Emission of volatile halogenated organic compounds over various Dead Sea landscapes

Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X is Br, Cl and I) and very short-lived halogenated substances (VSLSs; bromoform-CHBr3, dibromomethane-CH2Br2, bromodichloromethane-CHBrCl2, trichloroethylene-C2HCl3, chloroform-CHCl3- A nd dibromochloromethane-CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere and for their key role in aerosol formation. Insufficient characterization of the sources and the emission rate of VHOCs limits our ability to understand and assess their impact in both the troposphere and stratosphere. Over the last two decades, several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge of emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and fluxes of several chlorinated and brominated VHOCs from different landscapes and natural and agricultural vegetated sites at the Dead Sea during different seasons. Fluxes were generally positive (emission into the atmosphere), corresponding to elevated mixing ratios, but were highly variable. Fluxes (and mixing ratios) for the investigated VHOCs ranged as follows: CHBr3 from 79 to 187 nmolm2 d1 (1.9 to 22.6 pptv), CH2Br2 from 55 to 71 nmolm2 d1 (0.7 to 19 pptv), CHBr2Cl from 408 to 768 nmolm2 d1 (0.4 to 11 pptv), CHBrCl2 from 29 to 45 nmolm2 d1 (0.5 to 9.6 pptv), CHCl3 from 577 to 883 nmolm2 d1 (15 to 57 pptv), C2HCl3 from 74 to 884 nmolm2 d1 (0.4 to 11 pptv), methyl chloride (CH3Cl) from-5300 to 10,800 nmolm2 d1 (530 to 730 pptv), methyl bromide (CH3Br) from 111 to 118 nmolm2 d1 (7.5 to 14 pptv) and methyl iodide (CH3I) from 25 to 17 nmolm2 d1 (0.4 to 2.8 pptv). Taking into account statistical uncertainties, the coastal sites (particularly those where soil is mixed with salt deposits) were identified as sources of all VHOCs, but this was not statistically significant for CHCl3. Further away from the coastal area, the bare soil sites were sources for CHBrCl2, CHBr2Cl, CHCl3, and probably also for CH2Br2 and CH3I, and the agricultural sites were sources for CHBr3, CHBr2Cl and CHBrCl2. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHCl3 > CHBr3 > CHBrCl2 and lowest positive flux incidence for CHCl3 among all trihalomethanes; this finding can be explained by the soil's enrichment with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the emission of CHBr2Cl and CHBrCl2 and likely also for CHBr3. There were no indications for correlation of the brominated trihalomethanes with CHCl3. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the flux correlations between these compounds and methyl halides (particularly CH3I) suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevated emission of VHOCs from bare soil under semiarid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes

Incidental threat during visuospatial working memory in adolescent anxiety: an emotional memory-guided saccade task

BackgroundPediatric anxiety disorders are among the most common psychiatric mental illnesses in children and adolescents, and are associated with abnormal cognitive control in emotional, particularly threat, contexts. In a series of studies using eye movement saccade tasks, we reported anxiety-related alterations in the interplay of inhibitory control with incentives, or with emotional distractors. The present study extends these findings to working memory (WM), and queries the interaction of spatial WM with emotional stimuli in pediatric clinical anxiety. MethodsParticipants were 33 children/adolescents diagnosed with an anxiety disorder, and 22 age-matched healthy comparison youths. Participants completed a novel eye movement task, an affective variant of the memory-guided saccade task. This task assessed the influence of incidental threat on spatial WM processes during high and low cognitive load. ResultsHealthy but not anxious children/adolescents showed slowed saccade latencies during incidental threat in low-load but not high-load WM conditions. No other group effects emerged on saccade latency or accuracy. ConclusionsThe current data suggest a differential pattern of how emotion interacts with cognitive control in healthy youth relative to anxious youth. These findings extend data from inhibitory processes, reported previously, to spatial WM in pediatric anxiety

Emission of volatile halogenated organic compounds over various landforms at the Dead Sea

Abstract. Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X = Br, Cl and I) and very short-lived halogenated substances (VSLS; CHBr3, CH2Br2, CHBrCl2, C2HCl3, CHCl3 and CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere, and for their key role in aerosol formation. Insufficient characterization of the sources and emission rate of VHOCs limits our present ability to understand and assess their impact in both the troposphere and the stratosphere. Over the last two decades several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge about emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and the fluxes of several chlorinated and brominated VHOCs from different landforms and vegetated sites at the Dead Sea during different seasons. Fluxes were highly variable but were generally positive (emissive), corresponding with elevated mixing ratios for all of the VHOCs investigated in the four investigated site types – bare soil, coastal, cultivated and natural vegetated sites – except for fluxes of CH3I and C2HCl3 over the vegetated sites. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHBr3 > CHBrCl2 > CHCl3. This finding can be explained by the enrichment of soil with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the formation and emission of all the above trihalomethanes but also for CH2Br2. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the high correlations of flux with methyl halides, and particularly with CH3I, suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevate emission of VHOCs from bare soil under semi-arid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes, and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes

Relaxed Models for Adversarial Streaming: The Advice Model and the Bounded Interruptions Model

Streaming algorithms are typically analyzed in the oblivious setting, where we assume that the input stream is fixed in advance. Recently, there is a growing interest in designing adversarially robust streaming algorithms that must maintain utility even when the input stream is chosen adaptively and adversarially as the execution progresses. While several fascinating results are known for the adversarial setting, in general, it comes at a very high cost in terms of the required space. Motivated by this, in this work we set out to explore intermediate models that allow us to interpolate between the oblivious and the adversarial models. Specifically, we put forward the following two models: (1) *The advice model*, in which the streaming algorithm may occasionally ask for one bit of advice. (2) *The bounded interruptions model*, in which we assume that the adversary is only partially adaptive. We present both positive and negative results for each of these two models. In particular, we present generic reductions from each of these models to the oblivious model. This allows us to design robust algorithms with significantly improved space complexity compared to what is known in the plain adversarial model

A Framework for Adversarial Streaming via Differential Privacy and Difference Estimators

Classical streaming algorithms operate under the (not always reasonable) assumption that the input stream is fixed in advance. Recently, there is a growing interest in designing robust streaming algorithms that provide provable guarantees even when the input stream is chosen adaptively as the execution progresses. We propose a new framework for robust streaming that combines techniques from two recently suggested frameworks by Hassidim et al. [NeurIPS 2020] and by Woodruff and Zhou [FOCS 2021]. These recently suggested frameworks rely on very different ideas, each with its own strengths and weaknesses. We combine these two frameworks into a single hybrid framework that obtains the "best of both worlds", thereby solving a question left open by Woodruff and Zhou

The structural basis of RNA-catalyzed RNA polymerization

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Biology, 2010.Cataloged from PDF version of thesis.Includes bibliographical references.The Class I ligase is an artificial ribozyme that catalyzes a reaction chemically identical to a single turnover of RNA-dependent RNA polymerization. Such an activity would have been requisite for the emergence of a self-replicase ribozyme, an enzyme that, according to the RNA World hypothesis, would be fundamental for the emergence of life. Demonstrating the plausibility of RNA-catalyzed self-replication, the Class I ligase catalytic machinery was previously harnessed to produce general RNA polymerase ribozymes. Hence, this ligase represents a robust model system for studying both the potential role RNA may have played in the origins of life and RNA catalysis in general. Through a combination of crystallographic and biochemical experiments, we have sought to elucidate the structure and mechanism of this ribozyme. As a starting point for our experiments, the crystal structure of the self-ligated product was solved to 3.0 Angstrom resolution, revealing a tripodal architecture in which three helical domains converge in the vicinity of the ligation junction. A handful of tertiary interactions decorate this tripod scaffold; among them were two instances of a novel motif, the A-minor triad. The structure elucidated interactions that recognize and bind the primer-template duplex and those that position the reaction electrophile. It furthermore revealed functional groups that compose the active site. Biochemical evidence and the position of these groups lead us to propose a reaction mechanism similar to that used by proteinaceous polymerases. Using a slowly reacting mutant, 3.05-3.15 Angstrom crystal structures were solved of unreacted, kinetically trapped ligase-substrate complexes bound to different metal ions. Comparison of the Ca2+- and Mg2+-bound structures explains the preference of the ligase for Mg 2+. Moreover, these structures revealed features missing in the product structure: interactions to the 5'-triphosphate and an active site catalytic metal ion. While this metal is positioned in a manner similar to the canonical "Metal A" of proteinaceous polymerases, the role of "Metal B" might have been supplanted by functional groups on the RNA. Kinetic isotope experiments and atomic mutagenesis of two active site functional groups imply that they may act in concert to electrostatically aid transition-state stabilization.by David M. Shechner.Ph.D

A portable RNA sequence whose recognition by a synthetic antibody facilitates structural determination

RNA crystallization and phasing represent major bottlenecks in RNA structure determination. Seeking to exploit antibody fragments as RNA crystallization chaperones, we have used an arginine-enriched synthetic Fab library displayed on phage to obtain Fabs against the class I ligase ribozyme. We solved the structure of a Fab–ligase complex at 3.1-Å resolution using molecular replacement with Fab coordinates, confirming the ribozyme architecture and revealing the chaperone's role in RNA recognition and crystal contacts. The epitope resides in the GAAACAC sequence that caps the P5 helix, and this sequence retains high-affinity Fab binding within the context of other structured RNAs. This portable epitope provides a new RNA crystallization chaperone system that easily can be screened in parallel to the U1A RNA-binding protein, with the advantages of a smaller loop and Fabs′ high molecular weight, large surface area and phasing power.National Institutes of Health (U.S.) (GM61835

Regulation of mTOR complex 1 in response to growth factors and nutrients

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Biology, 2010.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections."June 2010." Cataloged from student submitted PDF version of thesis.Includes bibliographical references.In multicellular organisms, cells ensure the simultaneous availability of growth factors and nutrients before they invest in cellular processes that lead to growth. The TOR kinase is a master regulator of cellular growth and nucleates two distinct protein complexes known as TOR complex 1 and 2 (TORC1 and 2). The activity of TORC2 is mainly regulated by growth factors, whereas TORC1 activity is responsive to both growth factors and nutrients, and thus acts as a detector of favorable growth conditions. The consequence of TORC1 activation is increased protein translation through its substrates S6K and 4E-BP1. Many of the upstream signals that lead to activation of TOR pathway are tumor suppressors and deregulation of the pathway leads to disease. We aim to better understand the regulation of mammalian TORC1 (mTORC1) by upstream signals. In the work described here, we identified PRAS40 as a new component of mTORC1. PRAS40 is phosphorylated in response to growth factors and this phosphorylation event leads to mTORC1 activation. We also showed that the small GTPase Rheb, a major upstream activator of mTORC1, activates it by directly interacting with mTORC1. Both PRAS40 and Rheb relay information from growth factors to mTORC1, and do not seem to be regulated by nutrients, particularly amino acids. In this work, we also investigated how amino acids lead to mTORC1 activation. We showed that amino acids activate mTORC1 by recruiting the complex to lysosomal surface through the action of evolutionarily conserved Rag GTPases. We also indentified a complex of three proteins (p14, p18 and MP1), that we call the "Ragulator" complex, as Rag GTPase interacting proteins. The Ragulator itself localizes to lysosomes through lipid modifications on p18, and tethers the Rag GTPases on the lysosomal surface. We speculate that amino acid-induced lysosomal localization of mTORC1 enables its encounter with Rheb. Through this work, we propose a model for growth factor and amino acid-induced mTORC1 activation.by Yasemin S. Sancak.Ph.D

Brief Training to Modify the Breadth of Attention Influences the Generalisation of Fear

Background: Generalisation of fear from dangerous to safe stimuli is an important process associated with anxiety disorders. However, factors that contribute towards fear (over)-generalisation remain poorly understood. The present investigation explored how attentional breadth (global/holistic and local/analytic) influences fear generalisation and, whether people trained to attend in a global vs. local manner show more or less generalisation. Methods: Participants (N = 39) were shown stimuli which comprised of large ‘global’ letters and smaller ‘local’ letters (e.g. an F comprised of As) and they either had to identify the global or local letter. Participants were then conditioned to fear a face by pairing it with an aversive scream (75% reinforcement schedule). Perceptually similar, but safe, faces, were then shown. Self-reported fear levels and skin conductance responses were measured. Results: Compared to participants in Global group, participants in Local group demonstrated greater fear for dangerous stimulus (CS +) as well as perceptually similar safe stimuli. Conclusions: Participants trained to attend to stimuli in a local/analytical manner showed higher magnitude of fear acquisition and generalisation than participants trained to attend in a global/holistic way. Breadth of attentional focus can influence overall fear levels and fear generalisation and this can be manipulated via attentional training