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At least 235 records · Page 13

Atmospheric composition - Influence of biology

The variability of atmospheric constituents influenced by biological organisms over various time scales is examined, together with the human contribution to atmospheric sulfur. The biogeochemistry of nitrogen is discussed, with an emphasis on N2O, NO, and microbially mediated reactions in soil and water. Carbon species are bound up mainly in sediments and the deep ocean, but human activities involving combustion may cause a doubling of the atmospheric levels of CO2 in the near future, which could produce a general low-level atmospheric warming. Longer term measurements are required to assess the effects of CH4 augmentation in the atmosphere through fuel combustion. Coal burning effectively doubles the amount of SO2 produced by natural sources, and reduces the pH of rainwater, thus posing hazards to fish, plankton, and mollusc life.

Mcelroy, M. B.↗

Isotopic compositions and probable origins of organic molecules in the Eocene Messel shale

It is shown here that the carbon isotopic compositions of biomarkers from the Eocene Messel shale, accumulated 47 + or - 2 million years ago in anaerobic waters at the bottom of a lake, allow identification of specific sources for some materials and reconstruction of carbon flows within the lake and its sediments. The C-13 content of organic matter synthesized by lacustrine primary producers can be estimated from the observed C-13 content of the geoporphyrins derived from their chlorophylls. Total organic material in the shale is depleted in C-13 by six parts per thousand relative to that input. This difference cannot be explained by selective loss of components enriched in C-13, nor, as shown by isotopic compositions of other biomarkers, by inputs from land plants surrounding the lake or from methanogenic bacteria.

Hayes, J. M.↗

Polygenetic origin of Hrad Vallis region of Mars

A variety of apparently genetically related landforms in the Hrad Vallis region of Mars is examined. It is found that the outer valley of Hrad and the neighboring valley are composite features formed by karst or thermokarst processes and the growth and coalescence of smaller fault-aligned depressions. The materials in the vicinity may be soluble carbonates or sulfates or clay-rich sediment subject to thixotropic collapse. Water circulating within fault and fissure systems removed materials or altered the stability of materials to allow formation of steep-sided depressions. After the emplacement of surface materials in early Amazonian time, water was probably discharged to the surface. Isolate topographic depressions probably formed synchronously with the early release of water. Open lakes may have existed for a time.

De Hon, Rene A.↗

The regulation of methane oxidation in soil

The atmospheric concentration of methane, a greenhouse gas, has more than doubled during the past 200 years. Consequently, identifying the factors influencing the flux of methane into the atmosphere is becoming increasingly important. Methanotrophs, microaerophilic organisms widespread in aerobic soils and sediments, oxidize methane to derive energy and carbon for biomass. In so doing, they play an important role in mitigating the flux of methane into the atmosphere. Several physico-chemical factors influence rates of methane oxidation in soil, including soil diffusivity; water potential; and levels of oxygen, methane, ammonium, nitrate, nitrite, and copper. Most of these factors exert their influence through interactions with methane monooxygenase (MMO), the enzyme that catalyzes the reaction converting methane to methanol, the first step in methane oxidation. Although biological factors such as competition and predation undoubtedly play a role in regulating the methanotroph population in soils, and thereby limit the amount of methane consumed by methanotrophs, the significance of these factors is unknown. Obtaining a better understanding of the ecology of methanotrophs will help elucidate the mechanisms that regulate soil methane oxidation.

Review, Academic↗

Land-Use and Land-Cover Change around Mobile Bay, Alabama from 1974-2008

This document summarizes the major findings of a Gulf of Mexico Application Pilot project led by NASA Stennis Space Center (SSC) in conjunction with a regional collaboration network of the Gulf of Mexico Alliance (GOMA). NASA researchers processed and analyzed multi-temporal Landsat data to assess land-use and land-cover (LULC) changes in the coastal counties of Mobile and Baldwin, AL between 1974 and 2008. Our goal was to create satellite-based LULC data products using methods that could be transferable to other coastal areas of concern within the Gulf of Mexico. The Mobile Bay National Estuary Program (MBNEP) is the primary end-user, however, several other state and local groups may benefit from the project s data products that will be available through NOAA-NCDDC s Regional Ecosystem Data Management program. Mobile Bay is a critical ecologic and economic region in the Gulf of Mexico and to the entire country. Mobile Bay was designated as an estuary of national significance in 1996. This estuary receives the fourth largest freshwater inflow in the United States. It provides vital nursery habitat for commercially and recreationally important fish species. It has exceptional aquatic and terrestrial bio-diversity, however, its estuary health is influenced by changing LULC patterns, such as urbanization. Mobile and Baldwin counties have experienced a population growth of 1.1% and 20.5% from 2000-2006. Urban expansion and population growth are likely to accelerate with the construction and operation of the ThyssenKrupp steel mill in the northeast portion of Mobile County. Land-use and land-cover change can negatively impact Gulf coast water quality and ecological resources. The conversion of forest to urban cover types impacts the carbon cycle and increases the freshwater and sediment in coastal waters. Increased freshwater runoff decreases salinity and increases the turbidity of coastal waters, thus impacting the growth potential of submerged aquatic vegetation (SAV), which is critical nursing ground for many Gulf fish species. A survey of Mobile Bay SAV showed widespread decreases since the 1940s. Prior to our project, coastal environmental managers in Baldwin and Mobile counties needed more understanding of the historical LULC for properly assessing the impacts of urbanization. In particular, more information on the location and extent of changing urbanization LULC patterns was needed to aid LULC planning and to assess predictions of future LULC patterns. Our products will assist the coastal environmental managers and land-use planners in making better community growth planning decisions. Our project also will help to establish a historical baseline of LULC distributions, which is a fundamental need in any stewardship plan. The primary research objective of our project was to produce historic and current geospatial LULC change products across a 34-year time frame. A multi-decadal coastal LULC change product was the major project deliverable. The geographic extent and nature of change was quantified and assessed for the upland herbaceous, barren, open water, urban, upland forest, woody wetland, and non-woody wetlanddominated land cover types. We focused on regional analyses of decadal-scale urban expansion and watershed-scaled analyses of LULC change for multiple areas of concern to the Mobile Bay NEP (Figure A). We used the following dates to derive LULC classification products from Landsat data: 1974, 1979, 1984, 1988, 1991, 1996, 2001, 2005, and 2008. We assessed the accuracy of our products using randomly sampled locations and digital geospatial reference data including field survey data, high resolution orthorectified aerial photography, high resolution multispectral and panchromatic satellite data displays (from QuickBird and Corona sensors), digital elevation model data, and National Wetlands Inventory wetland cover type data. NOAA s Coastal Change Assessment Program s (C-CAP) and National Land Cover Database (NLCD) procts were used for qualitative comparison in assessing map accuracy. We calculated an average overall classification accuracy of 87% with similar overall accuracies for the older (MSS) and newer (TM and ETM) Landsat LULC products.

Ellis, Jean↗

An Experimental Flow-Through Assessment of Acidic Fe/Mg Smectite Formation on Early Mars

Orbital observations have detected the phyllosilicate smectite in layered material hundreds of meters thick, intracrater depositional fans, and plains sediments on Mars; however, the detection of carbonate deposits is limited. Instead of neutral/alkaline conditions during the Noachian, early Mars may have experienced mildly acidic conditions derived from volcanic acid-sulfate solutions that allowed Fe/Mg smectite formation but prevented widespread carbonate formation. The detection of acid sulfates (e.g., jarosite) associated with smectite in Mawrth Vallis supports this hypothesis. Previous work demonstrated smectite (saponite) formation in closed hydrologic systems (batch reactor) from basaltic glass at pH 4 and 200°C (Peretyazhko et al., 2016 GCA). This work presents results from alteration of basaltic glass from alkaline to acidic conditions in open hydrologic systems (flow-through reactor). Preliminary experiments exposed basaltic glass to deionized water at 190°C at 0.25 ml/min where solution pH equilibrated to 9.5. These initial high pH experiments were conducted to evaluate the flow-through reactor system before working with lower pHs. Smectite at this pH was not produced and instead X-ray diffraction results consistent with serpentine was detected. Experiments are in progress exposing basaltic glass from pH 8 down to pH 3 to determine what range of pHs could allow for smectite formation in this experimental opensystem. The production of smectite under an experimental open-system at low pHs if successful, would support a significant paradigm shift regarding the geochemical evolution of early Mars: Early Mars geochemical solutions were mildly acidic, not neutral/alkaline. This could have profound implications regarding early martain microbiology where acid conditions instead of neutral/alkaline conditions will require further research in terrestrial analogs to address the potential for biosignature preservation on Mars.

Sutter, Brad↗

Scientific Highlights and Status of the Mars Science Laboratory Mission, Years 9 through 12

We present the scientific highlights and status from years 9-12 of NASA’s Mars Science Laboratory mission, with its Curiosity rover. A thermochemolysis-based sample analysis revealed a variety of organic molecules preserved in clay mineral-rich lake/lake margin deposits of the Glen Torridon region. The stratigraphically higher clay-sulfate mineral transition on Aeolis Mons was found to be associated with a lithological change from lacustrine to dry aeolian depositional environments. Water intermittently returned to the surface after the increase in aridity, including during the deposition of wave ripple strata which indicate a climate capable of sustaining an ice-free lake in the early Hesperian. The overlying Mg sulfate-bearing unit has both poly- and monohydrated Mg sulfates and is also enriched in iron carbonate of a purity consistent with chemical sedimentation and therefore atmospheric sequestration. A channel-incised canyon within Gediz Vallis and distal alluvial deposits recorded numerous fluvial and debris flow events after the deposition, lithification, and erosion of the clay- and sulfate-bearing units. Bright clasts found in Gediz Vallis canyon are composed of native sulfur. The investigation of the modern atmosphere and environment focused on the influence of the crater and mountain topography and captured high-altitude noctilucent and iridescent clouds. Radiation monitoring now spans an 11-year solar cycle. Rover systems and science instruments remain capable of addressing mission scientific objectives. All ten scientific instruments continue to return high-value data despite degradation of the Chemistry and Camera instrument’s high-voltage system, loss of multispectral imaging capability, and loss of active neutron spectroscopy. The mission has mitigated the loss of redundant brakes on two arm joints, additional wheel wear, and highly reduced capability of the redundant flight computer. Efficiency improvements in rover energy utilization and operations staffing have allowed the mission team to maintain a high level of productivity despite declining rover power generation and funding.

Mars↗

Isotopic, petrologic and biogeochemical investigations of banded iron-formations

It is recognized that the first occurrence of banded iron-formations (BIFs) clearly predates biological oxygenation of the atmosphere-hydrosphere system and that their last occurrences extend beyond plausible dates of pervasive biological oxygenation. For this reason, and because enormous quantities of oxidizing power have been sequestered in them, it is widely thought that these massive, but enigmatic, sediments must encode information about the mechanism and timing of the rise of atmospheric O2. By coupling isotopic analyses of iron-formation carbonates with biogeochemical and petrologic investigations, we are studying (1) the mechanism of initial sedimentation of iron; (2) the role of iron in microbially mediated diagenetic processes in fresh iron-formation sediments; and (3) the logical integration of mechanisms of deposition with observed levels of banding. Thus far, it has been shown that (1) carbonates in BIFs of the Hamersley Group of Western Australia are isotopically inhomogenous; (2) the nature and pattern of isotopic ordering is not consistent with a metamorphic origin for the overall depletion of C-13 observed in the carbonates; (3) if biological, the origin of the C-13 depleted carbonate could be either respiratory or fermentative; (4) iron may have been precipitate d as Fe(3+), then reduced to Fe(2+) within the sediment; and (5) sedimentary biogeochemical systems may have been at least partially closed to mass transport of carbonate species.

Hayes, J. M.↗

Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

Nuth, J. A.↗

Local structure and distortions of mixed methane-carbon dioxide hydrates

A vast source of methane is found in gas hydrate deposits, which form naturally dispersed throughout ocean sediments and arctic permafrost. Methane may be obtained from hydrates by exchange with hydrocarbon byproduct carbon dioxide. It is imperative for the development of safe methane extraction and carbon dioxide sequestration to understand how methane and carbon dioxide co-occupy the same hydrate structure. Pair distribution functions (PDFs) provide atomic-scale structural insight into intermolecular interactions in methane and carbon dioxide hydrates. We present experimental neutron PDFs of methane, carbon dioxide and mixed methane-carbon dioxide hydrates at 10 K analyzed with complementing classical molecular dynamics simulations and Reverse Monte Carlo fitting. Mixed hydrate, which forms during the exchange process, is more locally disordered than methane or carbon dioxide hydrates. The behavior of mixed gas species cannot be interpolated from properties of pure compounds, and PDF measurements provide important understanding of how the guest composition impacts overall order in the hydrate structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring Mars for Evidence of Habitable Environments and Life

The climate of Mars has been more similar to that of Earth than has the climate of any other planet in our Solar System. But Mars still provides a valuable alternative example of how planetary processes and environments can affect the potential presence of life elsewhere. For example, although Mars also differentiated very early into a core, mantle and crust, it then evolved mostly if not completely without plate tectonics and has lost most of its early atmosphere. The Martian crust has been more stable than that of Earth, thus it has probably preserved a more complete record of its earliest history. Orbital observations determined that near-surface water was once pervasive. Orbiters have identified the following diverse aqueous sedimentary deposits: layered phyllosilicates, phyllosilicates in intracrater fans, plains sediments potentially harboring evaporitic minerals, deep phyllosilicates, carbonate-bearing deposits, intracrater clay-sulfate deposits, Meridiani-type layered deposits, valles-type layered deposits, hydrated silica-bearing deposits, and gypsum plains. These features, together with evidence of more vigorous past geologic activity, indicate that early climates were wetter and perhaps also somewhat warmer. The denser atmosphere that was required for liquid water to be stable on the surface also provided more substantial protection from radiation. Whereas ancient climates might have favored habitable environments at least in some localities, clearly much of the Martian surface for most of its history has been markedly less favorable for life. The combination of dry conditions, oxidizing surface environments and typically low rates of sedimentation are not conducive to the preservation of evidence of ancient environments and any biota. Thus a strategy is required whereby candidate sites are first identified and then characterized for their potential to preserve evidence of past habitable environments. Rovers are then sent to explore the most promising candidates. The Mars Exploration Rover (MER) Opportunity revealed that water once flowed to the surface across the vast Meridiani plains, creating saline lakes whose waters were roiled by ancient winds that also sculptured their salt deposits into sand dunes. Opportunity then drove more than 30 km to explore even older deposits on a crater rim. MER Spirit found evidence that thermal waters (heated by volcanism or by impacts?) altered rocks to create sulfate salts, and siliceous sinters. These discoveries indicate that an early hydrological cycle apparently sustained precipitation, streams and lakes. Liquid water participated in rock weathering reactions, such as iron and sulfur oxidation, that created distinctive weathering regimes. Volcanism, impacts, groundwater and ice interacted at least locally. Redox chemical energy from volcanism, hydrothermal activity and weathering of crustal materials would have been available for any life. Thus conditions might have supported life in the past, at least locally. The main objective of the Mars Science Laboratory (MSL) Curiosity rover is to determine the extent to which Gale crater hosted environments capable of supporting microbial life. The rover has already found stream gravels as well as sediments that might have been deposited in an ancient lake. The rover is now traversing to Mt. Sharp, a 5 km-high mound that is located on the crater floor and that exhibits layered sedimentary rocks having diverse minerals (sulfates and clays) that apparently formed in the presence of liquid water. This rock sequence was deposited over an extended time period in diverse potentially habitable watery environments. Curiosity is poised to characterize a a well-preserved rock record of hundreds of millions of years of diverse environments and profound climate change.

layered phyllosilicates↗

Mineralogical Studies of Experimentally Shocked Dolomite: Implications for the Outgassing of Carbonates

Common rock-forming rhombohedral carbonates - calcite and dolomite - constitute a considerable fraction of terrestrial sediments that may be shocked during hypervelocity impacts, such as during the Cretaceous-Tertiary (K/T) event or at the Haughton structure. The relatively modest temperatures needed to decompose carbonates and to release their CO2 are easily attained during such impacts. However, detailed and quantitative understanding of the CO2 release of carbonates as a function of shock stress is still the subject of controversy, as are a number of other reactions and phase transitions that were suggested for carbonates. The first devolatilization studies of carbonates in the early 1980s suggested that incipient devolatilization of calcite and/or dolomite commences at modest pressures, in the range < 10-18 GPa (amounting to 0.03-0.3% CO2 loss), with massive decarbonation (30-40% CO2 loss) occurring at shock pressure of 20 GPa and above. However, most later studies revealed that both calcite and dolomite are unexpectedly stable under shock conditions and no significant outgassing has been observed at pressures as high as 40 GPa for calcite and 60 GPa for dolomite. Despite these uncertainties, the calculations of O'Keefe and Ahrens (and others) serve to illustrate that the K/T bolide liberated sufficient CO2 that a substantial temperature increase of the global atmosphere is possible due to CO2-triggered greenhouse effects. The quantitative understanding of the devolatilization of carbonates as a function of shock stress is obviously critical to refine such calculations. Additional information is contained in the original extended abstract.

Skala, R.↗

Evaluating sulfurization as a blue carbon sink in a southern California salt marsh

Blue carbon ecosystems such as seagrass meadows, mangrove forests, and salt marshes are important carbon sinks that can store carbon for millennia. Recently, organic matter sulfurization and pyritization have been proposed as mechanisms of net carbon storage in blue carbon ecosystems. At our study site, organic sulfur that is resistant to acid hydrolysis (protokerogen) is an order of magnitude less abundant than pyrite sulfur, suggesting a dominance of pyritization over sulfurization. The C/N ratios and carbon isotope compositions suggest that nearly half of total organic carbon and ≥ 80% of protokerogen is composed of marsh plant material. Sediment protokerogen appears to be sulfurized based on its low δ 34 S values (− 10‰), abundance of disulfides, and higher S/C ratio (~ 1.0%) relative to potential biogenic sulfur sources. However, the interpretation of protokerogen δ 34 S values is complicated by the wide range in sulfur isotope compositions of marsh plants. Evidence for sulfurization occurs within the shallowest sediments across different vegetation zones, yielding consistent products, while pyritization appears to be more sensitive to alterations in sediment redox conditions. Based on organic sulfur and pyrite content, sulfurization may be a more spatially consistent process than pyritization, with implications for carbon storage. The relative abundance of pyrite and protokerogen organic sulfur indicates that pyritization is favored at our study site, but this is likely to vary across the spectrum of blue carbon ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Spatial Study 2022: Water Column, Sediment, and Total Ecosystem Respiration Rates across the Yakima River Basin, Washington, USA (v2)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin and is associated with the manuscript “Sediment-associated processes account for most of the spatial variation in ecosystem respiration in the Yakima River basin” submitted to Nature Communications Earth & Environment (Garayburu-Caruso et al., in review). The dataset provides ecosystem metabolism estimates generated from streamMetabolizer (Appling et al.; 2018) using data collected during the same five-week period at 48 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. Additionally, it includes the scripts used for the analysis and producing the figures in the manuscript. The contents include streamMetabolizer inputs and outputs and additional relevant data needed to generate the main manuscript results. The data included are: total ecosystem respiration, water respiration, calculated sediment-associated respiration, gross primary production outputs from the river corridor model for the Yakima River Basin, median grain size (d50), depth, dissolved oxygen, water temperature, pressure, and annual oxygen consumption. The associated GitHub repository can be found at https://github.com/river-corridors-sfa/SSS_metabolism. Samples collected during this study were labeled as “Second Spatial Study” or “SSS.” Raw time series sensor data, total suspended solids, and depth data from SSS were published at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1969566. A subset of data from the SSS samples were published in the contiguous United States (CONUS)-Scale Model-Sample (CM) study data package available at https://data.ess-dive.lbl.gov/view/doi:10.15485/1923689 that presents data from across the CONUS. They include dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), total nitrogen (TN), grain size, aerobic sediment respiration, dissolved oxygen (DO), and temperature. Parent IDs and Site IDs are consistent between the SSS and CM data packages, and they can be mapped directly so data across packages can be used together. Field metadata for the samples in this da This dataset is comprised of one main data folder with four subfolders. The main data folder contains of (1) file-level metadata; (2) data dictionary; (3) total/water column/sediment respiration; (4) gross primary production (GPP); (5) median grain size (d50); and (6) annual oxygen consumption. The “Figures” subfolder contains the figures used in the paper and all intermediate files (including geospatial files). The “Published_Data” contains a readme directing the user to download the public data to reproduce analyses and figures. The “Scripts” folder contains all scripts used in the analyses that were not part of running StreamMetabolizer. Lastly, the “Stream_Metabolizer” folder contains all files associated with running StreamMetabolizer including (1) model input files, (2) model output files, (3) processing scripts, (4) histogram plots of the outputs, and (5) an R project. All files are .csv, .pdf, .R, .Rmd, .Rproj, .html, .png, .txt, .qgz, .cpg, .dbf, .prj, .shp, .shp.ea.iso.xml, .shp.iso.xml, .shx, .sbn. ta package can be found at either link. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

Un-Numbered Operational Areas PRL 229 Railroad Tie Disposal Area Pond Confirmation Sampling Report

This Confirmatory Sampling (CS) Report (CSR) was prepared for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida in accordance with the CS Work Plan (CSWP) (HGL, 2022a). The CSR summarizes investigation activities performed on the Railroad Tie Disposal Area (RTDA) of the Un-Numbered Operational Areas (UNOA), Potential Release Location (PRL) 229 located at KSC. HydroGeoLogic, Inc. (HGL) prepared this report under Contract Number 80KSC019D0012. The purpose of the CSR is to provide information to evaluate the level of potential contamination in surface water and sediment samples collected from the RTDA PRL 229 Pond and determine if contaminants pose unacceptable risks to ecological receptors. The CSR provides analytical data of 10 sets of surface water and sediment samples collected in 2021. Surface water samples were analyzed for volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), polynuclear aromatic hydrocarbon (PAHs), metals, hardness, and salinity, while sediment samples were analyzed for metals, total organic carbon (TOC), SVOCs, PAHs, and total petroleum hydrocarbons (TPH). The CSR includes a Screening Level Ecological Risk Assessment (SLERA) conducted under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program to determine if unacceptable risks to ecological receptors exist at PRL 229 Pond. Metals and PAHs were detected in surface water samples, including detections of antimony, arsenic, barium, calcium, copper, lead, magnesium, thallium, zinc, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Based on measured salinity (1.03 to 1.21 parts per thousand), the pond was identified as freshwater. Sediment analytical results also contained detections of metals and PAHs, including antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, zinc, anthracene benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Potential risks to ecological receptors were evaluated in accordance with the SLERA Work Plan and the Decision Process Document for the Resource Conservation and Recovery Act (RCRA) Corrective Action Program at KSC (DPD) (Geosyntec, 2019), and using the 2021 sediment and surface water analytical results. Potential ecological receptors evaluated in the SLERA include the aquatic community, benthic invertebrates, aquatic birds, and aquatic mammals. The SLERA included Steps 2a through 2c of the Ecological Risk Assessment (ERA) process in accordance with the DPD. Using multiple lines of evidence, the SLERA concluded that many of the detected analytes are present at concentrations similar to those in background or reference locations at KSC, and/or at concentrations that would not pose a significant risk to ecological communities. There are no screening values available for the avian community, and PAHs are bioaccumulative compounds. For this reason, food web modeling was completed as a supplement to Step 2c to provide a quantitative evaluation of this exposure pathway. Food web modeling indicates that PAHs are unlikely to pose a risk to birds exposed to site sediment and surface water. Based on the results of the SLERA, the contaminants in sediment and surface water pose no to minimal risk to the ecological communities that could live or forage at the site. Based on the results of the SLERA, no further study is recommended for the RTDA Pond at PRL 229.

Confirmation Sampling↗

High resolution chronology of late Cretaceous-early Tertiary events determined from 21,000 yr orbital-climatic cycles in marine sediments

A number of South Atlantic sites cored by the Deep Sea Drilling Project (DSDP) recovered late Cretaceous and early Tertiary sediments with alternating light-dark, high-low carbonate content. The sedimentary oscillations were turned into time series by digitizing color photographs of core segments at a resolution of about 5 points/cm. Spectral analysis of these records indicates prominent periodicity at 25 to 35 cm in the Cretaceous intervals, and about 15 cm in the early Tertiary sediments. The absolute period of the cycles that is determined from paleomagnetic calibration at two sites is 20,000 to 25,000 yr, and almost certainly corresponds to the period of the earth's precessional cycle. These sequences therefore contain an internal chronometer to measure events across the K/T extinction boundary at this scale of resolution. The orbital metronome was used to address several related questions: the position of the K/T boundary within magnetic chron 29R, the fluxes of biogenic and detrital material to the deep sea immediately before and after the K/T event, the duration of the Sr anomaly, and the level of background climatic variability in the latest Cretaceous time. The carbonate/color cycles that were analyzed contain primary records of ocean carbonate productivity and chemistry, as evidenced by bioturbational mixing of adjacent beds and the weak lithification of the rhythmic sequences. It was concluded that sedimentary sequences that contain orbital cyclicity are capable of providing resolution of dramatic events in earth history with much greater precision than obtainable through radiometric methods. The data show no evidence for a gradual climatic deterioration prior to the K/T extinction event, and argue for a geologically rapid revolution at this horizon.

Herbert, Timothy D.↗

Importance of Quantifying the Full-depth Carbon Reservoir of Jamaica Bay Salt Marshes, New York

Constraining uncertainty in the global carbon cycle requires valid assessment of both surface and stored carbon in marine and coastal ecosystems (Blue Carbon) as well as terrestrial carbon (forests, peatlands, and soils) [Pendleton et al., 2012]. Quantifying the global carbon stock of coastal salt marshes, potentially the most efficient carbon-burying ecosystems in the world per area, is a key area of further research in both of these fields Pendleton et al., 2012. One of the largest challenges is that despite the fact that salt marshes often sequester carbon several meters deep, nearly all estimates of salt marsh carbon stocks consider only the upper 1 m of sediment (Windham-Myers et al., 2015) [54]. This is particularly concerning because coastal wetlands are increasingly at risk due to climate change, sea level rise, and anthropogenic disturbance and destruction (Deegan et al., 2012) [15]. Using full-depth measurements from marsh cores, we estimate the carbon stock of five salt marshes in the highly urbanized estuary of Jamaica Bay, New York and argue that partial-depth measurements can underestimate carbon stocks. These estimates use calculated carbon content and probe depth data of these marshes collected between 2000 and 2019, applying this data across the full area of the marsh obtained from satellite imagery. Carbon density measurements are then multiplied by the full-depth volume of the marshes to create an estimate of total carbon stock. In addition to calculating present-day estimates, we compare our carbon stock estimates to historical Jamaica Bay imagery to calculate historical carbon stocks and carbon loss. The carbon stock estimates presented here show a 95% carbon stock loss between 1885 and 2019 in Jamaica Bay and highlight the severe underestimation of carbon stocks without full-depth calculations. These findings have important implications for disappearing salt marshes with regard to the global carbon cycle and the incorporation of belowground carbon into global climate models. The findings are increasingly relevant for advocacy efforts aiming to conserve these marshes with sea level rise.

Tidal wetlands↗

Evaluation of the Change in Uranium Mobility in Sediments from the Hanford 300-FF-5 Stage B Polyphosphate Field Injection

The purpose of this study was to evaluate the change in uranium mobility in the periodically re-wetted zone (PRZ) and upper unconfined aquifer of the Hanford Site’s 300-FF-5 operable unit as a result of Stage B polyphosphate (PO 4 ) injections. These 300 Area sediments are beneath or near the former North Process Pond, which has previously been shown to contain metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 •8H 2 O] and uranophane [Ca(UO 2 ) 2 (SiO 3 OH) 2 •5H 2 O], along with aqueous and adsorbed uranium (U), and small amounts of U in calcite as a result of acidic disposal with a significant number of co-contaminants. Previous laboratory-scale studies have identified multiple mechanisms that decrease uranium mobility with polyphosphate injection: (a) precipitation of a low-solubility uranium-phosphate mineral (autunite); (b) precipitation of a Ca-phosphate solid that incorporates U; (c) precipitation of Ca-phosphate mineral (apatite group minerals) that coats existing uranium phases (i.e., U in calcite, U in Fe-oxides), reducing uranium leaching; and (d) aqueous Ca-U-carbonate species adsorption onto apatite. Given the significant amount of apatite precipitation, other U phases such as carbonates could also coprecipitate with apatite. To quantify differences in solubility, leachability, and phases of uranium between pre- and post-PO 4 -treated sediments, different types of analyses were conducted, including analysis of uranium in (a) a carbonate solution extraction from sediment over 1000 h (41.67 days), (b) six sequential liquid extractions from sediment over approximately 1 week, (c) leaching of uranium from sediments in one dimensional (1-D) column experiments over 2 months, and (d) solid phase characterization of select sediments. An additional extraction and solid phase measurements were conducted to evaluate phosphate precipitate formation. Metals were also analyzed in sequential liquid extractions as indicators of (a) amendment injection delivery, (b) co-contaminant movement, and (c) changes in solid phases. Aqueous and solid phase carbonate measurements were also conducted to evaluate changes in carbonates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗