removal. A seawater enrichment culture oxidized 14CH2Br2 to 14CO2 as well as 14CH3Br to 14CO2. The rates of CH2Br2 degradation in laboratory experiments suggest that bacterial degradation of CH2Br2 in a kelp bed accounts for <1% of the CH2Br2 produced by the kelp. However, the half-life of CH2Br2 due to bacterial removal appears faster than hydrolysis and within an order of magnitude of volatilization to the atmosphere.

Environmental Science & Technology↗

Retention of NO3/- in an upland stream environment: A mass balance approach

Models of the effects of atmospheric N deposition in forested watersheds have not adequately accounted for the effects of aquatic and near-stream processes on the concentrations and loads of NO3/- in surface waters. This study compared the relative effects of aquatic and near-stream processes with those from the terrestrial ecosystem on the retention and transport of NO3/- in two contrasting stream reaches of the Neversink River, a forested watershed in the Catskill Mountains of New York that receives among the highest load of atmospheric N deposition in the northeastern United States. Stream water samples were collected every two hours and ground-water and tributary samples were collected daily at base flow conditions during four 48-hour periods from April to October 1992, and NO3/- mass balances were calculated for each site. Results indicated diurnal variations in stream NO3/- concentrations in both reaches during all four sampling periods; this is consistent with uptake of NO3/- by photoautotrophs during daylight hours. Mass-balance results revealed significant stream reach losses of NO3/- at both sites during all sampling periods. The diurnal variations in NO3/- concentrations and the retention of NO3/- relative to terrestrial contributions to the stream reaches were greater downstream than upstream because physical factors such as the head gradients of inflowing ground water and the organic matter content of sediment are more favorable to uptake and denitrification downstream. The mass retention of NO3/- increased as the mean 48-hr stream discharge increased at each site, indicating that the responsible processes are dependent on NO3/- supply. Low stream temperatures during the April sampling period, however, probably reduced the rate of retention processes, resulting in smaller losses of NO3/- than predicted from stream discharge alone. Water samples collected from the stream, the hyporheic zone, and the alluvial ground water at sites in both reaches indicated that the net effect of hyporheic processes on downstream NO3/- transport ranged from conservative mixing to complete removal by denitrification. The relative effects of biological uptake and denitrification as retention mechanisms could not be quantified, but the results indicate that both processes are significant. These results generally confirm that aquatic and near-stream processes cause significant losses of NO3/- in the Neversink River, and that the losses by these processes at downstream locations can exceed the NO3/- contributions to the stream from the terrestrial environment during summer and fall base-flow conditions. Failure to consider these aquatic and near-stream processes in models of watershed response to atmospheric N deposition could result in underestimates of the amount of NO3/- leaching from forested ecosystems and to an inability to unequivocally relate geographic differences in NO3/- concentrations of stream waters to corresponding differences in terrestrial processes.

Biogeochemistry↗

Contaminants in arctic snow collected over northwest Alaskan sea ice

Snow cores were collected over sea ice from four northwest Alaskan Arctic estuaries that represented the annual snowfall from the 1995-1996 season. Dissolved trace metals, major cations and anions, total mercury, and organochlorine compounds were determined and compared to concentrations in previous arctic studies. Traces (<4 nanograms per liter, ng L-1) of cis- and trans-chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, dieldrin, endosulfan II, and PCBs were detected in some samples, with endosulfan I consistently present. High chlorpyrifos concentrations (70-80 ng L-1) also were estimated at three sites. The snow was highly enriched in sulfates (69- 394 mg L-1), with high proportions of nonsea salt sulfates at three of five sites (9 of 15 samples), thus indicating possible contamination through long-distance transport and deposition of sulfate-rich atmospheric aerosols. Mercury, cadmium, chromium, molybdenum, and uranium were typically higher in the marine snow (n = 15) in relation to snow from arctic terrestrial studies, whereas cations associated with terrigenous sources, such as aluminum, frequently were lower over the sea ice. One Kasegaluk Lagoon site (Chukchi Sea) had especially high concentrations of total mercury (mean = 214 ng L-1, standard deviation = 5 ng L-1), but no methyl mercury was detected above the method detection limit (0.036 ng L-1) at any of the sites. Elevated concentrations of sulfate, mercury, and certain heavy metals might indicate mechanisms of contaminant loss from the arctic atmosphere over marine water not previously reported over land areas. Scavenging by snow, fog, or riming processes and the high content of deposited halides might facilitate the loss of such contaminants from the atmosphere. Both the mercury and chlorpyrifos concentrations merit further investigation in view of their toxicity to aquatic organisms at low concentrations.

Water, Air, & Soil Pollution↗

Historical and projected carbon balance of mature black spruce ecosystems across north america: The role of carbon-nitrogen interactions

The role of carbon (C) and nitrogen (N) interactions on sequestration of atmospheric CO2 in black spruce ecosystems across North America was evaluated with the Terrestrial Ecosystem Model (TEM) by applying parameterizations of the model in which C-N dynamics were either coupled or uncoupled. First, the performance of the parameterizations, which were developed for the dynamics of black spruce ecosystems at the Bonanza Creek Long-Term Ecological Research site in Alaska, were evaluated by simulating C dynamics at eddy correlation tower sites in the Boreal Ecosystem Atmosphere Study (BOREAS) for black spruce ecosystems in the northern study area (northern site) and the southern study area (southern site) with local climate data. We compared simulated monthly growing season (May to September) estimates of gross primary production (GPP), total ecosystem respiration (RESP), and net ecosystem production (NEP) from 1994 to 1997 to available field-based estimates at both sites. At the northern site, monthly growing season estimates of GPP and RESP for the coupled and uncoupled simulations were highly correlated with the field-based estimates (coupled: R2= 0.77, 0.88 for GPP and RESP; uncoupled: R2 = 0.67, 0.92 for GPP and RESP). Although the simulated seasonal pattern of NEP generally matched the field-based data, the correlations between field-based and simulated monthly growing season NEP were lower (R2 = 0.40, 0.00 for coupled and uncoupled simulations, respectively) in comparison to the correlations between field-based and simulated GPP and RESP. The annual NEP simulated by the coupled parameterization fell within the uncertainty of field-based estimates in two of three years. On the other hand, annual NEP simulated by the uncoupled parameterization only fell within the field-based uncertainty in one of three years. At the southern site, simulated NEP generally matched field-based NEP estimates, and the correlation between monthly growing season field-based and simulated NEP (R2 = 0.36, 0.20 for coupled and uncoupled simulations, respectively) was similar to the correlations at the northern site. To evaluate the role of N dynamics in C balance of black spruce ecosystems across North America, we simulated historical and projected C dynamics from 1900 to 2100 with a global-based climatology at 0.5?? resolution (latitude ?? longitude) with both the coupled and uncoupled parameterizations of TEM. From analyses at the northern site, several consistent patterns emerge. There was greater inter-annual variability in net primary production (NPP) simulated by the uncoupled parameterization as compared to the coupled parameterization, which led to substantial differences in inter-annual variability in NEP between the parameterizations. The divergence between NPP and heterotrophic respiration was greater in the uncoupled simulation, resulting in more C sequestration during the projected period. These responses were the result of fundamentally different responses of the coupled and uncoupled parameterizations to changes in CO2 and climate. Across North American black spruce ecosystems, the range of simulated decadal changes in C storage was substantially greater for the uncoupled parameterization than for the coupled parameterization. Analysis of the spatial variability in decadal responses of C dynamics revealed that C fluxes simulated by the coupled and uncoupled parameterizations have different sensitivities to climate and that the climate sensitivities of the fluxes change over the temporal scope of the simulations. The results of this study suggest that uncertainties can be reduced through (1) factorial studies focused on elucidating the role of C and N interactions in the response of mature black spruce ecosystems to manipulations of atmospheric CO2 and climate, (2) establishment of a network of continuous, long-term measurements of C dynamics across the range of mature black spruce ecosystems in North America, and (3) ancillary measureme

Conference Paper↗

100 years of Pb deposition and transport in soils in Champaign, Illinois, U.S.A

In Illinois, atmospheric deposition is one major source of heavy metal inputs to agricultural land. The atmospheric Pb deposition and transport record in agricultural soils in Champaign, Illinois, was established by studying surface and subsurface soil samples collected during the past 100 years from the Morrow Plots on the campus of the University of Illinois at Urbana-Champaign. The Pb content in the soil samples was measured and the Ph deposition fluxes were calculated. The Pb content in surface soils increased sharply in the first half of the 20th century, and stayed invariant since. The maximum Pb flux from the atmosphere was estimated to be 27 (??14) ??g cm-2 yr-1 around 1940. The major pollution source for this increase probably was residential coal burning. It was estimated that in 50 yr, more than 50% of the Pb input had been lost from the surface soils.

Water, Air, & Soil Pollution↗

Attention turns to naturally occurring methane seepage

Methane is the most abundant organic compound in the Earth's atmosphere. As a powerful greenhouse gas, it has implications for global climate change. Sources of methane to the atmosphere are varied. Depending on the source, methane can contain either modern or ancient carbon. Methane exiting from swamps and wetlands contains modern carbon, whereas methane leaking from petroleum reservoirs contains ancient carbon. The total annual source of methane to the atmosphere has been constrained to about 540 teragrams (Tg) per year “ Cicerone and Oremland , 1988”. Notably absent from any identified sources is the contribution of geologically sourced methane from naturally occurring seepage.

Eos, Earth and Space Science News↗

Methane flux in subalpine wetland and unsaturated soils in the southern Rocky Mountains

Methane exchange between the atmosphere and subalpine wetland and unsaturated soils was evaluated over a 15-month period during 1995-1996. Four vegetation community types along a moisture gradient (wetland, moist-grassy, moist-mossy, and dry) were included in a 100 m sampling transect situated at 3200 m elevation in Rocky Mountain National Park, Colorado. Methane fluxes and soil temperature were measured during snow-free and snow-covered periods, and soil moisture content was measured during snow-free periods. The range of mean measured fluxes through all seasons (a positive value represents CH4 efflux to the atmosphere) were: 0.3 to 29.2 mmol CH4 m-2 d-1 wetland area; 0.1 to 1.8 mmol CH4 m-2 d-1, moist-grassy area; -0.04 to 0.7 mmol CH4 m-2 d-1, moist-mossy area; and -0.6 to 0 mmol CH4 m-2 d-1, dry area. Methane efflux was significantly correlated with soil temperature (5 cm) at the continuously saturated wetland area during snow-free periods. Consumption of atmospheric methane was significantly correlated with moisture content in the upper 5 cm of soil at the dry area. A model based on the wetland flux-temperature relationship estimated an annual methane emission of 2.53 mol CH4 m-2 from the wetland. Estimates of annual methane flux based on field measurements at the other sites were 0.12 mol CH4 m-2, moist-grassy area; 0.03 mol CH4 m-2, moist-mossy area; and -0.04 mol CH4 m-2, dry area. Methane fluxes during snow-covered periods were responsible for 25, 73, 23, and 43% of the annual fluxes at the wetland, moist-grassy, moist-mossy, and dry sites, respectively.

Global Biogeochemical Cycles↗

The potential for calcium depletion in forest ecosystems of southeastern United States: Review and analysis

Biogeochemical mass balance assessments of calcium status in southeastern forests indicate that losses through harvesting and soil leaching often exceed inputs from atmospheric deposition and weathering. Many forest soils of the southeastern United States are particularly sensitive because these soils and the underlying saprolite from which these soils are derived are largely depleted of weatherable calcium. At most of the intensively studied sites in the southeastern United States, it is estimated that calcium depletion has already reduced or will likely reduce exchangeable soil calcium reserves to less than the estimated requirement for a merchantable forest stand in 150 years or less. At most sites, calcium uptake into merchantable wood equals or exceeds soil leaching losses. Chronic atmospheric deposition of sulfate and nitrate and declining atmospheric deposition of calcium are likely to accelerate calcium depletion. The southeastern U.S. regional distribution of soil calcium pools and calcium fluxes (deposition and uptake in merchantable wood) indicates that the depletion status of the intensively studied sites is representative of a substantially larger area. Where weathering inputs are insufficient to replace leaching and uptake losses, there is a potential for a regional problem in forest nutrition over the long term.

Alabama, Arkansas, Florida, Georgia, Louisiana, Ma↗

Identification of a basaltic component on the Martian surface from Thermal Emission Spectrometer data

The Mars Global Surveyor Thermal Emission Spectrometer (TES) instrument collected 4.8×10 6 spectra of Mars during the initial aerobraking and science‐phasing periods of the mission (September 14, 1997, through April 29, 1998). Two previously developed atmosphere‐removal models were applied to data from Cimmeria Terra (25°S, 213°W). The surface spectra derived for these two models agree well, indicating that the surface and atmosphere emission can be separated and that the exact atmosphere‐removal model used has little effect on the derived surface composition. The Cimmeria spectra do not match terrestrial high‐silica igneous rocks (granite and rhyolite), ultramafic igneous rocks, limestone, or quartz‐ and clay‐rich sandstone and siltstone. A particulate (sand‐sized) sample of terrestrial flood basalt does provide an excellent match in both spectral shape and band depth to the Cimmeria spectrum over the entire TES spectral range. No unusual particle size effects are required to account for the observed spectral shape and depth. The implied grain size is consistent with the thermal inertia and albedo of this region, which indicate a sand‐sized surface with little dust. The identification of basalt is consistent with previous indications of pyroxene and basalt‐like compositions from visible/near‐infrared and thermal‐infrared spectral measurements. A linear spectral deconvolution model was applied to both surface‐only Cimmeria spectra using a library of 60 minerals to determine the composition and abundance of the component minerals. Plagioclase feldspar (45%; 53%) and clinopyroxene (26%; 19%) were positively identified above an estimated detection threshold of 10–15% for these minerals. The TES observations provide the first identification of feldspars on Mars. The best fit to the Mars data includes only clinopyroxene compositions; no orthopyroxene compositions are required to match the Cimmeria spectra. Olivine (12%; 12%) and sheet silicate (15%; 11%) were identified with lower confidence. Carbonates, quartz, and sulfates were not identified in Cimmeria at detection limits of ∼5, 5, and 10%, respectively. Their presence elsewhere, however, remains open. The Cimmeria spectra are not well matched by any one SNC meteorite spectrum, indicating that this region is not characterized by a single SNC lithology. The occurrence of unweathered feldspar and pyroxene in Cimmeria, together with the inferred presence of pyroxene and unweathered basalts in other dark regions and at the Viking and Pathfinder landing sites, provides evidence that extensive global chemical weathering of materials currently exposed on the Martian surface has not occurred.

Journal of Geophysical Research: Planets↗

Carbon gas exchange at a southern Rocky Mountain wetland, 1996-1998

Carbon dioxide (CO2) and methane (CH4) exchange between the atmosphere and a subalpine wetland located in Rocky Mountain National Park, Colorado, at 3200 m elevation were measured during 1996-1998. Respiration, net CO2 flux, and CH4 flux were measured using the closed chamber method during snow-free periods and using gas diffusion calculations during snow-covered periods. The ranges of measured flux were 1.2-526 mmol CO2 m-2 d-1 (respiration), -1056-100 mmol CO2 m-2 d-1 (net CO2 exchange), and 0.1-36.8 mmol CH4 m-2 d-1 (a positive value represents efflux to the atmosphere). Respiration and CH4 emission were significantly correlated with 5 cm soil temperature. Annual respiration and CH4 emission were modeled by applying the flux-temperature relationships to a continuous soil temperature record during 1996-1998. Gross photosynthesis was modeled using a hyperbolic equation relating gross photosynthesis, photon flux density, and soil temperature. Modeled annual flux estimates indicate that the wetland was a net source of carbon gas to the atmosphere each of the three years: 8.9 mol C m-2 yr-1 in 1996, 9.5 mol C m-2 yr-1 in 1997, and 9.6 mol C m-2 yr-1 in 1998. This contrasts with the long-term carbon accumulation of ???0.7 mol m-2 yr-1 determined from 14C analyses of a peat core collected from the wetland.

Global Biogeochemical Cycles↗

Mars Global Surveyor Thermal Emission Spectrometer experiment: Investigation description and surface science results

The Thermal Emission Spectrometer (TES) investigation on Mars Global Surveyor (MGS) is aimed at determining (1) the composition of surface minerals, rocks, and ices; (2) the temperature and dynamics of the atmosphere; (3) the properties of the atmospheric aerosols and clouds; (4) the nature of the polar regions; and (5) the thermophysical properties of the surface materials. These objectives are met using an infrared (5.8- to 50-μm) interferometric spectrometer, along with broadband thermal (5.1- to 150-μm) and visible/near-IR (0.3- to 2.9-μm) radiometers. The MGS TES instrument weighs 14.47 kg, consumes 10.6 W when operating, and is 23.6×35.5×40.0 cm in size. The TES data are calibrated to a 1-σ precision of 2.5 −6 ×10 −8 W cm −2 sr −1 /cm −1 , 1.6×10 −6 W cm −2 sr −1 , and ∼0.5 K in the spectrometer, visible/near-IR bolometer, and IR bolometer, respectively. These instrument subsections are calibrated to an absolute accuracy of ∼4×10 −8 W cm −2 sr −1 /cm −1 (0.5 K at 280 K), 1–2%, and ∼1–2 K, respectively. Global mapping of surface mineralogy at a spatial resolution of 3 km has shown the following: (1) The mineralogic composition of dark regions varies from basaltic, primarily plagioclase feldspar and clinopyroxene, in the ancient, southern highlands to andesitic, dominated by plagioclase feldspar and volcanic glass, in the younger northern plains. (2) Aqueous mineralization has produced gray, crystalline hematite in limited regions under ambient or hydrothermal conditions; these deposits are interpreted to be in-place sedimentary rock formations and indicate that liquid water was stable near the surface for a long period of time. (3) There is no evidence for large-scale (tens of kilometers) occurrences of moderate-grained (>50-μm) carbonates exposed at the surface at a detection limit of ∼10%. (4) Unweathered volcanic minerals dominate the spectral properties of dark regions, and weathering products, such as clays, have not been observed anywhere above a detection limit of ∼10%; this lack of evidence for chemical weathering indicates a geologic history dominated by a cold, dry climate in which mechanical, rather than chemical, weathering was the significant form of erosion and sediment production. (5) There is no conclusive evidence for sulfate minerals at a detection limit of ∼15%. The polar region has been studied with the following major conclusions: (1) Condensed CO 2 has three distinct end-members, from fine-grained crystals to slab ice. (2) The growth and retreat of the polar caps observed by MGS is virtually the same as observed by Viking 12 Martian years ago. (3) Unique regions have been identified that appear to differ primarily in the grain size of CO 2 ; one south polar region appears to remain as black slab CO 2 ice throughout its sublimation. (4) Regional atmospheric dust is common in localized and regional dust storms around the margin and interior of the southern cap. Analysis of the thermophysical properties of the surface shows that (1) the spatial pattern of albedo has changed since Viking observations, (2) a unique cluster of surface materials with intermediate inertia and albedo occurs that is distinct from the previously identified low-inertia/bright and high-inertia/dark surfaces, and (3) localized patches of high-inertia material have been found in topographic lows and may have been formed by a unique set of aeolian, fluvial, or erosional processes or may be exposed bedrock.

Journal of Geophysical Research E: Planets↗

Carbon cycling under 300 years of land use change: importance of the secondary vegetation sink

We have developed a dynamic land model (LM3V) able to simulate ecosystem dynamics and exchanges of water, energy, and CO 2 between land and atmosphere. LM3V is specifically designed to address the consequences of land use and land management changes including cropland and pasture dynamics, shifting cultivation, logging, fire, and resulting patterns of secondary regrowth. Here we analyze the behavior of LM3V, forced with the output from the Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric model AM2, observed precipitation data, and four historic scenarios of land use change for 1700-2000. Our analysis suggests a net terrestrial carbon source due to land use activities from 1.1 to 1.3 GtC/a during the 1990s, where the range is due to the difference in the historic cropland distribution. This magnitude is substantially smaller than previous estimates from other models, largely due to our estimates of a secondary vegetation sink of 0.35 to 0.6 GtC/a in the 1990s and decelerating agricultural land clearing since the 1960s. For the 1990s, our estimates for the pastures' carbon flux vary from a source of 0.37 to a sink of 0.15 GtC/a, and for the croplands our model shows a carbon source of 0.6 to 0.9 GtC/a. Our process-based model suggests a smaller net deforestation source than earlier bookkeeping models because it accounts for decelerated net conversion of primary forest to agriculture and for stronger secondary vegetation regrowth in tropical regions. The overall uncertainty is likely to be higher than the range reported here because of uncertainty in the biomass recovery under changing ambient conditions, including atmospheric CO 2 concentration, nutrients availability, and climate. Copyright 2009 by the American Geophysical Union.

Global Biogeochemical Cycles↗

Dating groundwater with trifluoromethyl sulfurpentafluoride (SF 5CF3), sulfur hexafluoride (SF6), CF 3Cl (CFC-13), and CF2Cl2 (CFC-12)

[1] A new groundwater dating procedure using the transient atmospheric signal of the environmental tracers SF5CF3, CFC-13, SF6, and CFC-12 was developed. The analytical procedure determines concentrations of the four tracers in air and water samples. SF 5CF3 and CFC-13 can be used to date groundwaters in some environments where the CFCs and SF6 have previously failed because these new tracers have increasing atmospheric input functions, no known terrigenic source, and are believed to be stable under reducing conditions. SF5CF3 has a dating range from 1970 to modern; the mixing ratio (mole fraction) in North American air has increased from the detection limit of 0.005 parts per trillion (ppt) to the 2006 mole fraction of about 0.16 ppt. No evidence was found for degradation of SF5CF3 in laboratory anaerobic systems. The solubility of SF5CF3 was measured in water from 1 to 35??C. Groundwater samples that contained large amounts of terrigenic SF6 did not contain terrigenic SF 5CF3. CFC-13 is a trace atmospheric gas with a dating range in groundwater of about 1965 to modem. CFC-13 has been used primarily in very low-temperature refrigeration; thus groundwater environments are less likely to be contaminated with nonatmospheric sources as compared to other widely used CFCs. Because of the low solubility of SF5CF3 and CFC-13 in water, an excess air correction must be applied to the apparent ages. The new dating procedure was tested in water samples from wells and springs from Maryland, Virginia, and West Virginia.

Water Resources Research↗

Hydrologic support of carbon dioxide flux revealed by whole-lake carbon budgets

Freshwater lakes are an important component of the global carbon cycle through both organic carbon (OC) sequestration and carbon dioxide (CO 2 ) emission. Most lakes have a net annual loss of CO 2 to the atmosphere and substantial current evidence suggests that biologic mineralization of allochthonous OC maintains this flux. Because net CO 2 flux to the atmosphere implies net mineralization of OC within the lake ecosystem, it is also commonly assumed that net annual CO 2 emission indicates negative net ecosystem production (NEP). We explored the relationship between atmospheric CO 2 emission and NEP in two lakes known to have contrasting hydrologie characteristics and net CO 2 emission. We calculated NEP for calendar year 2004 using whole-lake OC and inorganic carbon (IC) budgets, NEP oc and NEP IC , respectively, and compared the resulting values to measured annual CO 2 flux from the lakes. In both lakes, NEP Ic and NEP Ic were positive, indicating net autotrophy. Therefore CO 2 emission from these lakes was apparently not supported by mineralization of allochthonous organic material. In both lakes, hydrologie CO 2 inputs, as well as CO 2 evolved from netcalcite precipitation, could account for the net CO 2 emission. NEP calculated from diel CO 2 measurements was also affected by hydrologie inputs of CO 2 . These results indicate that CO 2 emission and positive NEP may coincide in lakes, especially in carbonate terrain, and that all potential geologic, biogeochemical, and hydrologie sources of CO 2 need to be accounted for when using CO 2 concentrations to infer lake NEP. Copyright 2009 by the American Geophysical Union.

Journal of Geophysical Research G: Biogeosciences↗

Is the northern high-latitude land-based CO2 sink weakening?

Studies indicate that, historically, terrestrial ecosystems of the northern high-latitude region may have been responsible for up to 60% of the global net land-based sink for atmospheric CO2. However, these regions have recently experienced remarkable modification of the major driving forces of the carbon cycle, including surface air temperature warming that is significantly greater than the global average and associated increases in the frequency and severity of disturbances. Whether Arctic tundra and boreal forest ecosystems will continue to sequester atmospheric CO2 in the face of these dramatic changes is unknown. Here we show the results of model simulations that estimate a 41 Tg C yr-1 sink in the boreal land regions from 1997 to 2006, which represents a 73% reduction in the strength of the sink estimated for previous decades in the late 20th century. Our results suggest that CO 2 uptake by the region in previous decades may not be as strong as previously estimated. The recent decline in sink strength is the combined result of (1) weakening sinks due to warming-induced increases in soil organic matter decomposition and (2) strengthening sources from pyrogenic CO2 emissions as a result of the substantial area of boreal forest burned in wildfires across the region in recent years. Such changes create positive feedbacks to the climate system that accelerate global warming, putting further pressure on emission reductions to achieve atmospheric stabilization targets. Copyright 2011 by the American Geophysical Union.

Global Biogeochemical Cycles↗

Opportunity Mars Rover mission: Overview and selected results from Purgatory ripple to traverses to Endeavour crater

Opportunity has been traversing the Meridiani plains since 25 January 2004 (sol 1), acquiring numerous observations of the atmosphere, soils, and rocks. This paper provides an overview of key discoveries between sols 511 and 2300, complementing earlier papers covering results from the initial phases of the mission. Key new results include (1) atmospheric argon measurements that demonstrate the importance of atmospheric transport to and from the winter carbon dioxide polar ice caps; (2) observations showing that aeolian ripples covering the plains were generated by easterly winds during an epoch with enhanced Hadley cell circulation; (3) the discovery and characterization of cobbles and boulders that include iron and stony-iron meteorites and Martian impact ejecta; (4) measurements of wall rock strata within Erebus and Victoria craters that provide compelling evidence of formation by aeolian sand deposition, with local reworking within ephemeral lakes; (5) determination that the stratigraphy exposed in the walls of Victoria and Endurance craters show an enrichment of chlorine and depletion of magnesium and sulfur with increasing depth. This result implies that regional-scale aqueous alteration took place before formation of these craters. Most recently, Opportunity has been traversing toward the ancient Endeavour crater. Orbital data show that clay minerals are exposed on its rim. Hydrated sulfate minerals are exposed in plains rocks adjacent to the rim, unlike the surfaces of plains outcrops observed thus far by Opportunity. With continued mechanical health, Opportunity will reach terrains on and around Endeavour's rim that will be markedly different from anything examined to date.

Journal of Geophysical Research E: Planets↗