Geology and wall rock alteration at the Hercynian Draa Sfar Zn–Pb–Cu massive sulphide deposit, Morocco

International audienceDraa Sfar is a siliciclastic–felsic, volcanogenic massive sulphide (VMS) Zn–Pb–Cu deposit located 15 km north of Marrakesh within the Jebilet massif of the western Moroccan Meseta. The Draa Sfar deposit occurs within the Sarhlef series, a volcano-sedimentary succession that hosts other massive sulphide deposits (e.g., Hajar, Kettara) within the dominantly siliciclastic sedimentary succession of the lower Central Jebilet. At Draa Sfar, the footwall lithofacies are dominated by grey to black argillite, carbonaceous argillite and intercalated siltstone with localized rhyodacitic flows and domes, associated in situ and transported autoclastic deposits, and lesser dykes of aphanitic basalt and gabbro. Thin- to thick-bedded, black carbonaceous argillite, minor intercalated siltstone, and a large gabbro sill dominate the hanging wall lithofacies. The main lithologies strike NNE–SSW, parallel to a pronounced S1 foliation, and have a low-grade, chlorite–muscovite–quartz–albite–oligoclase metamorphic assemblage. The Draa Sfar deposit consists of two stratabound sulphide orebodies, Tazakourt to the south and Sidi M'Barek to the north. Both orebodies are hosted by argillite in the upper part of the lower volcano-sedimentary unit. The Tazakourt and Sidi M'Barek orebodies are highly deformed, sheet-like bodies of massive pyrrhotite (up to 95% pyrrhotite) with lesser sphalerite, galena, chalcopyrite, and pyrite. The Draa Sfar deposit formed within a restricted, sediment-starved, fault-controlled, anoxic, volcano-sedimentary rift basin. The deposit formed at and below the seafloor within anoxic, pelagic muds. The argillaceous sedimentary rocks that surround the Draa Sfar orebodies are characterized by a pronounced zonation of alteration assemblages and geochemical patterns. In the more proximal volcanic area to the south, the abundance of medium to dark green chlorite progressively increases within the argillite toward the base of the Tazakourt orebody. Chlorite alteration is manifested by the replacement of feldspar and a decrease in muscovite abundance related to a net addition of Fe and Mg and a loss of K and Na. In the volcanically distal and northern Sidi M'Barek orebody alteration within the footwall argillite is characterized by a modal increase of sericite relative to chlorite. A calcite–quartz–muscovite assemblage and a pronounced decrease in chlorite characterize argillite within the immediate hanging wall to the entire Draa Sfar deposit. The sympathetic lateral change from predominantly sericite to chlorite alteration within the footwall argillite with increasing volcanic proximity suggests that the higher temperature part of the hydrothermal system is coincident with a volcanic vent defined by localized rhyodacitic flow/domes within the footwall succession

Draa Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcanogenic massive sulphide deposit in a Hercynian sediment-dominant terrane

International audienceDraa Sfar is a Visean, stratabound, volcanogenic massive sulphide ore deposit hosted by a Hercynian carbonaceous, black shale-rich succession of the Jebilet terrane, Morocco. The ore deposit contains 10 Mt grading 5.3 wt.% Zn, 2 wt.% Pb, and 0.3 wt.% Cu within two main massive sulphides orebodies, Tazakourt (Zn-rich) and Sidi M'Barek (Zn–Cu rich). Pyrrhotite is by far the dominant sulphide (70 to 95% of total sulphides), sphalerite is fairly abundant, chalcopyrite and galena are accessory, pyrite, arsenopyrite and bismuth minerals are rare. Pyrrhotite is monoclinic and mineralogical criteria indicate that it is of primary origin and not formed during metamorphism. Its composition is very homogeneous, close to Fe7S8, and its absolute magnetic susceptibility is 2.10− 3 SI/g. Ar–Ar dating of hydrothermal sericites from a coherent rhyolite flow or dome within the immediate deposit footwall indicates an age of 331.7 ± 7.9 Ma for the Draa Sfar deposit and rhyolite volcanism. The Draa Sfar deposit has undergone a low-grade regional metamorphic event that caused pervasive recrystallization, followed by a ductile–brittle deformation event that has locally imparted a mylonitic texture to the sulphides and, in part, is responsible for the elongated and sheet-like morphology of the sulphide orebodies. Lead isotope data fall into two compositional end-members. The least radiogenic end-member, (206Pb/204Pb = 18.28), is characteristic of the Tazakourt orebody, whereas the more radiogenic end-member (206Pb/204Pb not, vert, similar 18.80) is associated with the Sidi M'Barek orebody, giving a mixing trend between the two end-members. Lead isotope compositions at Draa Sfar testify to a significant continental crust source for the base metals, but are different than those of the Hajar and South Iberian Pyrite Belt VMS deposits. The abundance of pyrrhotite versus pyrite in the orebodies is attributed to low fO2 conditions and neither a high temperature nor a low aH2S (below 10− 3) is required. The highly anoxic conditions required to stabilize pyrrhotite over pyrite are consistent with formation of the deposit within a restricted, sediment-starved, anoxic basin characterized by the deposition of carbonaceous, pelagic sediments along the flank of a rhyolitic flow-dome complex that was buried by pelitic sediments. Deposition of sulphides likely occurred at and below the seafloor within anoxic and carbonaceous muds. Draa Sfar and other Moroccan volcanogenic massive sulphide deposits occur in an epicontinental volcanic domain within the outer zone of the Hercynian belt and formed within a sedimentary environment that has a high pelagic component. In spite of the diachronous emplacement between the IPB deposits (late Devonian to Visean) and Moroccan deposits (Dinantian), all were formed around 340 ± 10 Ma following a major phase of the Devonian compression

The influence of repressive legislation on the structure of a social media network

Social media have been widely used to organize citizen movements. In 2012, 75% university and college students in Quebec, Canada, participated in mass protests against an increase in tuition fees, mainly organized using social media. To reduce public disruption, the government introduced special legislation designed to impede protest organization. Here, we show that the legislation changed the behaviour of social media users but not the overall structure of their social network on Twitter. Thus, users were still able to spread information to efficiently organize demonstrations using their social network. This natural experiment shows the power of social media in political mobilization, as well as behavioural flexibility in information flow over a large number of individuals.Comment: 4 pages, 4 figures, submitted to EP

Firefighting with a Distance-Based Restriction

In the classic version of the game of firefighter, on the first turn a fire breaks out on a vertex in a graph $G$ and then $k$ firefighters protect $k$ vertices. On each subsequent turn, the fire spreads to the collective unburnt neighbourhood of all the burning vertices and the firefighters again protect $k$ vertices. Once a vertex has been burnt or protected it remains that way for the rest of the game. A common objective with respect to some infinite graph $G$ is to determine how many firefighters are necessary to stop the fire from spreading after a finite number of turns, commonly referred to as containing the fire. We introduce the concept of distance-restricted firefighting where the firefighters' movement is restricted so they can only move up to some fixed distance $d$ per turn rather than being able to move without restriction. We establish some general properties of this new game in contrast to properties of the original game, and we investigate specific cases of the distance-restricted game on the infinite square, strong, and hexagonal grids. We conjecture that two firefighters are insufficient on the square grid when $d = 2$, and we pose some questions about how many firefighters are required in general when $d = 1$

Sels de tétraarylphosphonium : synthèse et application à la synthèse de la (–)-coniine ; capacité trans-directrice du groupement amide en cyclopropanation d’oléfines

Le développement ainsi que l’amélioration des différentes techniques de purification sont des défis importants pour la chimie d’aujourd’hui. Certaines des méthodes actuelles, tel que le greffage d’un réactif sur un support solide permettant d’accéder à un produit pur par simple filtration du milieu, comportent toutefois certains inconvénients. En effet, les propriétés de solubilité de ces polymères rendent la mise en œuvre des réactions plus difficiles. C’est dans ce contexte que le groupe du Pr. Charette a rapporté l’utilisation de réactifs liés à un sel de tétraarylphosphonium (TAP). Ces sels peuvent être solubilisés dans un solvant tel que le dichlorométhane et aisément retirés du milieu réactionnel par précipitation à l’aide d’éther diéthylique (Chapitre 1). L’un des objectifs de cette thèse a donc été lié à la découverte de deux méthodes complémentaires qui, jusqu’à présent, sont considérées comme des méthodes de choix pour la synthèse des sels de TAP fonctionnalisés (Chapitre 2). L’une d’entre elles est utilisée par Soluphase inc., une entreprise qui commercialise ces sels de TAP. L’efficacité des sels en tant que support dans la synthèse de petites molécules a été démontrée lors de la synthèse d’un produit naturel, la (–)-coniine (Chapitre 3). L’isolement des intermédiaires synthétiques instables par simple précipitation à l’aide d’un support de TAP a permis de rendre cette synthèse plus efficace que celle déjà connue. Dans le deuxième volet de cette thèse, plusieurs problèmes reliés à la synthèse de dérivés cyclopropaniques 1,1-disubstitués ont été étudiés. Ces derniers font partie intégrale de plusieurs produits naturels et de médicaments. Cependant, leur formation par une réaction de cyclopropanation d’alcènes utilisant des réactifs diazoïques possédant deux groupements de type accepteur n’est pas tâche facile (Chapitre 4). En effet, cette réaction souffre d’un faible contrôle diastéréosélectif. Par le fait même, très peu de méthodologies de synthèse ont rapporté l’utilisation de ce type de réactifs diazoïques dans des réactions de cyclopropanation stéréosélectives. L’étude du mécanisme de la réaction de cyclopropanation catalysée au Rh(II) a proposé des indices favorisant un modèle ayant des précédents dans la littérature (Chapitre 5). Ces études nous ont mené à la découverte de la «capacité trans-directrice» du groupement amide lors des réactions de cyclopropanation d’oléfines. Nous avons donc utilisé cette propriété afin de résoudre plusieurs problèmes rencontrés dans la littérature. Nous avons montré qu’elle permet l’accès à des dérivés cyclopropaniques possédant deux groupements carboxyliques géminaux avec des sélectivités élevées (Chapitre 6). Ces produits étaient accessibles que par des séquences synthétiques nécessitant plusieurs étapes. De plus, nous avons démontrés que ces nouveaux dérivés cyclopropaniques sont des outils synthétiques fort utiles dans la synthèse de produits naturels d’intérêt biologique. Cette formidable «capacité trans-directrice» du groupement amide nous a permi de résoudre le problème de la synthèse asymétrique de dérivés carboxyliques α-cyano cyclopropaniques (Chapitre 7). De plus, ce projet nous a menées à la découverte de l’effet de divers additif achiraux permettant d’augmenter la sélectivité dans certaines réactions. Cette réaction possède une vaste étendue et l’utilité de ces nouveaux dérivés cyclopropaniques a été démontrée par plusieurs transformations de groupements fonctionnels.The development of new purification techniques is an important challenge for today’s academic and industrial chemists. Present methods in which a given reagent is linked to a solid support to facilitate recovery still have some issues. Indeed, the solubility properties of these supports, mainly polymers, are not always reliable. In this context, the group of Pr. Charette has recently reported the use of a tetraarylphosphonium salt (TAP) as a solubility control group. TAPs are soluble in solvents such dichloromethane and can be quantitatively precipitated by the addition of diethyl ether (Chapter 1). However, the preparation of these TAPs still remains a synthetic challenge. One of the goal of this thesis lead to the discovery of two complementary methods that are considered among the most versatile ways to access functionalized TAPs (Chapter 2). One of these methods is utilized by Soluphase Inc., which markets these salts. The efficiency of the TAP moiety as a solubility control group in the synthesis of small molecules has been demonstrated by the synthesis of (–)-coniine (Chapter 3). All of the synthetic intermediates were isolated by a simple precipitation/filtration sequence. The TAP-supported synthesis has proven to be more efficient than the unsupported one. The second part of this thesis has focused on the synthesis of different 1,1-disubstituted cyclopropanes. Such cyclopropanes are a common motif in many natural products and synthetic drugs. However, the cyclopropanation reaction between an alkene and a metal carbene bearing two acceptor groups still remains a synthetic challenge (Chapter 4). Indeed, this reaction suffers from a low level of diastereocontrol. Therefore, little data have been reported to date on the stereoselective cyclopropanation with such carbenes. Studying the Rh(II)-catalyzed cyclopropanation of alkenes, we have brought strong evidence in favor of a postulated model of this reaction (Chapter 5). This study has also led to the discovery of the «trans-directing ability» of the amide group in Rh(II)-catalyzed cyclopropanation. We have thus utilized this «trans-directing ability» of the amide group in the Rh(II)-catalyzed cyclopropanation to solve different problems observed in the literature. We first showed that it could enable the synthesis of 1,1-dicarboxy cyclopropanes (Chapter 6). Multi-step syntheses were previously necessary to access such products. We have also demonstrated that these new cyclopropanes are useful synthetic tools for the rapid synthesis of a variety of natural products and biologically active molecules. We have also used this «trans-directing ability» of the amide group in Rh(II)-catalyzed cyclopropanation to enable the synthesis of 1-cyano-1-carboxy cyclopropanes (Chapter 7). Achiral additives were found to increase the selectivity of different metal catalyzed cyclopropanation reactions. The wide scope and synthetic utility of these new cyclopropanes has been further demonstrated by several functional group transformations

What is ambiguous about ambiguous goods?

Ambiguous goods are not a category of things. No goods are ambiguous by default, not even digital virtual ones. Ambiguity may arise in many ways, but this article examines one specific process: ambiguity that occurs when entities appear as objects that blur category boundaries. Ambiguity is created around pre-existing categories through socio-material entanglements. This article explores how a central category in consumer capitalist societies-property-takes on ambiguous forms in distributions and recirculations of prestige items in the massively multi-player online role-playing game Final Fantasy XI. Prestige objects are powerful, sought-after armour and weapons acquired in the game world by completing difficult battlefields or tasks, often in large groups. When discussing these items, respondents are not confused actors trying to make sense of slippery things. Instead, they produce ambiguities around property by blurring distinctions between gifts and commodities. Blurred boundaries help resolve tensions arising from different orderings of people, relations and things. Hybridised property forms allow selective alienation of goods, allowing participants to privilege some relations and connections over others. With this article, I hope to spark further debate on building a conceptual toolkit to explore ambiguities, and contribute to increasing interest in non-dyadic gift relations in consumer culture research. 'Ambiguous goods' is not a viable category for thinking about things, people and relations or digital virtual objects. But ambiguity can be a useful way to think about how people and things-whether they are digital, virtual or neither-are related. © 2014 John Wiley & Sons, Ltd

Distance-Restricted Firefighting on Finite Graphs

In the classic version of the game of firefighter, on the first turn a fire breaks out on a vertex in a graph $G$ and then $b$ firefighters protect $b$ vertices. On each subsequent turn, the fire spreads to the collective unburnt neighbourhood of all the burning vertices and the firefighters again protect $b$ vertices. Once a vertex has been burnt or protected it remains that way for the rest of the game. We previously introduced the concept of $\textit{distance-restricted firefighting}$ where the firefighters' movement is restricted so they can only move up to some fixed distance $d$ and they may or may not be permitted to move through burning vertices. In this paper we establish the NP-Completeness of the distance-restricted versions of the $\textit{Maximum Vertices Saved}$ problem and present an integer program for solving these problems. In the penultimate section we also discuss some interesting properties of the $\textit{Expected Damage}$ function

Adverse childhood experiences predict treatment drop out in adolescents and young adults with eating disorders

Objective: Childhood adversity is associated with elevated risk of developing an eating disorder. The objective of the current study was to examine whether different types of childhood adversity, such as parental separation or abuse exposure, predicted treatment completion in a sample of adolescents and young adults with eating disorders. Method: A retrospective chart review was conducted at an eating disorders clinic in Calgary, Canada. Childhood adversity was measured using the adverse childhood experiences (ACEs) scale. Eating disorders diagnoses were determined by physicians following a comprehensive assessment. Logistic regressions were performed with ACEs as predictors of likelihood to complete treatment and including diagnoses and age as covariates. Results: Data were analyzed for 128 patients aged 11–24. Higher ACE scores were associated with a reduced likelihood of completing treatment before and after adjusting for diagnosis and age (adjusted odds ratio = 0.76). Examining individual ACE items, people were less likely to complete treatment if they were exposed to verbal abuse, physical abuse, emotional neglect, or if they witnessed intimate partner violence or substance abuse in the home. However, after adjusting for diagnosis, age, and other ACE exposures, no individual ACE was an independent predictor of treatment completion. Discussion: This study suggests that ACE exposure increases youth attrition from eating disorders treatment in a stepwise manner. Treatment programs for youth with eating disorders should focus additional effort on early intervention for youth who have dealt with childhood adversities, potentially by implementing trauma-informed practice into assessments and treatment.</p