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Assessment of environments for Mars Science Laboratory entry, descent, and surface operations

The Mars Science Laboratory mission aims to land a car-sized rover on Mars' surface and operate it for at least one Mars year in order to assess whether its field area was ever capable of supporting microbial life. Here we describe the approach used to identify, characterize, and assess environmental risks to the landing and rover surface operations. Novel entry, descent, and landing approaches will be used to accurately deliver the 900-kg rover, including the ability to sense and "fly out" deviations from a best-estimate atmospheric state. A joint engineering and science team developed methods to estimate the range of potential atmospheric states at the time of arrival and to quantitatively assess the spacecraft's performance and risk given its particular sensitivities to atmospheric conditions. Numerical models are used to calculate the atmospheric parameters, with observations used to define model cases, tune model parameters, and validate results. This joint program has resulted in a spacecraft capable of accessing, with minimal risk, the four finalist sites chosen for their scientific merit. The capability to operate the landed rover over the latitude range of candidate landing sites, and for all seasons, was verified against an analysis of surface environmental conditions described here. These results, from orbital and model data sets, also drive engineering simulations of the rover's thermal state that are used to plan surface operations.

Space Science Reviews

Stability of streams and lakes on Mars

Under present climatic conditions streams and lakes on Mars will freeze. Freezing is slow and would have a negligible effect in impeding flow of the large floods that are believed to have eroded the outflow channels. Valley networks are more difficult to form under current climatic conditions since they appear to have formed by slow erosion by streams of modest discharges. Freezing of small Martian streams was modeled for a variety of climatic conditions on the supposition that the Martian atmosphere may have been considerably thicker in the past when the valley networks formed. The modeling involves examination of the energy balance at the upper and lower surfaces of ice on streams to determine the rate at which the ice thickens with time. The results indicate that freezing rates are not strongly dependent on atmospheric pressure. With no wind, increasing the pressure by a factor of 10 cuts the time taken to freeze solid only by about a factor of about 2. Under windy conditions dependence on atmospheric pressure is even weaker. The distance that water could travel in a stream before flow is arrested by freezing is also calculated. The distances depend on the initial temperature of the stream and when icings develop, but in general, if a stream deeper than 2 m can be initiated and sustained, the water within it can survive long enough to cut most of the valley networks observed. The main problem with forming the valley is initiating the flow. Groundwater seepage alone appears inadequate because of the difficulty of recharging the groundwater system. Melting of ice precipitated onto the surface following injection of water into the atmosphere by large impacts is a possible source of water, but the climatic conditions under which the ice could melt and the water be collected into streams that can survive long enough to cut the valley is uncertain.

Icarus

Heating rates in furnace atomic absorption using the L'vov platform

Heating rate profiles for the furnace tube wall, the furnace atmosphere, and a L'vov platform were established for a range of conditions in a cyclically heated graphite atomizer. The tube wall profile was made by direct observation with a recording optical pyrometer. The sodium line reversal method was used to establish the heating rate of the furnace atmosphere, and appearance temperatures for a series metals of differing volatility was used to establish platform profiles. The tube wall heating rate was nearly linear at 2240°C s − until the desired temperature was reached after which the temperature remained constant. The furnace atmosphere reached a given temperature 0.2–0.4 s later than the tube wall through most of the atomize cycle. The platform lagged the tube wall 0.5–0.8 s. Under typical operating conditions the furnace atmosphere was 100–200°C cooler than the tube wall and at nearly constant temperature when the analyte vaporized from the platform. The L'vov platform causes the cyclically heated commercial furnace to approximate the behavior of a constant temperature furnace during atomization.

Spectrochimica Acta Part B: Atomic Spectroscopy

A new sampler for the collection and retrieval of dry dust deposition

Atmospheric dust can influence biogeochemical cycles, accelerate snowmelt, and affect air, water quality, and human health. Yet, the bulk of atmospherically transported material remains poorly quantified in terms of total mass fluxes and composition. This lack of information stems in part from the challenges associated with measuring dust deposition. Here we report on the design and efficacy of a new dry deposition sampler (Dry Deposition Sampling Unit (DSU)) and method that quantifies the gravitational flux of dust particles. The sampler can be used alone or within existing networks such as those employed by the National Atmospheric Deposition Program (NADP). Because the samplers are deployed sterile and the use of water to remove trapped dust is not required, this method allows for the recovery of unaltered dry material suitable for subsequent chemical and microbiological analyses. The samplers were tested in the laboratory and at 15 field sites in the western United States. With respect to material retention, sampler performance far exceeded commonly used methods. Retrieval efficiency was >97% in all trials and the sampler effectively preserved grain size distributions during wind exposure experiments. Field tests indicated favorable comparisons to dust-on-snow measurement across sites ( r 2 0.70, p < 0.05) and within sites to co-located aerosol data ( r 2 0.57–0.99, p < 0.05). The inclusion of dust deposition and composition monitoring into existing networks increases spatial and temporal understanding of the atmospheric transport on materials and substantively furthers knowledge of the effects of dust on terrestrial ecosystems and human exposure to dust and associated deleterious compounds.

Arizona, California, Colorado, Idaho, Nevada, Utah

The fate of cyanide in leach wastes at gold mines: an environmental perspective

This paper reviews the basic chemistry of cyanide, methods by which cyanide can be analyzed, and aspects of cyanide behavior that are most relevant to environmental considerations at mineral processing operations associated with gold mines. The emphasis is on research results reported since 1999 and on data gathered for a series of U.S. Geological Survey studies that began in the late 1990s. Cyanide is added to process solutions as the CN &minus; anion, but ore leaching produces numerous other cyanide-containing and cyanide-related species in addition to the desired cyanocomplex of gold. These can include hydrogen cyanide (HCN); cyanometallic complexes of iron, copper, zinc, nickel, and many other metals; cyanate (CNO &minus; ); and thiocyanate (SCN &minus; ). The fate of these species in solid wastes and residual process solutions that remain once gold recovery activities are terminated and in any water that moves beyond the ore processing facility dictates the degree to which cyanide poses a risk to aquatic organisms and aquatic-dependent organisms in the local environment. Cyanide-containing and cyanide-related species are subject to attenuation mechanisms that lead to dispersal to the atmosphere, chemical transformation to other carbon and nitrogen species, or sequestration as cyanometallic precipitates or adsorbed species on mineral surfaces. Dispersal to the atmosphere and chemical transformation amount to permanent elimination of cyanide, whereas sequestration amounts to storage of cyanide in locations from which it can potentially be remobilized by infiltrating waters if conditions change. From an environmental perspective, the most significant cyanide releases from gold leach operations involve catastrophic spills of process solutions or leakage of effluent to the unsaturated or saturated zones. These release pathways are unfavorable for two important cyanide attenuation mechanisms that tend to occur naturally: dispersal of free cyanide to the atmosphere and sunlight-catalyzed dissociation of strong cyanometallic complexes, which produces free cyanide that can then disperse to the atmosphere. The widest margins of environmental safety will be achieved where mineral processing operations are designed so that time for offgassing, aeration, and sunlight exposure are maximized in the event that cyanide-bearing solutions are released inadvertently.

Applied Geochemistry

Mars chronology: Assessing techniques for quantifying surficial processes

Currently, the absolute chronology of Martian rocks, deposits and events is based mainly on crater counting and remains highly imprecise with epoch boundary uncertainties in excess of 2 billion years. Answers to key questions concerning the comparative origin and evolution of Mars and Earth will not be forthcoming without a rigid Martian chronology, enabling the construction of a time scale comparable to Earth's. Priorities for exploration include calibration of the cratering rate, dating major volcanic and fluvial events and establishing chronology of the polar layered deposits. If extinct and/or extant life is discovered, the chronology of the biosphere will be of paramount importance. Many radiometric and cosmogenic techniques applicable on Earth and the Moon will apply to Mars after certain baselines (e.g. composition of the atmosphere, trace species, chemical and physical characteristics of Martian dust) are established. The high radiation regime may pose a problem for dosimetry-based techniques (e.g. luminescence). The unique isotopic composition of nitrogen in the Martian atmosphere may permit a Mars-specific chronometer for tracing the time-evolution of the atmosphere and of lithic phases with trapped atmospheric gases. Other Mars-specific chronometers include measurement of gas fluxes and accumulation of platinum group elements (PGE) in the regolith. Putting collected samples into geologic context is deemed essential, as is using multiple techniques on multiple samples. If in situ measurements are restricted to a single technique it must be shown to give consistent results on multiple samples, but in all cases, using two or more techniques (e.g. on the same lander) will reduce error. While there is no question that returned samples will yield the best ages, in situ techniques have the potential to be flown on multiple missions providing a larger data set and broader context in which to place the more accurate dates. ?? 2004 Elsevier B.V. All rights reserved.

Earth-Science Reviews

Elevated CO2 enables brackish marsh transgression into freshwater forested wetlands while stimulating CH4 emissions

Wetlands are significant carbon (C) sinks and are expected to promote greater C assimilation as atmospheric CO 2 concentrations rise. However, the fate of C with environmental change along fresh-to-oligohaline wetland transitions is not well understood. We established an ex-situ mesocosm experiment to mimic future elevated atmospheric CO 2 concentrations ( e CO 2 , 720 ppm) versus current (380 ppm), and we exposed four co-occurring coastal wetland communities that naturally transgress (i.e., freshwater forest, mixed forest and marsh, marsh, mudflat) to these concentrations for two years. Overall, wetland communities with marsh plants in monoculture and mixed culture maintained high ecosystem C uptake with e CO 2 versus freshwater forested wetlands or mudflats, likely from superior plant species photosynthetic adjustment versus leaf area increases. e CO 2 promoted greater CO 2 uptake by leaves in all communities except mudflats, while promoting CH 4 efflux from whole ecosystems only when marsh plants were present. e CO 2 is projected to stimulate C gain 2.2-fold for forested wetlands and oligohaline marsh and 2.9-fold for forest-marsh mixture through greater CO 2 uptake. However, this comes at a cost of stimulated CH 4 flux by 1.4-to-1.7-fold in mixed and marsh communities versus reduced CH 4 fluxes with e CO 2 by forest and mudflat communities, perhaps through different oxidation pathways. Freshwater forested wetlands limited greenhouse gas emissions compared with transitional habitats, oligohaline marshes, and mudflats as atmospheric CO 2 concentrations increased. Stimulated C uptake in marshes may not offset higher methane emissions from these systems, potentially facilitating greater warming in a future with elevated atmospheric CO 2 .

Estuarine, Coastal and Shelf Science

Cassini observations of Io's visible aurorae

More than 500 images of Io in eclipse were acquired by the Cassini spacecraft in late 2000 and early 2001 as it passed through the jovian system en route to Saturn (Porco et al., 2003, Science 299, 1541-1547). Io's bright equatorial glows were detected in Cassini's near-ultraviolet filters, supporting the interpretation that the visible emissions are predominantly due to molecular SO2. Detailed comparisons of laboratory SO2 spectra with the Cassini observations indicate that a mixture of gases contribute to the equatorial emissions. Potassium is suggested by new detections of the equatorial glows at near-infrared wavelengths from 730 to 800 nm. Neutral atomic oxygen and sodium are required to explain the brightness of the glows at visible wavelengths. The molecule S2 is postulated to emit most of the glow intensity in the wavelength interval from 390 to 500 nm. The locations of the visible emissions vary in response to the changing orientation of the external magnetic field, tracking the tangent points of the jovian magnetic field lines. Limb glows distinct from the equatorial emissions were observed at visible to near-infrared wavelengths from 500 to 850 nm, indicating that atomic O, Na, and K are distributed across Io's surface. Stratification of the atmosphere is demonstrated by differences in the altitudes of emissions at various wavelengths: SO2 emissions are confined to a region close to Io's surface, whereas neutral oxygen emissions are seen at altitudes that reach up to 900 km, or half the radius of the satellite. Pre-egress brightening demonstrates that light scattered into Jupiter's shadow by gases or aerosols in the giant planet's upper atmosphere contaminates images of Io taken within 13 minutes of entry into or emergence from Jupiter's umbra. Although partial atmospheric collapse is suggested by the longer timescale for post-ingress dimming than pre-egress brightening, Io's atmosphere must be substantially supported by volcanism to retain auroral emissions throughout the duration of eclipse. ?? 2004 Elsevier Inc. All rights reserved.

Icarus

Mars as one system: Insights from the 8th international conference on Mars polar science and exploration

The 8th International Conference on Mars Polar Science and Exploration (ICMPSE) provided new insights into the complex interplay between Martian ice, climate, and atmospheric dynamics. The conference emphasized a holistic view of Mars as a system, where surface processes, subsurface ice, atmospheric dynamics, and historical climate shifts are interconnected. Research updates spanned cutting-edge remote sensing techniques and observations, terrestrial analog studies, and theoretical modeling, providing a multidimensional view of Mars' dynamic history and present-day activity. Numerous presentations highlighted the importance of understanding Mars as an integrated and dynamic system where surface and atmospheric processes interact over various timescales. This paper synthesizes unresolved questions and the major themes discussed, including mid-latitude glaciation, the evolution of the polar layered deposits (PLDs), terrestrial analog studies, climate modeling, and future mission planning. The findings contributed to refining models of Martian climate history, assessing the potential for extant life, and planning future human exploration. We also discuss the historical perspective of Mars Polar Science and new findings since the 7th conference in this series and anticipate the next four to 20 years of science on Mars related to ice, climate, and the atmosphere.

Icarus

Decadal trends of mercury cycling and bioaccumulation within Everglades National Park

Mercury (Hg) contamination has been a persistent concern in the Florida Everglades for over three decades due to elevated atmospheric deposition and the system's propensity for methylation and rapid bioaccumulation. Given declines in atmospheric Hg concentrations in the conterminous United States and efforts to mitigate nutrient release to the greater Everglades ecosystem, it was vital to assess how Hg dynamics responded on temporal and spatial scales. This study used a multimedia approach (water and biota) to examine Hg and methylmercury (MeHg) dynamics across a 76-site network within the southernmost portion of the region, Everglades National Park (ENP), from 2008 to 2018. Atmospheric Hg deposition was evaluated over time using a long-term monitoring station. Hg concentrations across matrices showed that air, water, and biota from the system were inextricably linked. Temporal patterns across matrices were driven primarily by hydrologic and climatic changes in the park and no evidence of a decline in atmospheric Hg deposition from 2008 to 2018 was observed, unlike other regions of the United States. In the Shark River Slough (SRS), excess dissolved organic carbon and sulfate were also consistently delivered from upgradient canals and showed no evidence of decline over the study period. Within the SRS a strong positive correlation was observed between MeHg concentrations in surface water and resident fish. Within distinct geographic regions of ENP (SRS, Marsh, Coastal), the geochemical controls on MeHg dynamics differed and highlighted regions susceptible to higher MeHg bioaccumulation, particularly in the SRS and Coastal regions. This study demonstrates the strong influence that dissolved organic carbon and sulfate loads have on spatial and temporal distributions of MeHg across the ENP. Importantly, improved water quality and flow rates are two key restoration targets of the nearly 30-year Everglades restoration program, which if achieved, this study suggests would lead to reduced MeHg production and exposure.

Florida

Metal emissions from Kilauea, and a suggested revision of the estimated worldwide metal output by quiescent degassing of volcanoes

Measurements of a large suite of metals (Pb, Cd, Cu, Zn and several others) and sulfur at Kilauea volcano over an extended period of time has yielded a detailed record of the atmospheric injection of ordinarily-rare metals from this quiescently degassing volcano, representative of an important type. We have combined the Kilauea data with data of recent studies by others (emissions from volcanoes in the Indonesian arc; the large Laki eruption of two centuries ago; Etna: estimates of total volcanic emissions of sulfur) to form the basis for a new working estimate of the rate of worldwide injection of metals to the atmosphere by volcanoes. The new estimate is that volcanoes inject a substantially smaller mass of ordinarily-rare metals into the atmosphere than was stated in a widely cited previous estimate [J.O. Nriagu, A global assessment of natural sources of atmospheric trace metals, Nature 338 (1989) 47-49]. Our estimate, which is an upper limit, is an annual injection mass of about 10,000 tons of the metals considered, versus the earlier estimate of about 23,000 tons. Also, the proportions of the metals are substantially different in our new estimate.

Earth and Planetary Science Letters

Cloud characterization and clear-sky correction from Landsat-7

Landsat, with its wide swath and high resolution, fills an important mesoscale gap between atmospheric variations seen on a few kilometer scale by local surface instrumentation and the global view of coarser resolution satellites such as MODIS. In this important scale range, Landsat reveals radiative effects on the few hundred-meter scale of common photon mean-free-paths, typical of scattering in clouds at conservative (visible) wavelengths, and even shorter mean-free-paths of absorptive (near-infrared) wavelengths. Landsat also reveals shadowing effects caused by both cloud and vegetation that impact both cloudy and clear-sky radiances. As a result, Landsat has been useful in development of new cloud retrieval methods and new aerosol and surface retrievals that account for photon diffusion and shadowing effects. This paper discusses two new cloud retrieval methods: the nonlocal independent pixel approximation (NIPA) and the normalized difference nadir radiance method (NDNR). We illustrate the improvements in cloud property retrieval enabled by the new low gain settings of Landsat-7 and difficulties found at high gains. Then, we review the recently developed &ldquo;path radiance&rdquo; method of aerosol retrieval and clear-sky correction using data from the Department of Energy Atmospheric Radiation Measurement (ARM) site in Oklahoma. Nearby clouds change the solar radiation incident on the surface and atmosphere due to indirect illumination from cloud sides. As a result, if clouds are nearby, this extra side-illumination causes clear pixels to appear brighter, which can be mistaken for extra aerosol or higher surface albedo. Thus, cloud properties must be known in order to derive accurate aerosol and surface properties. A three-dimensional (3D) Monte Carlo (MC) radiative transfer simulation illustrates this point and suggests a method to subtract the cloud effect from aerosol and surface retrievals. The main conclusion is that cloud, aerosol, and surface retrievals are linked and must be treated as a combined system. Landsat provides the range of scales necessary to observe the 3D cloud radiative effects that influence joint surface-atmospheric retrievals.

Remote Sensing of Environment

Paleoclimate simulations for North America over the past 21,000 years: Features of the simulated climate and comparisons with paleoenvironmental data

Maps of upper-level and surface winds and of surface temperature and precipitation illustrate the results of a sequence of global paleoclimatic simulations spanning the past 21,000 yr for North America. We review (a) the large-scale features of circulation, temperature, and precipitation that appear in the simulations from the NCAR Community Climate Model Version 1 (CCM 1), (b) the implications of the simulated climate for the past continental-scale distributions of three plant taxa ( Picea spp., Pseudotsuga menziesii , and Artemisia tridentata ), which are broadly representative of the vegetation across the continent, and (c) the potential explanations in terms of atmospheric circulation or surface energy- and water-balance processes for mismatches between the simulations and observations. Most of the broad-scale features of previous paleoclimatic simulations with the NCAR CCM 0 for North America are present in the current simulations. Many of the elements of a conceptual model (based on previous climate simulations) that describes the controls of paleoclimatic variations across North America during the past 21,000 yr are found in simulations reviewed here. These include (1) displacement of the jet stream by the Laurentide Ice Sheet to the south of its present position in both winter and summer, (2) generation of a ‘glacial anticyclone’ over the ice sheet at the LGM, and the consequent induction of large-scale sinking motions induced over eastern North America, (3) changes in the strength of surface atmospheric circulation features through time, including weakening of the Aleutian low in winter, and strengthening of the eastern Pacific and Bermuda high-pressure systems in summer as the ice sheet decreased in size, (4) development of a ‘heat low’ at the surface and a strengthened ridge in the upper-atmosphere over the continent at the time of the maximum summer insolation anomaly, (5) increases in summer temperature earlier in regions remote from the ice sheet (these increases appear earlier in the present (CCM 1) simulations than in the previous (CCM 0) ones, however), and (6) continuation of negative winter temperature anomalies into the middle Holocene. In general, simulated surface conditions that are discordant with paleoenvironmental observations can be attributed to the simulation of particular atmospheric circulation patterns (e.g. those that suppress precipitation or advect warm air into a region), with these mismatches amplified in Beringia and the southeastern United States by surface energy- and water-balance processes.

Quaternary Science Reviews

The geochemical and magnetic record of coal combustion products in West Virginia reservoir sediments and soils

Western West Virginia lies downwind from numerous coal-fired power plants along the Ohio River Valley. To test whether geochemical and mineralogical impacts from these power plants are detectable on the West Virginia landscape, we obtained reservoir cores, soils, and rocks from two separate sites in West Virginia, one in Harrison County (Hinkel and Deegan Reservoirs) and the other in Roane County (Miletree Run Reservoir). Both have small drainage basins that have the effect of maximizing atmospheric inputs relative to weathering inputs. Sediments from Hinkel Reservoir were dated using the 137 Cs method, and by knowledge of the age of the base of the sedimentary section. Major elements in Hinkel Reservoir sediments do not vary systematically over time, suggesting that the depositional history of these sediments has been relatively constant. In contrast, minor elements and sulfur do show dramatic shifts. Zn, Pb, As, S, Cd, Ge, and Hg all peak during the late 1960s and early 1970s. Polyaromatic hydrocarbons associated with combustion processes likewise show this same behavior. Coincident with these maxima is a peak in isothermal remnant magnetization (IRM), a parameter that is proportional to magnetite abundance. We separated the magnetic fraction of the sediments and examined this fraction petrographically. It is dominated by magnetite with a spherical morphology, which is characteristic of magnetite produced by combustion processes. Chemical analyses on local rocks showed that they were not the likely source for the trace element and magnetite enrichments. To compare soils and reservoir sediments, we normalized geochemical data to Ti; the underlying assumption is that Ti will track physical inputs of soil materials into the reservoir sediments. The normalized sediment data for the elements Zn, Pb, As, and S are all higher for sediments deposited during the late 1960s and early 1970s compared to normalized soil data, implying that soils are not the source for the element enrichments. We thus attribute the enrichment to atmospheric inputs. However, a coal-burning zinc smelter within 10 km of the reservoir site that operated until 1971 may have supplied some or all of the anomalous input: There are no nearby major atmospheric pollution sites near Miletree Run Reservoir. A core from this reservoir was dated based on knowledge of the time it was impounded. Like Hinkel Reservoir, there are no systematic shifts in major element contents over its depositional history. Like Hinkel Reservoir, there are also significant shifts in trace elements and IRM that cannot be explained by local soil sources. Magnetic separates from this reservoir are also dominated by spherical combustion-produced magnetite. Covariance over the period 1930-1980 between magnetite and sulfur with US SO 2 production (which comes dominantly from coal combustion) is strongly suggestive of a significant atmospheric input into Miletree Run Reservoir sediments. The nearest upwind power plants are between 50 and 75 km distant. Thus, relatively long distance transmission of particulate matter from the power plants of the Ohio River Valley is likely in this case.

West Virginia

Use of stable isotope signatures to determine mercury sources in the Great Lakes

Sources of mercury (Hg) in Great Lakes sediments were assessed with stable Hg isotope ratios using multicollector inductively coupled plasma mass spectrometry. An isotopic mixing model based on mass-dependent (MDF) and mass-independent fractionation (MIF) (&delta; 202 Hg and &Delta; 199 Hg) identified three primary Hg sources for sediments: atmospheric, industrial, and watershed-derived. Results indicate atmospheric sources dominate in Lakes Huron, Superior, and Michigan sediments while watershed-derived and industrial sources dominate in Lakes Erie and Ontario sediments. Anomalous &Delta; 200 Hg signatures, also apparent in sediments, provided independent validation of the model. Comparison of &Delta; 200 Hg signatures in predatory fish from three lakes reveals that bioaccumulated Hg is more isotopically similar to atmospherically derived Hg than a lake&rsquo;s sediment. Previous research suggests &Delta; 200 Hg is conserved during biogeochemical processing and odd mass-independent fractionation (MIF) is conserved during metabolic processing, so it is suspected even is similarly conserved. Given these assumptions, our data suggest that in some cases, atmospherically derived Hg may be a more important source of MeHg to higher trophic levels than legacy sediments in the Great Lakes.

Lake Erie, Lake Huron, Lake Michigan, Lake Ontario

Lacustrine responses to decreasing wet mercury deposition rates: results from a case study in northern Minnesota

We present a case study comparing metrics of methylmercury (MeHg) contamination for four undeveloped lakes in Voyageurs National Park to wet atmospheric deposition of mercury (Hg), sulfate (SO 4 –2 ), and hydrogen ion (H + ) in northern Minnesota. Annual wet Hg, SO 4 –2 , and H + deposition rates at two nearby precipitation monitoring sites indicate considerable decreases from 1998 to 2012 (mean decreases of 32, 48, and 66%, respectively). Consistent with decreases in the atmospheric pollutants, epilimnetic aqueous methylmercury (MeHg aq ) and mercury in small yellow perch (Hg fish ) decreased in two of four lakes (mean decreases of 46.5% and 34.5%, respectively, between 2001 and 2012). Counter to decreases in the atmospheric pollutants, MeHg aq increased by 85% in a third lake, whereas Hg fish increased by 80%. The fourth lake had two disturbances in its watershed during the study period (forest fire; changes in shoreline inundation due to beaver activity); this lake lacked overall trends in MeHg aq and Hg fish . The diverging responses among the study lakes exemplify the complexity of ecosystem responses to decreased loads of atmospheric pollutants.

Minnesota

Application of a rule-based model to estimate mercury exchange for three background biomes in the continental United States

Ecosystems that have low mercury (Hg) concentrations (i.e., not enriched or impactedbygeologic or anthropogenic processes) cover most of the terrestrial surface area of the earth yet their role as a net source or sink for atmospheric Hg is uncertain. Here we use empirical data to develop a rule-based model implemented within a geographic information system framework to estimate the spatial and temporal patterns of Hg flux for semiarid deserts, grasslands, and deciduous forests representing 45% of the continental United States. This exercise provides an indication of whether these ecosystems are a net source or sink for atmospheric Hg as well as a basis for recommendation of data to collect in future field sampling campaigns. Results indicated that soil alone was a small net source of atmospheric Hg and that emitted Hg could be accounted for based on Hg input by wet deposition. When foliar assimilation and wet deposition are added to the area estimate of soil Hg flux these biomes are a sink for atmospheric Hg. ?? 2009 American Chemical Society.

Environmental Science & Technology

Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States

Perchlorate (ClO 4 − ) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO 4 − appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO 4 − indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO 4 − (δ 18 O, Δ 17 O, δ 37 Cl) and associated NO 3 − (δ 18 O, Δ 17 O, δ 15 N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO 3 − -rich surface caliche deposits near Death Valley, California. The data indicate natural ClO 4 − in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO 4 − from the Atacama Desert of Chile as well as all known synthetic ClO 4 − . ClO 4 − in Death Valley caliche has a range of high Δ 17 O values (+8.6 to +18.4 ‰), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O 3 ). However, the Death Valley δ 37 Cl values (−3.1 to −0.8 ‰) and δ 18 O values (+2.9 to +26.1‰) are higher than those of Atacama ClO 4 − . In contrast, ClO 4 − from western Texas and New Mexico has much lower Δ 17 O (+0.3 to +1.3‰), with relatively high δ 37 Cl (+3.4 to +5.1 ‰) and δ 18 O (+0.5 to +4.8 ‰), indicating either that this material was not primarily generated with O 3 as a reactant or that the ClO 4 − was affected by postdepositional O isotope exchange. High Δ 17 O values in ClO 4 − (Atacama and Death Valley) are associated with high Δ 17 O values in NO 3 − , indicating that both compounds preserve characteristics of O 3 -related atmospheric production in hyper-arid settings, whereas both compounds have low Δ 17 O values in less arid settings. Although Δ 17 O variations in terrestrial NO 3 − can be attributed to mixing of atmospheric (high Δ 17 O) and biogenic (low Δ 17 O) NO 3 − , variations in Δ 17 O of terrestrial ClO 4 − are not readily explained in the same way. This study provides important new constraints for identifying natural sources of ClO 4 − in different environments by multicomponent isotopic characteristics, while presenting the possibilities of divergent ClO 4 − formation mechanisms and(or) ClO 4 − isotopic exchange in biologically active environments.

Environmental Science & Technology