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Advanced Technologies for Monitoring CO2 Saturation and Pore Pressure in Geologic Formations: Linking the Chemical and Physical Effects to Elastic and Transport Properties

Ultrasonic P- and S-wave velocities were measured over a range of confining pressures while injecting CO2 and brine into the samples. Pore fluid pressure was also varied and monitored together with porosity during injection. Effective medium models were developed to understand the mechanisms and impact of observed changes and to provide the means for implementation of the interpretation methodologies in the field. Ultrasonic P- and S-wave velocities in carbonate rocks show as much as 20-50% decrease after injection of the reactive CO2-brine mixture; the changes were caused by permanent changes to the rock elastic frame associated with dissolution of mineral. Velocity decreases were observed under both dry and fluid-saturated conditions, and the amount of change was correlated with the initial pore fabrics. Scanning Electron Microscope images of carbonate rock microstructures were taken before and after injection of CO2-rich water. The images reveal enlargement of the pores, dissolution of micrite (micron-scale calcite crystals), and pitting of grain surfaces caused by the fluid- solid chemical reactivity. The magnitude of the changes correlates with the rock microtexture – tight, high surface area samples showed the largest changes in permeability and smallest changes in porosity and elastic stiffness compared to those in rocks with looser texture and larger intergranular pore space. Changes to the pore space also occurred from flow of fine particles with the injected fluid. Carbonates with grain-coating materials, such as residual oil, experienced very little permanent change during injection. In the tight micrite/spar cement component, dissolution is controlled by diffusion: the mass transfer of products and reactants is thus slow and the fluid is expected to be close to thermodynamical equilibrium with the calcite, leading to very little dissolution, or even precipitation. In the microporous rounded micrite and macropores, dissolution is controlled by advection: because of an efficient mass transfer of reactants and products, the fluid remains acidic, far from thermodynamical equilibrium and the dissolution of calcite is important. These conclusions are consistent with the lab observations. Sandstones from the Tuscaloosa formation in Mississippi were also subjected to injection under representative in situ stress and pore pressure conditions. Again, both P- and S-wave velocities decreased with injection. Time-lapse SEM images indicated permanent changes induced in the sandstone microstructure by chamosite dissolution upon injection of CO2-rich brine. After injection, the sandstone showed an overall cleaner microstructure. Two main changes are involved: (a) clay dissolution between grains and at the grain contact and (b) rearrangement of grains due to compaction under pressure Theoretical and empirical models were developed to quantify the elastic changes associated with injection. Permanent changes to the rock frame resulted in seismic velocity-porosity trends that mimic natural diagenetic changes. Hence, when laboratory measurments are not available for a candidate site, these trends can be estimated from depth trends in well logs. New theoretical equations were developed to predict the changes in elastic moduli upon substitution of pore-filling material. These equations reduce to Gassmann’s equations for the case of constant frame properties, low seismic frequencies, and fluid changes in the pore space. The new models also predict the change dissolution or precipitation of mineral, which cannot be described with the conventional Gassmann theory.

Mavko, G.↗

Project Execution Plan for the Remote Handled Low-Level Waste Disposal Project

As part of ongoing cleanup activities at the Idaho National Laboratory (INL), closure of the Radioactive Waste Management Complex (RWMC) is proceeding under the Comprehensive Environmental Response, Compensation, and Liability Act (42 USC 9601 et seq. 1980). INL-generated radioactive waste has been disposed of at RWMC since 1952. The Subsurface Disposal Area (SDA) at RWMC accepted the bulk of INL’s contact and remote-handled low-level waste (LLW) for disposal. Disposal of contact-handled LLW and remote-handled LLW ion-exchange resins from the Advanced Test Reactor in the open pit of the SDA ceased September 30, 2008. Disposal of remote-handled LLW in concrete disposal vaults at RWMC will continue until the facility is full or until it must be closed in preparation for final remediation of the SDA (approximately at the end of fiscal year FY 2017). The continuing nuclear mission of INL, associated ongoing and planned operations, and Naval spent fuel activities at the Naval Reactors Facility (NRF) require continued capability to appropriately dispose of contact and remote handled LLW. A programmatic analysis of disposal alternatives for contact and remote-handled LLW generated at INL was conducted by the INL contractor in Fiscal Year 2006; subsequent evaluations were completed in Fiscal Year 2007. The result of these analyses was a recommendation to the Department of Energy (DOE) that all contact-handled LLW generated after September 30, 2008, be disposed offsite, and that DOE proceed with a capital project to establish replacement remote-handled LLW disposal capability. An analysis of the alternatives for providing replacement remote-handled LLW disposal capability has been performed to support Critical Decision-1. The highest ranked alternative to provide this required capability has been determined to be the development of a new onsite remote-handled LLW disposal facility to replace the existing remote-handled LLW disposal vaults at the SDA. Several offsite DOE and commercial disposal options exist for contact-handled LLW; however, offsite disposal options are either not currently available (i.e., commercial disposal facilities), practical, or cost-effective for all remote-handled LLW streams generated at INL. Offsite disposal of all INL and tenant-generated remote-handled waste is further complicated by issues associated with transporting highly radioactive waste in commerce; and infrastructure and processing changes at the generating facilities, specifically NRF, that would be required to support offsite disposal. The INL Remote-Handled LLW Disposal Project will develop a new remote handled LLW disposal facility to meet mission-critical, remote-handled LLW disposal needs. A formal DOE decision to proceed with the project has been made in accordance with the requirements of National Environmental Policy Act (42 USC§ 4321 et seq.). Remote-handled LLW is generated from nuclear programs conducted at INL, including spent nuclear fuel handling and operations at NRF and operations at the Advanced Test Reactor. Remote-handled LLW also will be generated by new INL programs and from segregation and treatment (as necessary) of remote handled scrap and waste currently stored in the Radioactive Scrap and Waste Facility at the Materials and Fuels Complex.

99 GENERAL AND MISCELLANEOUS↗

Streamlined Approach for Environmental Restoration (SAFER) Plan for Corrective Action Unit 575: Area 15 Miscellaneous Sites, Nevada National Security Site, Nevada

This Streamlined Approach for Environmental Restoration (SAFER) Plan addresses the actions needed to achieve closure for Corrective Action Unit (CAU) 575, Area 15 Miscellaneous Sites, identified in the Federal Facility Agreement and Consent Order (FFACO). CAU 575 comprises the following four corrective action sites (CASs) located in Area 15 of the Nevada National Security Site: 15-19-02, Waste Burial Pit, 15-30-01, Surface Features at Borehole Sites, 15-64-01, Decontamination Area, 15-99-03, Aggregate Plant This plan provides the methodology for field activities needed to gather the necessary information for closing each CAS. There is sufficient information and process knowledge from historical documentation and investigations of similar sites regarding the expected nature and extent of potential contaminants to recommend closure of CAU 575 using the SAFER process. Additional information will be obtained by conducting a field investigation to document and verify the adequacy of existing information, to affirm the predicted corrective action decisions, and to provide sufficient data to implement the corrective actions. This will be presented in a closure report that will be prepared and submitted to the Nevada Division of Environmental Protection (NDEP) for review and approval.

54 ENVIRONMENTAL SCIENCES↗

Results of stainless steel canister corrosion studies and environmental sample investigations

This progress report describes work being done at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of used nuclear fuel. The work involves both characterization of the potential physical and chemical environment on the surface of the storage canisters and how it might evolve through time, and testing to evaluate performance of the canister materials under anticipated storage conditions. To evaluate the potential environment on the surface of the canisters, SNL is working with the Electric Power Research Institute (EPRI) to collect and analyze dust samples from the surface of in-service SNF storage canisters. In FY 13, SNL analyzed samples from the Calvert Cliffs Independent Spent Fuel Storage Installation (ISFSI); here, results are presented for samples collected from two additional near-marine ISFSI sites, Hope Creek NJ, and Diablo Canyon CA. The Hope Creek site is located on the shores of the Delaware River within the tidal zone; the water is brackish and wave action is normally minor. The Diablo Canyon site is located on a rocky Pacific Ocean shoreline with breaking waves. Two types of samples were collected: SaltSmart™ samples, which leach the soluble salts from a known surface area of the canister, and dry pad samples, which collected a surface salt and dust using a swipe method with a mildly abrasive ScotchBrite™ pad. The dry samples were used to characterize the mineralogy and texture of the soluble and insoluble components in the dust via microanalytical techniques, including mapping X-ray Fluorescence spectroscopy and Scanning Electron Microscopy. For both Hope Creek and Diablo Canyon canisters, dust loadings were much higher on the flat upper surfaces of the canisters than on the vertical sides. Maximum dust sizes collected at both sites were slightly larger than 20 μm, but Phragmites grass seeds ~1 mm in size, were observed on the tops of the Hope Creek canisters. At both sites, the surface dust could be divided into fractions generated by manufacturing processes and by natural processes. The fraction from manufacturing processes consisted of variably-oxidized angular and spherical particles of stainless steel and iron, generated by machining and welding/cutting processes, respectively. Dust from natural sources consisted largely of detrital quartz and aluminosilicates (feldspars and clays) at both sites. At Hope Creek, soluble salts were dominated by sulfates and nitrates, mostly of calcium. Chloride was a trace component and the only chloride mineral observed by SEM was NaCl. Chloride surface loads measured by the Saltsmart™ sensors were very low, less than 60 mg m –2 on the canister top, and less than 10 mg m –2 on the canister sides. At Diablo Canyon, sea-salt aggregates of NaCl and Mg-SO 4 , with minor K and Ca, were abundant in the dust, in some cases dominating the observed dust assemblage. Measured Saltsmart™ chloride surface loads were very low (<5 mg m –2 ); however, high canister surface temperatures damaged the Saltsmart™ sensors, and, in view of the SEM observations of abundant sea-salts on the package surfaces, the measured surface loads may not be valid. Moreover, the more heavily-loaded canister tops at Diablo Canyon were not sampled with the Saltsmart™ sensors. The observed low surface loads do not preclude chloride-induced stress corrosion cracking (CISCC) at either site, because (1) the measured data may not be valid for the Diablo Canyon canisters; (2) the surface coverage was not complete (for instance, the 45º offset between the outlet and inlet vents means that near-inlet areas, likely to have heavier dust and salt loads, were not sampled); and (3) CISCC has been experimentally been observed at salt loads as low as 5-8 mg/m 2 . Experimental efforts at SNL to assess corrosion of interim storage canister materials include three tasks in FY14. First, a full-diameter canister mockup, made using materials and techniques identical to those used to make interim storage canisters, was designed and ordered from Ranor Inc., a cask vendor for Areva/TN. The mockup will be delivered prior to the end of FY14, and will be used for evaluating weld residual stresses and degrees of sensitization for typical interim storage canister welds. Following weld characterization, the mockup will be sectioned and provided to participating organizations for corrosion testing purposes. A test plan is being developed for these efforts. In a second task, experimental work was carried out to evaluate crevice corrosion of 304SS in the presence of limited reactants, as would be present on a dustcovered storage canister. This work tests the theory that limited salt loads will limit corrosion penetration over time, and is a continuation of work carried out in FY13. Laser confocal microscopy was utilized to assess the volume and depth of corrosion pits formed during the crevice corrosion tests. Results indicate that for the duration of the current experiments (100 days), no stifling of corrosion occurred due to limitations in the amount of reactants present at three different salt loadings. Finally, work has been carried out this year perfecting an instrument for depositing sea-salts onto metal surfaces for atmospheric corrosion testing purposes. The system uses an X-Y plotter system with a commercial airbrush, and deposition is monitored with a quartz crystal microbalance. The system is capable of depositing very even salt loadings, even at very low total deposition rates.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemical Waste Landfill Annual Post-Closure Care Report Calendar Year 2014

The CWL is a 1.9-acre remediated interim status landfill located in the southeastern corner of SNL/NM Technical Area III (Figures 2-1 and 2-2) undergoing post-closure care in accordance with the PCCP (NMED October 2009 and subsequent revisions). From 1962 until 1981, the CWL was used for the disposal of chemical and solid waste generated by SNL/NM research activities. Additionally, a small amount of radioactive waste was disposed of during the operational years. Disposal of liquid waste in unlined pits and trenches ended in 1981, and after 1982 all liquid waste disposal was terminated. From 1982 through 1985, only solid waste was disposed of at the CWL, and after 1985 all waste disposal ended. The CWL was also used as a hazardous waste drum-storage facility from 1981 to 1989. A summary of the CWL disposal history is presented in the Closure Plan (SNL/NM December 1992) along with a waste inventory based upon available disposal records and information.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Post-Closure Inspection Report for the Tonopah Test Range, Nevada, for Calendar Year 2014

This report provides the results of the annual post-closure inspections conducted at the closed Corrective Action Units (CAUs) located on the Tonopah Test Range (TTR), Nevada. This report covers calendar year 2014 and includes inspection and repair activities completed at the following CAUs; CAU 400: Bomblet Pit and Five Points Landfill (TTR); CAU 407: Roller Coaster RadSafe Area (TTR); CAU 424: Area 3 Landfill Complexes (TTR); CAU 453: Area 9 UXO Landfill (TTR); and CAU 487: Thunderwell Site (TTR) Inspections were conducted according to the post-closure plans in the approved Closure Reports and subsequent correspondence with the Nevada Division of Environmental Protection. The post-closure inspection plans and subsequent correspondence modifying the requirements for each CAU are included in Appendix B. The inspection checklists are included in Appendix C. Photographs taken during inspections are included in Appendix D. The annual post-closure inspections were conducted on May 28, 2014. Maintenance was required at CAU 407. Animal burrows were backfilled and erosion repairs were performed. Vegetation monitoring was performed at CAU 407 in June 2014. The vegetation monitoring report is included in Appendix E.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Request for a Class 1 Permit Modification to the Los Alamos National Laboratory (LANL) Hazardous Waste Facility Permit, Attachment K EPA ID No. NM0890010515 (Rev. 1)

The following submittal has been prepared by the U.S. Department of Energy and Los Alamos National Security, LLC (collectively the Permittees) to request a modification to the November 2010 Los Alamos National Laboratory (LANL) Hazardous Waste Facility Permit (Permit). This modification has been prepared as a Class 1 permit modification requiring prior approval by the New Mexico Environment Department-Hazardous Waste Bureau (NMEDHWB) (also known as a Class 1 * permit modification) as described in the New Mexico Administrative Code, Title 20, Chapter 4, Part 1 (20.4.1.900 NMAC) [incorporating Code of Federal Regulations (CFR), Title 40 §§ 270.42 (a) ]. LANL's Environmental Protection Agency (EPA) identification number is EPA ID No. NM0890010515. The permit modification includes revisions to Table K-l , SWMUs (Solid Waste Management Units) and AOCs (Areas of Concern) Requiring Corrective Action, which is included in Permit Attachment K, Listings ofSWMUs and AOCs. The following summary describes the proposed modification and rationale behind the modification and contains a revised version of the relevant page of Table K-l incorporating the modification (Attachment 1). The Permittees request that the revised Table K-I be included in the Permit by the NMED-HWB upon approval of this permit modification request. Pits 38 (AOC 54-023) and 39 (AOC 54-024) were recently designated as areas of concern (AOCs) and shall be included in Table K-l of Attachment K, Listings ofSWMUs and AOCs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Technical Summary of MIS Studies of Cl Transport and Reactivity

Chloride containing deposits have been detected during destructive examination (DE) of 3013 inner and convenience containers that had contained impure plutonium oxide/salt mixtures. The deposits were found on surfaces that were not in direct contact with the oxide/salt mixtures. EDX analysis of deposits associated with corrosion pits in the inner container closure weld region (ICCWR) show Cl but no metal cations from the oxide/salt mixture (Na, K, Ca, Mg, or Pu) that would indicate particulate transport of the chlorine to that location. Powder x-ray diffraction analysis identified a coating found on the wall of a convenience container as ammonium chloride (NH4Cl).1 The location of the NH4Cl coating on the wall above the material suggest that it was made by a gas-phase reaction, one possibility being a reaction between ammonia (NH3) and hydrogen chloride (HCl) gases as shown in equation (1). It has been shown that NH3 can be formed in a gasphase reaction between nitrogen (N2) and hydrogen (H2) in a radiation environment, equation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High Fluence, Multi-pulse Laser Surface Damage: absorbers, mechanisms and mitigation

All optical systems designed to guide high photon fluxes are limited by optical damage and optical stress induced degradation to key optical components including lenses, frequency conversion crystals, antireflection coatings and dielectric multilayer mirrors. These systems include continuous wave (CW) and Giga-shot high average power (HAP) systems for laser machining and DoD applications, and systems for laser driven inertial confinement fusion (ICF) and inertial fusion energy (IFE). Optical degradation and damage begin with near surface defect absorption of sub band-gap light; these effects appear beginning in the near IR (1eV) and become progressively worse for light in the near UV (3 to 4eV). At high enough per pulse fluences (Φ), localized energy deposition is sufficient to create damage sites through explosive ejection of material; this process, optical damage initiation, results in micron sized surface pits which can grow exponentially upon exposure to additional pulses.

42 ENGINEERING↗

Evaluation of Settler Tank Thermal Stability during Solidification and Disposition to ERDF

Ten 16-foot-long and 20-inch diameter horizontal tanks currently reside in a stacked 2×5 (high) array in the ~20,000-gallon water-filled Weasel Pit of the 105-KW Fuel Storage Basin on the US-DOE Hanford Site. These ten tanks are part of the Integrated Water Treatment System used to manage water quality in the KW Basin and are called “settler” tanks because of their application in removing particles from the KW Basin waters. Based on process knowledge, the settler tanks are estimated to contain about 124 kilograms of finely divided uranium metal, 22 kg of uranium dioxide, and another 55 kg of other radioactive sludge. The Sludge Treatment Project (STP), managed by CH2MHill Plateau Remediation Company (CHPRC) is charged with managing the settler tanks and arranging for their ultimate disposal by burial in ERDF. The presence of finely divided uranium metal in the sludge is of concern because of the potential for thermal runaway reaction of the uranium metal with water and the formation of flammable hydrogen gas as a product of the uranium-water reaction. Thermal runaway can be instigated by external heating. The STP commissioned a formal Decision Support Board (DSB) to consider options and provide recommendations to manage and dispose of the settler tanks and their contents. Decision criteria included consideration of the project schedule and longer-term deactivation, decontamination, decommissioning, and demolition (D4) of the KW Basin. The DSB compared the alternatives and recommended in-situ grouting, size-reduction, and ERDF disposal as the best of six candidate options for settler tank treatment and disposal. It is important to note that most grouts contain a complement of Portland cement as the binding agent and that Portland cement curing reactions generate heat. Therefore, concern is raised that the grouting of the settler tank contents may produce heating sufficient to instigate thermal runaway reactions in the contained uranium metal sludge.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Passage Distribution and Federal Columbia River Power System Survival for Steelhead Kelts Tagged Above and at Lower Granite Dam, Year 2 (Rev. 1)

Steelhead (Oncorhynchus mykiss) populations have declined throughout their range in the last century and many populations, including those of the Snake River Basin are listed under the Endangered Species Act of 1973. The reasons for their decline are many and complex, but include habitat loss and degradation, overharvesting, and dam construction. The 2008 Biological Opinion calls for an increase in the abundance of female steelhead through an increase in iteroparity (i.e., repeat spawning) and this can be realized through a combination of reconditioning and in-river survival of migrating kelts. The goal of this study is to provide the data necessary to inform fisheries managers and dam operators of Snake River kelt migration patterns, survival, and routes of dam passage. Steelhead kelts (n = 487) were captured and implanted with acoustic transmitters and passive integrated transponder (PIT)-tags at the Lower Granite Dam (LGR) Juvenile Fish Facility and at weirs located in tributaries of the Snake and Clearwater rivers upstream of LGR. Kelts were monitored as they moved downstream through the Federal Columbia River Power System (FCRPS) by 15 autonomous and 3 cabled acoustic receiver arrays. Cabled receiver arrays deployed on the dam faces allowed for three-dimensional tracking of fish as they approached the dam face and were used to determine the route of dam passage. Overall, 27.3% of the kelts tagged in this study successfully migrated to Martin Bluff (rkm 126, as measured from the mouth of the Columbia River), which is located downstream of all FCRPS dams. Within individual river reaches, survival per kilometer estimates ranged from 0.958 to 0.999; the lowest estimates were observed in the immediate forebay of FCRPS dams. Steelhead kelts tagged in this study passed over the spillway routes (spillway weirs, traditional spill bays) in greater proportions and survived at higher rates compared to the few fish passed through powerhouse routes (turbines and juvenile bypass systems). The results of this study provide information about the route of passage and subsequent survival of steelhead kelts that migrated through the Snake and Columbia rivers from LGR to Bonneville Dam in 2013. These data may be used by fisheries managers and dam operators to identify potential ways to increase the survival of kelts during their seaward migrations.

13 HYDRO ENERGY↗

Comparison of Uncertainty of Two Precipitation Prediction Models at Los Alamos National Lab Technical Area 54

Meteorological inputs are an important part of subsurface flow and transport modeling. The choice of source for meteorological data used as inputs has significant impacts on the results of subsurface flow and transport studies. One method to obtain the meteorological data required for flow and transport studies is the use of weather generating models. This paper compares the difference in performance of two weather generating models at Technical Area 54 of Los Alamos National Lab. Technical Area 54 is contains several waste pits for low-level radioactive waste and is the site for subsurface flow and transport studies. This makes the comparison of the performance of the two weather generators at this site particularly valuable.

54 ENVIRONMENTAL SCIENCES↗

Post-Closure Inspection Report for the Tonopah Test Range, Nevada. For Calendar Year 2015, Revision 0

This report provides the results of the annual post-closure inspections conducted at the closed corrective action units (CAUs) located on the Tonopah Test Range (TTR), Nevada. This report covers calendar year 2015 and includes inspection and repair activities completed at the following CAUs; CAU 400: Bomblet Pit and Five Points Landfill (TTR); CAU 407: Roller Coaster RadSafe Area (TTR); CAU 424: Area 3 Landfill Complexes (TTR); CAU 453: Area 9 UXO Landfill (TTR); and CAU 487: Thunderwell Site (TTR) Inspections were conducted according to the post-closure plans in the approved closure reports and subsequent correspondence with the Nevada Division of Environmental Protection. The post-closure inspection plans and subsequent correspondence modifying the requirements for each CAU are included in Appendix B. The inspection checklists are included in Appendix C. Field notes are included in Appendix D. The annual post-closure inspections were conducted on May 12, 2015. Maintenance was required at CAU 453. Cracking along the north trench was repaired. One monument is missing at CAU 424; it will be replaced in 2016. Postings at CAUs 407, 424, 453, and 487 contain contact information for TTR Security. It was noted that protocols may not be in place to ensure that the U.S. Department of Energy, National Nuclear Security Administration Nevada Field Office (NNSA/NFO) is notified if access is needed at these sites. NNSA/NFO is working with the U.S. Air Force and Sandia to determine whether more appropriate contact information or new protocols are warranted for each CAU. Based on these inspections, there has not been a significant change in vegetation, and vegetation monitoring was not recommended at CAU 400 or CAU 407 in 2015.

54 ENVIRONMENTAL SCIENCES↗

Post-Closure Report for Closed Resource Conservation and Recovery Act Corrective Action Units, Nevada National Security Site, Nevada: For Fiscal Year 2015 (October 2014–September 2015), Revision 0

This report serves as the combined annual report for post-closure activities for the following closed corrective action units (CAUs); CAU 90, Area 2 Bitcutter Containment; CAU 91, Area 3 U-3fi Injection Well; CAU 92, Area 6 Decon Pond Facility; CAU 110, Area 3 WMD U-3ax/bl Crater; CAU 111, Area 5 WMD Retired Mixed Waste Pits; and CAU 112, Area 23 Hazardous Waste Trenches. This report covers fiscal year 2015 (October 2014 through September 2015). The post-closure requirements for these sites are described in Resource Conservation and Recovery Act Permit Number NEV HW0101 and are summarized in each CAU-specific section in Section 1.0 of this report. The results of the inspections, a summary of maintenance activities, and an evaluation of monitoring data are presented in this report.

54 ENVIRONMENTAL SCIENCES↗

Arctic Black Carbon Loading and Profile Using the Single-Particle Soot Photometer (SP2) Field Campaign Report

One of the major issues confronting aerosol climate simulations of the Arctic and Antarctic cryospheres is the lack of detailed data on the vertical and spatial distribution of aerosols with which to test these models. This is due, in part, to the inherent difficulty of conducting such measurements in extreme environments. However given the pronounced sensitivity of the polar regions to radiative balance perturbations, it is incumbent upon our community to better understand and quantify these perturbations, and their unique feedbacks, so that robust model predictions of this region can be realized. One class of under-measured radiative forcing agents in the polar region is the absorbing aerosol—black carbon and brown carbon. Black carbon (BC; also referred to as light-absorbing carbon [LAC], refractory black carbon [rBC], and soot) is second only to CO2 as a positive forcing agent. Roughly 60% of BC emissions can be attributed to anthropogenic sources (fossil fuel combustion and open-pit cooking), with the remaining fraction being due to biomass burning. Brown carbon (BrC), a major component of biomass burning, collectively refers to non-BC carbonaceous aerosols that typically possess minimal light absorption at visible wavelengths but exhibit pronounced light absorption in the near-ultraviolet (UV) spectrum. Both species can be sourced locally or be remotely transported to the Arctic region and are expected to perturb the radiative balance. The work conducted in this field campaign addresses one of the more glaring deficiencies currently limiting improved quantification of the impact of BC radiative forcing in the cryosphere: the paucity of data on the vertical and spatial distributions of BC. By expanding the Gulfstream aircraft (G-1) payload for the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility-sponsored ACME-V campaign to include the Single-Particle Soot Photometer (SP2)) and leveraging the ACME-V campaign’s deployment within the Arctic Circle during the summer of 2015 (Deadhorse, Alaska [70° 12' 20" N, 148° 30' 42" W]), the truly unique opportunity presented itself to acquire profile data on BC loading at little additional cost. Since the SP2 is a particle-resolved measurement, the resulting data set provides refractory black carbon (rBC) mass loadings, size and mass distributions, and rBC-containing particle mixing state, all of which are expected to readily find value in the modeling community. As part of the ACME-V (http://www.arm.gov/campaigns/aaf2014armacmev) campaign, CO, CO2, and CH4 were also measured, providing the unique opportunity for carbon closure. We will also work closely with modelers who require such data and expect this collaboration will lead directly to a better understanding of the climate impacts of BC in the Arctic. The primary measurement objective was to acquire airborne data on the vertical and spatial distributions of refractory black carbon (rBC) loading, size and mass distribution, and particle mixing state. The primary scientific objective was to provide a targeted data set of rBC particle distributions to better understand and constrain the impact of black carbon radiative forcing in the cryosphere. The SP2-based data set during this campaign is available in the DOE-ARM archive (http://www.arm.gov/campaigns/aaf2015abclp).

54 ENVIRONMENTAL SCIENCES↗

Pico-second laser materials interactions: mechanisms, material lifetime and performance optimization Ted Laurence(14-ERD-014)

Laser-induced damage with ps pulse widths straddles the transition from intrinsic, multiphoton ionization- and avalanche ionization-based ablation with fs pulses to defectdominated, thermal-based damage with ns pulses. We investigated the morphology and scaling of damage for commonly used silica and hafnia coatings as well as fused silica. Using carefully calibrated laser-induced damage experiments, in situ imaging, and high-resolution optical microscopy, atomic force microscopy, and scanning electron microscopy, we showed that defects play an important role in laser-induced damage for pulse durations as short as 1 ps. Three damage morphologies were observed: standard material ablation, ultra-high density pits, and isolated absorbers. For 10 ps and longer, the isolated absorbers limited the damage performance of the coating materials. We showed that damage resulting from the isolated absorbers grows dramatically with subsequent pulses for sufficient fluences. For hafnia coatings, we used electric field modeling and experiments to show that isolated absorbers near the surface were affected by the chemical environment (vacuum vs. air) for pulses as short as 10 ps. Coupled with the silica results, these results suggested that improvements in the performance in the 10 -60 ps range have not reached fundamental limits. These findings motivate new efforts, including a new SI LDRD in improving the laser-damage performance of multi-layer dielectric coatings. A damage test facility for ps pulses was developed and automated, and was used for testing production optics for ARC. The resulting software was transferred to other laser test facilities for fs pulses and multiple wavelengths with 30 ps pulses. Additionally, the LDRD supported the retention and promotion of an important staff scientist in high-resolution dynamic microscopy and laser-damage testing.

36 MATERIALS SCIENCE↗

Weldon Spring, Missouri, Site Annual Report for Calendar Year 2015 June 2016

1.1 Purpose and Scope. This report summarizes the activities, compliance status, annual inspection, and environmental monitoring results from calendar year 2015 for the Weldon Spring, Missouri, Site. The U.S. Department of Energy (DOE) prepares this annual report as part of the site’s long-term surveillance and maintenance (LTS&M) activities, in accordance with the requirements of the Long-Term Surveillance and Maintenance Plan for the Weldon Spring, Missouri, Site (LTS&M Plan) (DOE 2008a) and the Federal Facility Agreement for the Weldon Spring Site (DOE 2006). The Weldon Spring site is a Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) site. 1.2 Site Description. The Weldon Spring site is located in St. Charles County, Missouri, about 30 miles west of St. Louis, Missouri (Figure 1). The site comprises two geographically distinct, DOE-owned properties: the former Weldon Spring Chemical Plant and Raffinate Pit sites (Chemical Plant) and the former Weldon Spring Quarry (Quarry). The former Chemical Plant is located about 2 miles southwest of the junction of Missouri State Route 94 and Interstate 64. The Quarry is about 4 miles southwest of the former Chemical Plant. Both sites are accessible from Missouri State Route 94. During the early 1940s, the Department of the Army acquired 17,232 acres of private land in St. Charles County for the construction of the Weldon Spring Ordnance Works facility. The former Ordnance Works site has since been divided into several contiguous areas under different ownership, as depicted in Figure 2. Current land use of the former Ordnance Works site includes the former Chemical Plant and Quarry, the U.S. Army Reserve Weldon Spring Training Area, the Missouri Department of Conservation (MDC), the Missouri Department of Natural Resources (MDNR) Division of State Parks (MDNR-Parks), Francis Howell High School, a St. Charles County highway maintenance (formerly Missouri Department of Transportation [MoDOT]) facility, the Public Water Supply District No. 2 water supply facility, the St. Charles County law enforcement training center, the village of Weldon Spring Heights, and a University of Missouri research park. The former Chemical Plant and Quarry areas total 228.16 acres. The Former Chemical Plant property occupies 219.50 acres, and the Quarry occupies 8.66 acres.

2015 Annual Report Weldon Spring↗

Container Surface Evaluation by Function Estimation

Container images are analyzed for specific surface features, such as, pits, cracks, and corrosion. The detection of these features is confounded with complicating features. These complication features include: shape/curvature, welds, edges, scratches, foreign objects among others. A method is provided to discriminate between the various features. The method consists of estimating the image background, determining a residual image and post processing to determine the features present. The methodology is not finalized but demonstrates the feasibility of a method to determine the kind and size of the features present.

36 MATERIALS SCIENCE↗