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At least 127 records · Page 7

Genotoxic effect of ethacrynic acid and impact of antioxidants

It is known that ethacrynic acid (EA) decreases the intracellular levels of glutathione. Whether the anticipated oxidative stress affects the structural integrity of DNA is unknown. Therefore, DNA damage was assessed in EA-treated HCT116 cells, and the impact of several antioxidants was also determined. EA caused both concentration-dependent and time-dependent DNA damage that eventually resulted in cell death. Unexpectedly, the DNA damage caused by EA was intensified by either ascorbic acid or trolox. In contrast, EA-induced DNA damage was reduced by N-acetylcysteine and by the iron chelator, deferoxamine. In elucidating the DNA damage, it was determined that EA increased the production of reactive oxygen species, which was inhibited by N-acetylcysteine and deferoxamine but not by ascorbic acid and trolox. Also, EA decreased glutathione levels, which were inhibited by N-acetylcysteine. But, ascorbic acid, trolox, and deferoxamine neither inhibited nor enhanced the capacity of EA to decrease glutathione. Interestingly, the glutathione synthesis inhibitor, buthionine sulfoxime, lowered glutathione to a similar degree as EA, but no noticeable DNA damage was found. Nevertheless, buthionine sulfoxime potentiated the glutathione-lowering effect of EA and intensified the DNA damage caused by EA. Additionally, in examining redox-sensitive stress gene expression, it was found that EA increased HO-1, GADD153, and p21mRNA expression, in association with increased nuclear localization of Nrf-2 and p53 proteins. In contrast to ascorbic acid, trolox, and deferoxamine, N-acetylcysteine suppressed the EA-induced upregulation of GADD153, although not of HO-1. Overall, it is concluded that EA has genotoxic properties that can be amplified by certain antioxidants. - Highlights: • Ethacrynic acid (EA) caused cellular DNA damage. • EA-induced DNA damage was potentiated by ascorbic acid or trolox. • EA increased ROS production, not inhibited by ascorbic acid or trolox. • EA decreased glutathione levels, not prevented by ascorbic acid or trolox. • Buthionine sulfoxime intensified the DNA damage caused by EA.

60 APPLIED LIFE SCIENCES↗

Purposes, paradigms and pressure groups: Accountability and sustainability in EU environmental assessment, 1985-2010

Twenty five years since the introduction of the European Union (EU) environmental impact assessment (EIA) Directive in 1985 this paper reflects on the extent to which environmental assessment (EA) processes, over the course of their evolution over the last 25 years in the EU, have provided a platform for enhancing accountability and sustainability. Surprisingly-in the context of legal mandates for EA-there is little reference in the EA literature explicitly to the literature on accountability and the role EA may play in this increasingly important aspect of governance. The paper explores EA implementation principally from an environmentalist perspective and particularly the way in which NGOs and other advocates for the environment in the UK and EU have used the EA legislation as a lever for increasing democratic, corporate and professional accountability of proponents and decision-makers alike. From an a historical analysis, including two historical EIA case studies and two contemporary SEA case studies, it becomes clear that EA has had an important role to play-at the legislative level in providing the requirements for accountability, and at the implementation level as the lever that can be used to hold individuals, organisations and authorities to account for their actions. The relationship with the shift to sustainability is a close one, since sustainable development demands greater public involvement in decision-making and greater accountability of executive decisions to the public. The lessons from this analysis allow the development of a nascent policy-oriented theory regarding EA's role in accountability, which provides a framework for a distinctive new area of EA research and policy analysis. Moreover, an accountability perspective on EA could help re-frame EA for policy makers from being purely an informational and procedural instrument to one which promotes better accountability and sustainability simultaneously. - Highlights: Black-Right-Pointing-Pointer Little attention in the literature to environmental assessment (EA) and accountability. Black-Right-Pointing-Pointer Evolution of EA in the EU influenced by shifting policy paradigms and demands for accountability. Black-Right-Pointing-Pointer EIA and SEA, as formal procedures, can provide platforms for accountability. Black-Right-Pointing-Pointer Four case studies illustrate how NGOs and others have used EA to further accountability. Black-Right-Pointing-Pointer A policy-oriented theory provides a basis for considering future evolution of EA in the EU.

54 ENVIRONMENTAL SCIENCES↗

Implementation of Enhanced Attenuation at the DOE Mound Site OU-1 Landfill: Accelerating Progress and Reducing Costs - 16270

A field demonstration of enhanced attenuation (EA) was initiated in 2014 to expedite the remediation of industrial solvents in the groundwater impacted by the former landfill Operable Unit 1 (OU-1) at the US Department of Energy (DOE) Mound, Ohio, Site. EA uses active engineering solutions to alter the target site so that the contaminant plume will passively stabilize and shrink. For OU-1, the EA was implemented by targeted injection of an electron donor (vegetable oil) to create 'structured geochemical zones'. Volatile organic compounds (VOCs) in the altered subsurface system encounter alternating anaerobic and aerobic environments along the plume flow path. The effect of these structured geochemical zones is effective and rapid degradation of parent compounds such as trichloroethene (TCE) and tetrachloroethene (PCE), and daughter compounds such as cis-1,2-dichloroethene and vinyl chloride. EA at Mound OU-1 provides a transition to natural attenuation and is an alternative to the baseline pump-and-treat (P and T) system. Industrial solvents (primarily TCE) and other VOCs that originated from the former solid-waste landfill contaminated the groundwater in the Buried Valley Aquifer beneath the Mound site. A groundwater P and T system was initiated in 1996 to control the plume, and a soil vapor extraction system was installed and operated from 1997 to 2003 to remove the bulk of the VOC sources from the vadose zone. Physical removal of the landfill waste and contaminated soil was performed between 2006 and 2010. Approximately 76,100 cubic meters (99,500 cubic yards) of material were removed from the OU-1 landfill area. Operation of the groundwater P and T system continued throughout this period. The principles and technical basis of the ongoing EA field demonstration were developed by the Interstate Technology and Regulatory Council. The goal of the EA implementation is to provide a bridge between active groundwater treatments and monitored natural attenuation. EA relies on understanding and manipulating the contaminant mass balance. Technologies are applied to sustainably reduce the contaminant loading from the source and/or increase the rate of natural attenuation processes within the plume. In 2014, a core team that included DOE, the US Environmental Protection Agency (EPA), the Ohio EPA, and technical support organizations evaluated remedial options for OU-1. During the 2014 evaluation, the team projected a cleanup time frame for the baseline P and T system of 26 additional years and a cleanup time frame for the EA remedy of 13 years. On the basis of that evaluation, EPA approved the implementation of the EA remedy that required the shutdown of the P and T system. The combination of technologies implemented for OU-1 EA included (a) neat vegetable oil in the vadose zone in the former landfill and (b) emulsified vegetable oil within the footprint of the groundwater plume. In the first part of the deployment, neat oil spreads laterally and forms a thin layer on the water table beneath residual soil sources to intercept and reduce future VOC loading and to reduce oxygen inputs to the local groundwater. In the second part of the deployment, emulsified oil forms active bioremediation anaerobic treatment zones within the plume footprint to degrade existing groundwater contaminants (via reductive dechlorination, co-metabolism, or both) and stimulates long-term attenuation capacity in the down-gradient aerobic plume (via co-metabolism). The results from the first year of the field demonstration indicate that the dissolved TCE and PCE plumes have decreased in size and mass. Statistical tests indicate that the VOC concentrations in the majority of the source-area wells are decreasing. The VOC concentrations throughout the plume are projected to be below the target maximum contaminant level of 2 to 5 μg/L within 5 to 10 years-sooner than the design projection of 13 years. The biogeochemistry and microbial community within the structured geochemical zones are consistent with the design and appear to be stable. At Mound OU-1, EA has accelerated progress toward the remedial action objectives and reduced costs. Ongoing monitoring will determine whether the EA remedy has transitioned the site into monitored natural attenuation status and whether the EA will continue to be effective, timely, and sustainable. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Echinocystic acid inhibits RANKL-induced osteoclastogenesis by regulating NF-κB and ERK signaling pathways

Receptor activator of nuclear factor-κB ligand (RANKL) is a key factor in the differentiation and activation of osteoclasts. Echinocystic acid (EA), a pentacyclic triterpene isolated from the fruits of Gleditsia sinensis Lam, was reported to prevent reduction of bone mass and strength and improve the cancellous bone structure and biochemical properties in ovariectomy rats. However, the molecular mechanism of EA on the osteoclast formation has not been reported. The purpose of this study was to investigate the effects and mechanism of EA on RANKL-induced osteoclastogenesis. Our results showed that EA inhibited the formation of osteoclast, as well as the expression of osteoclastogenesis-related marker proteins in bone marrow macrophages (BMMs). At molecular levels, EA inhibited RANKL-induced NF-κB activation and ERK phosphorylation in BMMs. In conclusion, the present study demonstrated that EA can suppress osteoclastogenesis in vitro. Moreover, we clarified that these inhibitory effects of EA occur through suppression of NF-κB and ERK activation. Therefore, EA may be a potential agent in the treatment of osteoclast-related diseases such as osteoporosis. - Highlights: • EA inhibited the formation of osteoclast in BMMs. • EA inhibits the expression of osteoclastogenesis-related marker proteins in BMMs. • EA inhibits RANKL-induced NF-κB activation in BMMs. • EA inhibits RANKL-induced ERK phosphorylation in BMMs.

60 APPLIED LIFE SCIENCES↗

Electrically-Assisted Tubing Processes for Enhancing Manufacturability of Oxide Dispersion Strengthened Structural Materials for Nuclear Reactor Applications

The overall goal of this project is to enhance the formability of Nanostructured Ferritic Alloys (NFAs) such that high-strength thin-walled claddings can be successfully and economically manufactured for use in future nuclear reactors. Specifically, four objectives were identified: Objective #1 – to achieve a good understanding of the mechanical behavior and resulting microstructure of 14YWT made from the powder form subjected to various Electrically- Assisted (EA) loading conditions. Objective #2 – to conduct EA-flat rolling of 14YWT completed and the prioritization/selection of two alternative designs of EA tube rolling processes. Objective #3 – to design and assemble a new EA tube rolling machine. Objective #4 – to conduct rolling using the new EA rolling machine. The above objectives were achieved and the findings can be further applied to establish other innovative fabrication processes. Specifically, the major accomplishments are summarized as: The use of an EA forming process was investigated to reduce the forming force of ODS ferritic steels. The effect of a continuous electric current on 14YWT during plastic deformation was evaluated. EA uniaxial tension tests show that the electric current is able to reduce the flow stress of 14YWT. 14YWT exhibits a ductility minimum at a current density of 34.5 A/mm2 which is consistent with fractography results. Hardness measurements and TEM results indicate that oxide particles are stable during the EA process. By following the tests, microstructure analysis was performed on the sample in its as-received state and after current treatment. The microstructures are stable when subjected to high current density. The related thermal model was developed to predict the Joule heating temperatures. The temperatures were compared with the experimental results. At last, a temperature-dependent hardening model was used to explore the mechanisms acting during EA deformation. Since the model can accurately predict the yield strength of 14YWT under EA conditions without the incorporation of non-thermal effects, it can be concluded that the reduction in yield strength is due to the Joule heating generated under continuous current loading conditions. An oven-heated pure thermal tension test was conducted to confirm this conclusion. The new EA tube rolling machine has been completely developed. The related work includes: (1) forming process design; (2) analysis of the effect of roll-tube contact geometry on rolling force; (3) analysis of machine performance under mechanical loading; (4) design of machine electrical setting path and insulation; (5) multi-pass process analysis; (6) design of power transmission system (axial/radial/torque feeding mechanisms), roll bearing system, cooling system, workpiece feeding mechanism, and other related mechanical connection support components; (7) design and optimization of roll profiles/dimensions; (8) analysis and simulation of the rolling process; (9) development of engineering drawings and fabrication; (10) assembly and calibration of the EA tube rolling machine; (11) design and integration of the electrical control system; (12) hardware integration for high power supply electrically-assisted rolling process; (13) induction heating system integration; (14) experimental tests for the new rolling process. Through the process from conceptual design to final machine calibration and experimental tests, there are many technical and physical works that have been implemented and improved for the best performance of the innovative prototype.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Effects of Mild Hypobaric Hypoxia on Visual Field Impairment

INTRODUCTION: The primary objective of the Exploration Atmosphere (EA) study is to validate a new prebreathe protocol necessary before exposure to a suited hypobaric environment during extravehicular activity (EVA) from a habitat ‘exploration atmosphere’ of 56.5kPa (8.2 psia), 34% O2, 66% N2. Prebreathe protocols must be time and resource efficient while also controlling Decompression Sickness (DCS) risk to within acceptable limits. The habitat hypobaric exploration atmosphere also results in a mildly hypoxic environment (piO2 = 128mmHg). As a secondary objective of the EA study, we characterized the effects of 11-day exposure to a mild hypobaric hypoxic environment on visual performance. METHODS: Two, 11-day hypobaric chamber tests were performed (EA-1and EA-2, n=8 each) in NASA’s 20-foot chamber at Johnson Space Center where subjects lived in the exploration atmosphere. Subjects also underwent simulated 6-hour EVAs at 85% O2 and 29.6 kPa during EVA on days 3, 5, 7, 9, and 11. Visual acuity (VA), a measure of spatial resolution, and contrast sensitivity (CS), a measure of ability to distinguish ever finer increments of brightness, were assessed on non-EVA days by using gapped Landolt C testing. The luminance was controlled by using a booth, a light monitor, and a lighting rheostat. EA-1 data had revealed problems in lighting control impacting consistency of the data. Procedures were subsequently updated for the EA-2 test. RESULTS: EA-1 data revealed large variance and data recording errors and was removed from the analysis. One participant left the study at Test Day 3 during EA-2. EA-2 ANOVA results showed CS (mean change=0.010 logCSWeber) and VA (mean change, -0.016 logMAR) between pre-test and 11-day test phases; however, neither VA nor CS changes were statistically significant. There were non-statistically significant declines in VA across test phases. DISCUSSION: Overall, visual field performance did not exhibit clinically significant changes (3 lines or greater change in LogMar chart) during exposure to the mild hypoxic exploration atmosphere environment compared to pre-test baseline. The consistency and stability of VA data during EA-2 suggests that the mild hypobaric hypoxic environment did not cause clinically significant negative impacts to participants’ visual field performance.

Visual Acuity↗

Effects of Mild Hypobaric Hypoxia on Visual Field Impairment

INTRODUCTION: The primary objective of the Exploration Atmosphere (EA) study is to validate a new prebreathe protocol necessary before exposure to a suited hypobaric environment during extravehicular activity (EVA) from a habitat ‘exploration atmosphere’ of 56.5kPa (8.2 psia), 34% O2, 66% N2. Prebreathe protocols must be time and resource efficient while also controlling Decompression Sickness (DCS) risk to within acceptable limits. The habitat hypobaric exploration atmosphere also results in a mildly hypoxic environment (piO2 = 128mmHg). As a secondary objective of the EA study, we characterized the effects of 11-day exposure to a mild hypobaric hypoxic environment on visual performance. METHODS: Two, 11-day hypobaric chamber tests were performed (EA-1and EA-2, n=8 each) in NASA’s 20-foot chamber at Johnson Space Center where subjects lived in the exploration atmosphere. Subjects also underwent simulated 6-hour EVAs at 85% O2 and 29.6 kPa during EVA on days 3, 5, 7, 9, and 11. Visual acuity (VA), a measure of spatial resolution, and contrast sensitivity (CS), a measure of ability to distinguish ever finer increments of brightness, were assessed on non-EVA days by using gapped Landolt C testing. The luminance was controlled by using a booth, a light monitor, and a lighting rheostat. EA-1 data had revealed problems in lighting control impacting consistency of the data. Procedures were subsequently updated for the EA-2 test. RESULTS: EA-1 data revealed large variance and data recording errors and was removed from the analysis. One participant left the study at Test Day 3 during EA-2. EA-2 ANOVA results showed CS (mean change=0.010 logCSWeber) and VA (mean change, -0.016 logMAR) between pre-test and 11-day test phases; however, neither VA nor CS changes were statistically significant. There were non-statistically significant declines in VA across test phases. DISCUSSION: Overall, visual field performance did not exhibit clinically significant changes (3 lines or greater change in LogMar chart) during exposure to the mild hypoxic exploration atmosphere environment compared to pre-test baseline. The consistency and stability of VA data during EA-2 suggests that the mild hypobaric hypoxic environment did not cause clinically significant negative impacts to participants’ visual field performance.

Visual Acuity↗

The effect of alkali-soluble lignin on purified core cellulase and hemicellulase activities during hydrolysis of extractive ammonia-pretreated lignocellulosic biomass

Removing alkali-soluble lignin using extractive ammonia (EA) pretreatment of corn stover (CS) is known to improve biomass conversion efficiency during enzymatic hydrolysis. In this study, we investigated the effect of alkali-soluble lignin on six purified core glycosyl hydrolases and their enzyme synergies, adopting 31 enzyme combinations derived by a five-component simplex centroid model, during EA-CS hydrolysis. Hydrolysis experiment was carried out using EA-CS(-) (approx. 40% lignin removed during EA pretreatment) and EA-CS(+) (where no lignin was extracted). Enzymatic hydrolysis experiments were done at three different enzyme mass loadings (7.5, 15 and 30 mg protein g -1 glucan), using a previously developed high-throughput microplate-based protocol, and the sugar yields of glucose and xylose were detected. The optimal enzyme combinations (based on % protein mass loading) of six core glycosyl hydrolases for EA-CS(-) and EA-CS(+) were determined that gave high sugar conversion. The inhibition of lignin on optimal enzyme ratios was studied, by adding fixed amount of alkali-soluble lignin fractions to EA-CS(-), and pure Avicel, beechwood xylan and evaluating their sugar conversion. The optimal enzyme ratios that gave higher sugar conversion for EA-CS(-) were CBH I: 27.2–28.2%, CBH II: 18.2–22.2%, EG I: 29.2–34.3%, EX: 9.0–14.1%, βX: 7.2–10.2%, βG: 1.0–5.0% (at 7.5–30 mg g -1 protein mass loading). Endoglucanase was inhibited to a greater extent than other core cellulases and xylanases by lignin during enzyme hydrolysis. We also found that alkali-soluble lignin inhibits cellulase more strongly than hemicellulase during the course of enzyme hydrolysis.

09 BIOMASS FUELS↗

Correlations of event activity with hard and soft processes in p + Au collisions at $\sqrt{s_{NN}}$ = 200 GeV at the RHIC STAR experiment

With the STAR experiment at the BNL Relativistic Heavy Ion Collider, we characterize $\sqrt{s_{NN}}$ = 200GeV p + Au collisions by event activity (EA) measured within the pseudorapidity range η ϵ[–5,–3.4] in the Au-going direction and report correlations between this EA and hard- and soft-scale particle production at midrapidity (η ϵ[–1,1]). At the soft scale, charged particle production in low-EA p + Au collisions is comparable to that in p + p collisions and increases monotonically with increasing EA. At the hard scale, we report measurements of high transverse momentum (p T ) jets in events of different EAs. In contrast with the soft particle production, high-p T particle production and EA are found to be inversely related. Furthermore, to investigate whether this is a signal of jet quenching in high-EA events, we also report ratios of p T imbalance and azimuthal separation of dijets in high- and low-EA events. Within our measurement precision, no significant differences are observed, disfavoring the presence of jet quenching in the highest 30% EA p + Au collisions at $\sqrt{s_{NN}}$ = 200GeV.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Innovative Electrostatic Adhesion Technologies

Developing specialized Electro-Static grippers (commercially used in Semiconductor Manufacturing and in package handling) will allow gentle and secure Capture, Soft Docking, and Handling of a wide variety of materials and shapes (such as upper-stages, satellites, arrays, and possibly asteroids) without requiring physical features or cavities for a pincher or probe or using harpoons or nets. Combined with new rigid boom mechanisms or small agile chaser vehicles, flexible, high speed Electro-Static Grippers can enable compliant capture of spinning objects starting from a safe stand-off distance. Electroadhesion (EA) can enable lightweight, ultra-low-power, compliant attachment in space by using an electrostatic force to adhere similar and dissimilar surfaces. A typical EA enabled device is composed of compliant space-rated materials, such as copper-clad polyimide encapsulated by polymers. Attachment is induced by strong electrostatic forces between any substrate material, such as an exterior satellite panel and a compliant EA gripper pad surface. When alternate positive and negative charges are induced in adjacent planar electrodes in an EA surface, the electric fields set up opposite charges on the substrate and cause an electrostatic adhesion between the electrodes and the induced charges on the substrate. Since the electrodes and the polymer are compliant and can conform to uneven or rough surfaces, the electrodes can remain intimately close to the entire surface, enabling high clamping pressures. Clamping pressures of more than 3 N/cm2 in shear can be achieved on a variety of substrates with ultra-low holding power consumption (measured values are less than 20 microW/Newton weight held). A single EA surface geometry can be used to clamp both dielectric and conductive substrates, with slightly different physical mechanisms. Furthermore EA clamping requires no normal force be placed on the substrate, as conventional docking requires. Internally funded research and development has demonstrated that EA can function effectively in space, even in the presence of strong ultraviolet radiation, atomic oxygen, and free electrons. We created a test setup in an existing vacuum chamber to simulate low-Earth-orbit conditions. An EA mechanism was fabricated and installed in the chamber, instrumented, operated in a vacuum, and subjected to ultraviolet photons and free electrons generated by an in-chamber multipactor electron emitter. Extensions to EA that can add value include proximity and contact sensing and transverse motion or rotation, both of which could enhance docking or assembly applications. Possible next steps include development of targeted applications for ground investigation or on-orbit subsystem performance demonstrations using low cost access to space such as CubeSats.

Bryan, Tom↗

The mediation of environmental assessment's influence: What role for power?

Considerable empirical research has been conducted on why policy tools such as environmental assessment (EA) often appear to have 'little effect' (after Weiss) on policy decisions. This article revisits this debate but looks at a mediating factor that has received limited attention to-date in the context of EA - political power. Using a tripartite analytical framework, a comparative analysis of the influence and significance of power in mediating environmental policy integration is undertaken. Power is analysed, albeit partially, through an exploration of institutions that underpin social order. Empirically, the research examines the case of a new approach to policy-level EA (essentially a form of Strategic Environmental Assessment) developed by the World Bank and its trial application to urban environmental governance and planning in Dhaka mega-city, Bangladesh. The research results demonstrate that power was intimately involved in mediating the influence of the policy EA approach, in both positive (enabling) and negative (constraining) ways. It is suggested that the policy EA approach was ultimately a manifestation of a corporate strategy to maintain the powerful position of the World Bank as a leading authority on international development which focuses on knowledge generation. Furthermore, as constitutive of an institution and reflecting the worldviews of its proponents, the development of a new approach to EA also represents a significant power play. This leads us to, firstly, emphasise the concepts of strategy and intentionality in theorising how and why EA tools are employed, succeed and fail; and secondly, reflect on the reasons why power has received such limited attention to-date in EA scholarship. - Highlights: Black-Right-Pointing-Pointer Conducts empirical research on the neglected issue of power. Black-Right-Pointing-Pointer Employs an interpretation of power in which it is viewed as a productive phenomenon. Black-Right-Pointing-Pointer Analyses the influence of power in the trial application of a new approach to policy environmental assessment. Black-Right-Pointing-Pointer Demonstrates the importance of power dynamics in understanding the successes and failures of environmental assessment.

54 ENVIRONMENTAL SCIENCES↗

The discretionary power of the environmental assessment practitioner

Discretion is an essential and unavoidable element of most decision-making and is thus often closely related to the judgment exercised by politicians and practitioners alike. It is evident that discretionary power can be executed in different ways, leading to different results. Therefore, it also has a significant influence on the effectiveness of the environmental assessment (EA) as examined in recent environment impact assessment (EIA) and strategic environment assessment (SEA) literature. However, limited attention has been given to the practitioners' role and how they exercise their discretion, while the effectiveness and implementation of decisions has been a recurrent theme in EA literature. This article explores the connections between discretion and some of the fundamental ideas behind how EIA and SEA function in our societies. Firstly, the article develops and presents a theoretical model of discretion, allowing us to explore the phenomena of discretion from four dimensions: source, form, value and dynamics of discretion. Secondly, a review of EA literature is performed with the purpose of mapping how discretion is studied and what kind of discretion is found in the context of EA – focusing on one of the dimensions – ‘source of discretion’. The results imply that it is prevalent for practitioners to exercise rule, value and task discretion in every choice they make at each stage of the EA implementation process, which influences EA effectiveness, either positively or negatively, depending on how discretionary power is exercised and reflected in EA practitioners' practice. It draws both the management's attention to how to regulate EA policies and the practitioners' attention to how to make a difference.

54 ENVIRONMENTAL SCIENCES↗

Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations

Two-dimensional (2D) halide perovskites have outstanding optoelectronic properties, and they feature a variety of organic cation spacers and cage A-site cations that can be incorporated into their structures. It has recently been reported that the Goldschmidt tolerance factor can be relaxed and expanded in iodide 2D perovskites. Bromide 2D perovskites, whose multilayer structures and optical properties are much less studied, provide a great platform for studying structure-property relationships for 2D perovskites with large Asite cations. Herein, we report the synthesis and structure of three new 2D bromide perovskites-(BA)(2)(MHy)(2)Pb3Br10 (BA, butylammonium; MHy, methylhydrazinium), (BA)(2)(EA)(2)Pb3Br10 (EA is ethylammonium), and (BA)(2)(DMA)Pb2Br7 (DMA is dimethylammonium). We compared them with other 2D perovskites with different A-site cations but with the same spacer and layer thickness. Single-crystal structures show that the Pb-Br bonds are elongated to accommodate the large A-site cations. Additionally, the octahedra in (BA)(2)(MHy)(2)Pb3Br10 and (BA)(2)(EA)(2)Pb3Br10 are highly distorted, and their different stacking patterns of the inner and outer layers lead to the formation of the n = 3 phases. Density functional theory calculations show that 2D perovskites with larger A-site cations (e.g., DMA, MHy, and EA) have smaller band dispersions and larger effective masses than those with Cs+ and MA. (BA)(2)(MHy)(2)Pb3Br10 also exhibits one of the largest Rashba splittings in the literature. Structures with large cage cations also exhibit high band gaps within the same n number and short photoluminescence (PL) lifetimes. Temperature- and power-dependent PL measurements reveal that the broad shoulder in the PL peak originates from the trap states.

Emission↗

Erratum: “Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga–Kr, In–Xe, and Tl–Rn” [J. Chem. Phys. 151, 024303 (2019)]

In Ref. 1 incorrect values for the spin-orbit effects on the electron affinities (EAs) of Ga and In were used in Table IV. The KRCI values shown in Table III of Ref. 1, -0.49 and -0.94 kcal/mol for Ga and In, respectively, should have been given. Correct use of these latter values results in final FPD EAs for Ga and In of 6.97 and 8.91 kcal/mol, respectively. The incorrect FPD values were also given in the Abstract and Conclusion sections of Ref. 1. In addition, the experimental EA for In shown in the last column of Table IV was incorrect and should be 8.85 kcal/mol (the actual value being 8.8534 but only two decimal places are displayed throughout this table). A complete replacement for Table IV is given below with the corrected values given in bold font. The corrected FPD and experimental EA values for In in particular changes some of the conclusions of Ref. 1, namely when it is stated both in the abstract and the main text (Sec. III.B and Conclusions) that the experimental EA values for all of the group 13 (Ga, In, and Tl) EAs are too large. This is obviously not true for the EA of In, where the actual FPD value and the experimental result of Walter et al. are in excellent agreement, to within 0.1 kcal/mol. The FPD EAs of the other two group 13 elements, Ga and Tl, differ from their experimental values by 2.5 and 1.3 kcal/mol, respectively, which is still outside of the estimated uncertainty limits of this FPD approach (conservatively ±0.5 kcal/mol), particularly for Ga, therefore the original conclusions for these two elements are largely unchanged.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Extractive Ammonia Pretreatment on the Ultrastructure and Glycan Composition of Corn Stover

Lignocellulosic biomass is highly recalcitrant and requires a pretreatment step to improve the enzyme accessibility and fermentable sugar yields during enzymatic hydrolysis. Our previous studies demonstrated the rearrangement of the hydrogen bond network within CIII, makes it “amorphous-like” and facilitates easier glucan chain extraction by enzyme. Also, these changes increase the number of solvent-exposed glucan chain hydrogen bonds with water ~50% lowering the surface-bound cellulase by 60–70%. Also, major chemical modifications to lignin occur via ammonolysis of ester-linked ferulate and coumarate linkage. These apparent ultrastructural changes help the enhancement of cellulase activity resulting in higher production of fermentable sugars during enzyme hydrolysis of EA pretreated corn stover relative to Ammonia Fiber Expansion (AFEX) pretreatment. To understand ultra-structural modifications that occur during EA pretreatment, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were used to examine untreated and EA-pretreated corn stover in an effort to visualize changes in the biomass resulting from the pretreatment. In addition, Immunofluorescence Microscopy was applied to both untreated and pretreated plant cell walls using glycan-directed monoclonal antibodies to reveal possible changes in the spatial distributions of wall glycan epitopes resulting from EA pretreatment. This evaluation was complemented with glycome profiling to determine the glycan epitope compositions of EA-pretreated cell walls relative to untreated and AFEX pretreated corn stover, where lignin and carbohydrates are not extracted. Distinct differences could be observed in the case of xyloglucan, unsubstituted and substituted pectin- and pectic-arabinogalactan-epitope levels in the plant cell wall after EA pretreatment compared with untreated and AFEX-pretreated walls. Liquid ammonia induced de-lignification of cell wall has helped to clearly identify the glucans that are intact after pretreatment. These studies support some of our hypothesis that liquid ammonia cleaves lignin–carbohydrate ester linkages, partially solubilizing lignin and its associated carbohydrates. Specifically, the imaging studies clearly show that some of the cell wall components are extracted as a separate liquid stream during the EA process, thereby creating porous, interconnected tunnel-like networks in the plant cell walls thereby providing better access of carbohydrate polymers to enzymes and thereby increasing the sugar yield from the EA-pretreated biomass.

09 BIOMASS FUELS↗

Sustainable Remediation of Radionuclides By a Common Sense Approach to Enhanced Attenuation - 16441

Development of in situ and relatively passive remedies for treatment of groundwater contaminated by metals and radionuclides is becoming more important because of the difficulty and cost - both to the environment and financially -- of removing these types of contaminants from the subsurface by pump-and-treat or excavation. In situ technologies rely on reactions that tend to remove contaminants from groundwater by partitioning them to solid phases in the aquifer. Monitored natural attenuation (MNA) relies solely on natural reactions to achieve remedial goals. Enhanced attenuation (EA) uses engineered approaches to supplement remediation when MNA is not sufficient to meet remedial goals. Both approaches leave contaminants in the subsurface and require a high burden of proof that contaminants will not be mobilized and become a risk in the future. Proof of the sustained effectiveness of an EA remedy is made much easier by strategic design. In multi-contaminant plumes, it is important to prioritize contaminants according to the risk they pose, with the recognition that one remedy rarely treats all contaminants. The goal for the engineered portion of the remedy should be maximum risk reduction with minimal engineering. Natural attenuation or negotiated alternate concentration levels will often allow low risk contaminants to go untreated. Whenever possible, the remedy should be consistent with the geochemical evolution of the waste site, insuring that the treated immobilized contaminants are likely to remain relatively immobile for long time frames. Finally, use what nature provides geologically, hydrologically, geochemically, or microbiologically in the remedy design. One of the impediments faced by waste site managers in implementing EA remedies is paralysis by perceived complexity. There are things that must be known to design an effective EA remedy, but there is always the temptation to know everything to eliminate the possibility of failure. Furthermore, there are plenty of people warning of failure if all is not known and they are usually willing to help the design team know all, for a price. Yet, the price of trying to eliminate all risk is never implementing an innovative remedy. All parties involved -- scientists/engineers, waste site managers, regulators and stakeholders must assume some degree of risk to deploy an EA remedy. If all parties are to assume some risk, then trust built through close communication from the start is required. The U.S. Department of Energy Office of Environmental Management has funded an applied field research initiative for several years focused, in part, on developing EA remedies for metals and radionuclides using these guiding principles. This approach to EA remedies grew out of developing and deploying a remediation strategy to replace a pump-and-treat system at the F-Area Seepage Basins on the Savannah River Site. The pump-and-treat system was energy intensive, produced several thousand cubic feet of solid radioactive waste per year, and cost $ 1 million per month to operate. The EA remedy that replaced the pump-and-treat is energy efficient, produces no waste, and costs approximately $1 million per year to maintain. At the F-Area Seepage Basins approximately 7 billion liters of low level radioactive waste solutions were disposed in three unlined basins resulting in contaminated groundwater containing various radionuclides and other contaminants. The primary contaminants of concern are tritium, strontium-90, uranium, and iodine-129. Other key features of the contaminant plume are its acidic nature with pH values as low as 3.2, its vertical stratification in the water table aquifer, and the tendency of the most contaminated portions to follow troughs in the top of the clay separating the upper aquifer zone from the lower aquifer zone. The geology was exploited by installing a funnel-and-gate system into the clay with the barrier portion blocking contaminant flow paths in the troughs in the clay. This forces the most contaminated water to flow through the gates where it encounters an in situ treatment zone created by periodic injections of alkaline solution. The flux of tritium has been reduced significantly by the barrier walls. Strontium-90 and uranium are treated by enhanced sorption in the circum-neutral pH treatment zone, consistent with natural geochemical evolution of the waste site from acidic to more neutral pH. An additional in situ treatment zone was created up-gradient of the one of the gates to treat iodine-129. Sub-micrometer diameter silver chloride particles were injected into the aquifer by direct push methods to create the treatment zone. In the laboratory and in a field pilot test the poorly soluble silver chloride particles reacted with iodide to form much less soluble silver iodide. Evaluation of the effectiveness of the silver chloride is ongoing. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reflecting on mainstreaming through environmental appraisal in times of financial crisis — From ‘greening’ to ‘pricing’?

The issue of mainstreaming has witnessed a revival over the last few years, not least because the latest financial crisis has triggered a renewed enthusiasm and a remarkable comeback amongst policy-making and environmental appraisal (EA) communities. Traditionally, environmental mainstreaming is linked to ideas of (environmental) integration and to the ‘greening’ of public policies. Yet, more recent mainstreaming efforts are building on the idea that the achievement of economic growth and of social well-being is not only dependent upon the protection of the environment, but on the fact that the environment should be valued as a source of goods and a provider of services, as well. In this context and despite the many shortcomings that EA has experienced as a mainstreaming tool over the last two decades, calls for EA to engage with ecosystem services and incorporate pricing valuations in its approach to mainstreaming are emerging, raising questions about the role and purpose of EA as an environmental mainstreaming tool. This paper aims to reflect on the role of EA as a mainstreaming tool, in terms of the extent to which it is mainstreaming the environment into policies for sustainable development and changing ‘the mainstream’ by breaking down the false dichotomy of environment and (economic) development. If mainstreaming through EA was to incorporate both greening and pricing logics, could EA be more effective in reframing the environment and development as correlated variables rather than competing variables? -- Highlights: ► Mainstreaming is witnessing a revival over the last few years and a comeback amongst environmental appraisal communities. ► Mainstreaming efforts through environmental appraisal have failed to challenge the deeply rooted belief in economic growth. ► Recent mainstreaming efforts are incorporated in “green deals” following ecological modernisation discourses. ► Environmental appraisal is urged to embrace ecosystem service approaches prompting a rethink of its advocacy role and purpose.

54 ENVIRONMENTAL SCIENCES↗

Uncovering the factors that can support and impede post-disaster EIA practice in developing countries: The case of Aceh Province, Indonesia

The close relationship between environmental degradation and the occurrence and severity of disaster events has in recent years raised the profile of environmental assessment (EA) in the disaster management field. EA has been identified as a potentially supportive tool in the global effort to reduce disaster risk. As a component of this, attention has been brought specifically to the importance of the application of EA in the aftermath of disaster events in order to help prevent recurrence and promote sustainability. At the same time, however, it has also been recognised that post-disaster environments may be unfavourable to such practices. Looking at the practice of environmental impact assessment (EIA), this paper reports on a study which sought to identify more specifically the factors which can both support and hinder such practice following disaster events in a developing country context. Analysing the situation in Aceh Province, Indonesia, after the impact of two tsunamigenic earthquakes in late 2004 and early 2005, it is concluded that if EIA is to have a central role in the post-disaster period, pre-disaster preparation could be a key. -- Highlights: • Close relationship between environmental degradation and occurrence/severity of disaster events has raised profile of EA. • EA as a potentially supportive tool in the global effort to reduce disaster risk • Application of EA in the aftermath of disaster events to help prevent recurrence and promote sustainability • The paper looks at factors which can both support and hinder EA following disaster events in a developing country context. • We analyse the situation in Aceh Province, Indonesia, after the impact of two tsunamigenic earthquakes in 2004 and 2005.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗