Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer : evidence for a gas phase alpha-effect

The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

Late Pleistocene stratigraphy of IODP Site U1396 and compiled chronology offshore of south and south west Montserrat, Lesser Antilles

Marine sediments around volcanic islands contain an archive of volcaniclastic deposits, which can be used to reconstruct the volcanic history of an area. Such records hold many advantages over often incomplete terrestrial datasets. This includes the potential for precise and continuous dating of intervening sediment packages, which allow a correlatable and temporally-constrained stratigraphic framework to be constructed across multiple marine sediment cores. Here, we discuss a marine record of eruptive and mass-wasting events spanning ~250 ka offshore of Montserrat, using new data from IODP Expedition 340, as well as previously collected cores. By using a combination of high-resolution oxygen isotope stratigraphy, AMS radiocarbon dating, biostratigraphy of foraminifera and calcareous nannofossils and clast componentry, we identify five major events at Soufriere Hills volcano since 250 ka. Lateral correlation of these events across sediment cores collected offshore of the south and south west of Montserrat, have improved our understanding of the timing, extent and associations between events in this area. Correlations reveal that powerful and potentially erosive density-currents travelled at least 33 km offshore, and demonstrate that marine deposits, produced by eruption-fed and mass-wasting events on volcanic islands, are heterogeneous in their spatial distribution. Thus, multiple drilling/coring sites are needed to reconstruct the full chronostratigraphy of volcanic islands. This multidisciplinary study will be vital to interpreting the chaotic records of submarine landslides at other sites drilled during Expedition 340 and provides a framework that can be applied to the stratigraphic analysis of sediments surrounding other volcanic islands.

Multi-stage collapse events in the South Soufrière Hills, Montserrat as recorded in marine sediment cores

We present new evidence for sector collapses of the South Soufrière Hills (SSH) edifice, Montserrat during the mid-Pleistocene. High-resolution geophysical data provide evidence for sector collapse, producing an approximately 1 km3 submarine collapse deposit to the south of SSH. Sedimentological and geochemical analyses of submarine deposits sampled by sediment cores suggest that they were formed by large multi-stage flank failures of the subaerial SSH edifice into the sea. This work identifies two distinct geochemical suites within the SSH succession on the basis of trace-element and Pb-isotope compositions. Volcaniclastic turbidites in the cores preserve these chemically heterogeneous rock suites. However, the subaerial chemostratigraphy is reversed within the submarine sediment cores. Sedimentological analysis suggests that the edifice failures produced high-concentration turbidites and that the collapses occurred in multiple stages, with an interval of at least 2 ka between the first and second failure. Detailed field and petrographical observations, coupled with SEM image analysis, shows that the SSH volcanic products preserve a complex record of magmatic activity. This activity consisted of episodic explosive eruptions of andesitic pumice, probably triggered by mafic magmatic pulses and followed by eruptions of poorly vesiculated basaltic scoria, and basaltic lava flows.

Electron tomography reveals the steps in filovirus budding

The filoviruses, Marburg and Ebola, are non-segmented negative-strand RNA viruses causing severe hemorrhagic fever with high mortality rates in humans and nonhuman primates. The sequence of events that leads to release of filovirus particles from cells is poorly understood. Two contrasting mechanisms have been proposed, one proceeding via a "submarine-like" budding with the helical nucleocapsid emerging parallel to the plasma membrane, and the other via perpendicular "rocketlike" protrusion. Here we have infected cells with Marburg virus under BSL-4 containment conditions, and reconstructed the sequence of steps in the budding process in three dimensions using electron tomography of plastic-embedded cells. We find that highly infectious filamentous particles are released at early stages in infection. Budding proceeds via lateral association of intracellular nucleocapsid along its whole length with the plasma membrane, followed by rapid envelopment initiated at one end of the nucleocapsid, leading to a protruding intermediate. Scission results in local membrane instability at the rear of the virus. After prolonged infection, increased vesiculation of the plasma membrane correlates with changes in shape and infectivity of released viruses. Our observations demonstrate a cellular determinant of virus shape. They reconcile the contrasting models of filovirus budding and allow us to describe the sequence of events taking place during budding and release of Marburg virus. We propose that this represents a general sequence of events also followed by other filamentous and rod-shaped viruses.

What is the apparent angle of a Kelvin ship wave pattern?

While the half-angle which encloses a Kelvin ship wave pattern is commonly accepted to be 19.47 degrees, recent observations and calculations for sufficiently fast-moving ships suggest that the apparent wake angle decreases with ship speed. One explanation for this decrease in angle relies on the assumption that a ship cannot generate wavelengths much greater than its hull length. An alternative interpretation is that the wave pattern that is observed in practice is defined by the location of the highest peaks; for wakes created by sufficiently fast-moving objects, these highest peaks no longer lie on the outermost divergent waves, resulting in a smaller apparent angle. In this paper, we focus on the problems of free surface flow past a single submerged point source and past a submerged source doublet. In the linear version of these problems, we measure the apparent wake angle formed by the highest peaks, and observe the following three regimes: a small Froude number pattern, in which the divergent waves are not visible; standard wave patterns for which the maximum peaks occur on the outermost divergent waves; and a third regime in which the highest peaks form a V-shape with an angle much less than the Kelvin angle. For nonlinear flows, we demonstrate that nonlinearity has the effect of increasing the apparent wake angle so that some highly nonlinear solutions have apparent wake angles that are greater than Kelvin's angle. For large Froude numbers, the effect on apparent wake angle can be more dramatic, with the possibility of strong nonlinearity shifting the wave pattern from the third regime to the second. We expect our nonlinear results will translate to other more complicated flow configurations, such as flow due to a steadily moving closed body such as a submarine.

The neural correlates of justified and unjustified killing: An fMRI study

Despite moral prohibitions on hurting other humans, some social contexts allow for harmful actions such as the killing of others. One example is warfare, where killing enemy soldiers is seen as morally justified. Yet, the neural underpinnings distinguishing between justified and unjustified killing are largely unknown. To improve understanding of the neural processes involved in justified and unjustified killing, participants had to imagine being the perpetrator whilst watching “first-person perspective” animated videos where they shot enemy soldiers (‘justified violence’) and innocent civilians (‘unjustified violence’). When participants imagined themselves shooting civilians compared to soldiers, greater activation was found in the lateral orbitofrontal cortex (OFC). Regression analysis revealed that the more guilt participants felt about shooting civilians, the greater the response in the lateral OFC. Effective connectivity analyses further revealed an increased coupling between lateral OFC and the tempoparietal junction (TPJ) when shooting civilians. The results show that the neural mechanisms typically implicated with harming others, such as the OFC, become less active when the violence against a particular group is seen as justified. This study therefore provides unique insight into how normal individuals can become aggressors in specific situations.

Bees at war: Interspecific battles and nest usurpation in stingless bees

We provide the first evidence for interspecific warfare in bees, a spectacular natural phenomenon that involves a series of aerial battles and leads to thousands of fatalities from both attacking and defending colonies. Molecular analysis of fights at a hive of the Australian stingless bee Tetragonula carbonaria revealed that the attack was launched by a related species, Tetragonula hockingsi, which has only recently extended its habitat into southeastern Queensland. Following a succession of attacks by the same T. hockingsi colony over a 4-month period, the defending T. carbonaria colony was defeated and the hive usurped, with the invading colony installing a new queen. We complemented our direct observations with a 5-year study of more than 260 Tetragonula hives and found interspecific hive changes, which were likely to be usurpation events, occurring in 46 hives over this period. We discuss how fighting swarms and hive usurpation fit with theoretical predictions on the evolution of fatal fighting and highlight the many unexplained features of these battles that warrant further study.

The Roman Republican Navy : from the sixth century to 167 BC

Työ käsittelee Rooman laivaston kehitystä, toimintaa ja osallistumista laajenemispolitiikkaan, jossa Rooma kasvoi kaupunkivaltiosta Välimeren hallitsijaksi. Rooma on aikaisemmissa tutkimuksissa nähty maavaltiona vailla kiinnostusta merenkulkuun. On katsottu, että ainoa merkittävä merisota Rooman historiassa on ensimmäinen puunilaissota (264-241 eKr.) ja että siinäkin roomalaiset (jotka historioitsija Polybius kuvaa vasta-alkajiksi) menestyivät Karthagoa vastaan turvautumalla laskusiltoihin, joiden avulla he saattoivat muuttaa meritaistelun maataisteluksi. Polybiuksen kuvaukseen on aina tähän asti luotettu. On katsottu että Roomalla ei ollut laivastoa ennen ensimmäistä puunilaissotaa ja että Rooma kaikissa sodissaan panosti merisodankäyntiin mahdollisimman vähän. Tämä työ pyrkii kumoamaan nämä käsitykset. Laivasto oli osallisena ja ehdottoman välttämätön kaikissa Rooman laajenemispolitiikan käänteissä. Arkeologian tiedot osoittavat, että ennen ensimmäistä puunilaissotaa Rooma kehittyi ja siitä tuli merkittävä kaupunki nimenomaan kaupankäynnin ja ulkomaisten kontaktien seurauksena. Se ei siis ollut puhdas agraarivaltio. Roomalaisilla oli laivasto jo viimeistään 500-luvulta lähtien eKr. ja sitä käytettiin Rooman laajentaessa valtaansa Italiassa. Näin ollen ensimmäisessä puunilaissodassa läntisen Välimeren herruudesta kilpaili kaksi merivaltiota, Rooma ja Karthago. Toinen puunilaissota (218-201) tunnetaan yleensä Hannibalin tulosta Alppien yli Italiaan, mutta se oli myöskin merkittävä merisota ja karthagolaiset hävisivät sen nimenomaan merellä. Rooma osallistui kilpailuun itäisen Välimeren hallinnasta ja kukisti Makedonian ja Syyrian laivastot, jotka eivät olleet mitenkään Rooman laivaston veroisia. Kaikista Rooman vastustajista Karthagolla olisi ollut suurin mahdollisuus pysäyttää Rooman laivaston voittokulu toisessa puunilaissodassa. Laivastoa käytettiin moniin eri tarkoituksiin. Suuret meritaistelut eivät ole ainoa osoitus laivastojen mukanaolosta ja merkityksestä, vaan on myös otettava huomion sotalaivojen rakenne ja toimintaedellytykset. Sotalaivat oli rakennettu taisteluita varten ja niissä oli hyvin niukasti säilytystilaa. Niiden oli päästävä laskemaan maihin aina kun miehistö tarvitsi vettä, ruokaa ja lepoa. Laivastot saattoivat toimia vain niiden rannikoiden tuntumassa, joiden satamiin ja laskupaikkoihin niillä oli turvallinen pääsy. Roomalaiset olivat hyvin tietoisia tästä. Suuret merentakaiset sotaretket Afrikkaan, Espanjaan, Kreikkaan ja Vähän-Aasian rannikolle perustuivat kaikki siihen, että Rooman laivasto hallitsi purjehdusreittejä ja sopivia laskupaikkoja ja saattoi huolehtia joukkojen ja varusteiden kuljettamisesta kaukana taisteleville armeijoille. Samalla Rooman laivasto kävi itsenäistä sotaa merellä ja haastoi ja kukisti kaikki Välimeren merivaltiot. 130-luvulle eKr. tultaessa se oli lyönyt vihollisensa ja riisunut aseista liittolaisensa; Rooman laivasto hallitsi Välimerta yksin.

Depositional model for the early Miocene turbidite sequence, the Whakataki Formation, NZ

This research examined the influence of tectonic activity on submarine sedimentation processes, through a deposit-based analysis of turbidites in outcrop. A comprehensive field study of the Miocene Whakataki Formation yielded significant data that was analysed using methods of process-sedimentology, stratigraphy, and ichnology. Signatures of the tectonically active depositional environment were identifiable at very high resolution, from grain composition and texture to trace-fossil assemblages, as well as on a broader-scale in stratigraphic stacking patterns and structural deformation. From these results and environmental interpretations, an original facies characterisation and conceptual depositional model have been established.

Strike Hard, Strike Sure - Operation Musketeer : British Military Planning during the Suez Crisis, 1956

This study analyses British military planning and actions during the Suez Crisis in 1956. It seeks to find military reasons for the change of concepts during the planning and compares these reasons with the tactical doctrines of the time. The thesis takes extensive advantage of military documents preserved in the National Archives, London. In order to expand the understanding of the exchange of views during the planning process, the private papers of high ranking military officials have also been consulted. French military documents preserved in the Service Historique de la Defence, Paris, have provided an important point of comparison. The Suez Crisis caught the British armed forces in the middle of a transition phase. The main objective of the armed forces was to establish a credible deterrence against the Soviet Union. However, due to overseas commitments the Middle East playing a paramount role because of its economic importance the armed forces were compelled to also prepare for Limited War and the Cold War. The armed forces were not fully prepared to meet this demand. The Middle Eastern garrison was being re-organised after the withdrawal from the Canal Base and the concept for a strategic reserve was unimplemented. The tactical doctrines of the time were based on experiences from the Second World War. As a result, the British view of amphibious operations and the subsequent campaigns emphasised careful planning, mastery of the sea and the air, sufficient superiority in numbers and firepower, centralised command and extensive administrative preparations. The British military had realized that Nasser could nationalise the Suez Canal and prepared an outline plan to meet this contingency. Although the plan was nothing more than a concept, it was accepted as a basis for further planning when the Canal was nationalised at the end of July. This plan was short-lived. The nominated Task Force Commanders shifted the landing site from Port Said to Alexandria because it enabled faster expansion of the bridgehead. In addition, further operations towards Cairo the hub of Nasser s power would be easier to conduct. The operational concept can be described as being traditional and was in accordance with the amphibious warfare doctrine. This plan was completely changed at the beginning of September. Apparently, General Charles Keightley, the Commander-in-Chief, and the Chairman of the Chiefs of Staff Committee developed the idea of prolonged aerial operations. The essence of the concept was to break the Egyptian will to resist by attacking the oil facilities, the transportation system and the armed forces. This victory through air concept would be supported by carefully planned psychological operations. This concept was in accordance with the Royal Air Force doctrine, which promoted a bomber offensive against selected target categories. General Keightley s plan was accepted despite suspicions at every planning level. The Joint Planning Staff and the Task Force Commanders opposed the concept from the beginning to the end because of its unpredictability. There was no information that suggested the bombing would persuade the Egyptians to submit. This problem was worsened by the fact that British intelligence was unable to provide reliable strategic information. The Task Force Commanders, who were responsible for the tactical plans, were not able to change Keightley s mind, but the concept was expanded to include a traditional amphibious assault on Port Said due to their resistance. The bombing campaign was never tested as the Royal Air Force was denied authorisation to destroy the transportation and oil targets. The Chiefs of Staff and General Keightley were too slow to realise that the execution of the plan depended on the determination of the Prime Minister. However, poor health, a lack of American and domestic support and the indecisiveness of the military had ruined Eden s resolve. In the end, a very traditional amphibious assault, which was bound to succeed at the tactical level but fail at the strategic level, was launched against Port Said.

Community, Power, and Colonialism: The U.S. Army in Southern Arizona and New Mexico, 1866-1886

Empire is central to U.S. history. When we see the U.S. projecting its influence on a global scale in today s world it is important to understand that U.S. empire has a long history. This dissertation offers a case study of colonialism and U.S. empire by discussing the social worlds, labor regimes, and culture of the U.S. Army during the conquest of southern Arizona and New Mexico (1866-1886). It highlights some of the defining principles, mentalities, and characteristics of U.S. imperialism and shows how U.S. forces have in years past constructed their power and represented themselves, their missions, and the places and peoples that faced U.S. imperialism/colonialism. Using insights from postcolonial studies and whiteness studies, this work balances its attention between discursive representations (army stories) and social experience (army actions), pays attention to silences in the process of historical production, and focuses on collective group mentalities and identities. In the end the army experience reveals an empire in denial constructed on the rule of difference and marked by frustration. White officers, their wives, and the white enlisted men not only wanted the monopoly of violence for the U.S. regime but also colonial (mental/cultural) authority and power, and constructed their identity, authority, and power in discourse and in the social contexts of the everyday through difference. Engaged in warfare against the Apaches, they did not recognize their actions as harmful or acknowledge the U.S. invasion as the bloody colonial conquest it was. White army personnel painted themselves and the army as liberators, represented colonial peoples as racial inferiors, approached colonial terrain in terms of struggle, and claimed that the region was a terrible periphery with little value before the arrival of white civilization. Officers and wives also wanted to place themselves at the top of colonial hierarchies as the refined and respectable class who led the regeneration of the colony by example: they tried to turn army villages into islands of civilization and made journeys, leisure, and domestic life to showcase their class sensibilities and level of sophistication. Often, however, their efforts failed, resulting in frustration and bitterness. Many blamed the colony and its peoples for their failures. The army itself was divided by race and class. All soldiers were treated as laborers unfit for self-government. White enlisted men, frustrated by their failures in colonial warfare and by constant manual labor, constructed worlds of resistance, whereas indigenous soldiers sought to negotiate the effects of colonialism by working in the army. As colonized labor their position was defined by tension between integration and exclusion and between freedom and colonial control.

Bysanttilaisten ja Akhaian ruhtinaskunnan väliset sotatoimet vuosina 1259-83 : Tapaustutkimus myöhäis-bysanttilaisesta sodankäynnistä

In my master thesis I analyse Byzantine warfare in the late period of the empire. I use military operations between Byzantines and crusader Principality of Achaia (1259–83) as a case study. Byzantine strategy was based (in “oriental manner”) on using ambushes, diplomacy, surprise attacks, deception etc. Open field battles that were risky in comparison with their benefits were usually avoided, but the Byzantines were sometimes forced to seek open encounter because their limited ability to keep strong armies in field for long periods of time. Foreign mercenaries had important place in Byzantine armies and they could simply change sides if their paymasters ran out of resources. The use of mercenaries with short contracts made it possible that the composition of an army was flexible but on the other hand heterogeneous – in result Byzantine armies were sometimes ineffective and prone to confusion. In open field battles Byzantines used formation that was made out from several lines placed one after another. This formation was especially suitable for cavalry battles. Byzantines might have also used other kinds of formations. The Byzantines were not considered equal to Latins in close combat. West-Europeans saw mainly horse archers and Latin mercenaries on Byzantine service as threats to themselves in battle. The legitimacy of rulers surrounding the Aegean sea was weak and in many cases political intrigues and personal relationships can have resolved the battles. Especially in sieges the loyalty of population was decisive. In sieges the Byzantines used plenty of siege machines and archers. This made fast conquests possible, but it was expensive. The Byzantines protected their frontiers by building castles. Military operations against the Principality of Achaia were mostly small scale raids following an intensive beginning. Byzantine raids were mostly made by privateers and mountaineers. This does not fit to the traditional picture that warfare belonged to the imperial professional army. It’s unlikely that military operations in war against the Principality of Achaia caused great demographic or economic catastrophe and some regions in the warzone might even have flourished. On the other hand people started to concentrate into villages which (with growing risks for trade) probably caused disturbance in economic development and in result birth rates might have decreased. Both sides of war sought to exchange their prisoners of war. These were treated according to conventional manners that were accepted by both sides. It was possible to sell prisoners, especially women and children, to slavery, but the scale of this trade does not seem to be great in military operations treated in this theses.

Memoirs of an immigrant and his ashtray

The memoirs were written in 1999. Childhood memories in a small town in Lower Austria. Passion for playing football (soccer). Recollections of daily life with rituals of coffeehouse visits and family dinners in the countryside. First experiences of antisemitism in the mid 1930s. Rising Nazi movement and illegal meetings in the local community. Annexation of Austria in 1938. First encounters with anti-Jewish regulations and discrimination by neighbors and acquaintances. Walter experienced severe difficulties at school and was frequently insulted and beaten up. Decision to leave school. The family was forced to leave Eggenburg soon thereafter, and the town declared itself "Judenfrei" (free of Jews). Move to Vienna, where they stayed with relatives. Walter, who had been brought up as a Catholic, suddenly saw himself confronted with orthodox Jewish people of different customs. Increasing restrictions for Jews. Walter was enrolled in a program at the Vienna Jewish community to learn carpentry. Recollections of the terror of Kristallnacht. Walter and his brother Ludwig were signed up for a children transport to England by the Quaker organization and left Vienna in December 1938. Difficult feeling to depart from their parents. Arrival in Harwige. They were taken to a camp in Lowestoft. Cultural differences. Walter and his brother were sent to a training farm in Parbold. Simple living conditions and difficult circumstances. Farm work and school lessons. Outbreak of the war. Scarce news of their parents, who tried to leave for Argentina. Walter's older brother Ludwig was sent to an internment camp in Adelaide, Australia. After two years he volunteered in the Pioneer Corps and returned to England. In 1941 their parents finally managed to emigrate to Argentina. Walter decided to join them, and in 1943 he left for Buenos Aires. During the passage on the Atlantic the ship was sunk by a German submarine. Rescue by the US Army. Continuation of his trip via New York.