The extent to which prehistoric migrations of farmers influenced the genetic pool of western North Africans remains unclear. Archaeological evidence suggests that the Neolithization process may have happened through the adoption of innovations by local Epipaleolithic communities or by demic diffusion from the Eastern Mediterranean shores or Iberia. Here, we present an analysis of individuals' genome sequences from Early and Late Neolithic sites in Morocco and from Early Neolithic individuals from southern Iberia. We show that Early Neolithic Moroccans (∼5,000 BCE) are similar to Later Stone Age individuals from the same region and possess an endemic element retained in present-day Maghrebi populations, confirming a long-term genetic continuity in the region. This scenario is consistent with Early Neolithic traditions in North Africa deriving from Epipaleolithic communities that adopted certain agricultural techniques from neighboring populations. Among Eurasian ancient populations, Early Neolithic Moroccans are distantly related to Levantine Natufian hunter-gatherers (∼9,000 BCE) and Pre-Pottery Neolithic farmers (∼6,500 BCE). Late Neolithic (∼3,000 BCE) Moroccans, in contrast, share an Iberian component, supporting theories of trans-Gibraltar gene flow and indicating that Neolithization of North Africa involved both the movement of ideas and people. Lastly, the southern Iberian Early Neolithic samples share the same genetic composition as the Cardial Mediterranean Neolithic culture that reached Iberia ∼5,500 BCE. The cultural and genetic similarities between Iberian and North African Neolithic traditions further reinforce the model of an Iberian migration into the Maghreb.
A new method for the spatially-resolved measurement of pH during corrosion processes with the scanning electrochemical microscope (SECM) is presented. Antimony tips are employed because the dual-function characteristics of this material allow the combined amperometric/potentiometric operation of the SECM. The applicability of this technique is illustrated by considering the galvanic corrosion of a model zinc-iron pair immersed in 0.1 M NaCl aqueous solution. Spatially resolved images of pH and oxygen concentration above the metal specimens could be obtained in the same experiment.
The electrochemical behaviour of three ZrTi alloys (Zr5Ti, Zr25Ti and Zr45Ti) in Ringer's solution has been investigated. Their resistance against localized corrosion has been determined from cyclic potentiodynamic polarization (CCP) and electrochemical impedance spectroscopy (EIS) measurements, whereas scanning electrochemical microscopy (SECM) was applied to investigate the local reactivity of the passive films developed on the materials, and scanning electron microscopy (SEM) was employed to characterize the surface morphology of the alloys subjected to anodic polarization. An increased reactivity could be detected with SECM when the metal samples were polarized at +0.50 VSHE, though the extent of this feature greatly depended on the nature of the metallic material. At 37 0 C, the Zr5Ti alloy was susceptible to localized corrosion. Though Zr25Ti alloy presented rather low pitting potential, the spontaneous corrosion potential of the material was sufficiently negative to require overpotentials around 600 mV for breakdown to occur. Finally, the Zr45Ti alloy exhibited a larger passive range in the polarization curve, and it was resistant to localized corrosion.
The fabrication of a solid-contact, micropipette-based magnesium ion-selective micro-tipped electrode (ISME) suitable for scanning electrochemical microscopy is reported and compared against a conventional micro-tipped ISME having a conventional aqueous internal reference electrode. Measurements showed that the solid-contact ISME had a lower internal resistance and a faster response time than the one with a liquid-contact. These advantages increased the spatial distribution and improved 2D images depicting concentration distributions of Mg 2+ . The ability of the microelectrode to image local ionic concentration has been tested over magnesium surfaces freely corroding or galvanically coupled to iron in aqueous chloride-containing solution. Scans of magnesium ion distribution, in the absence of corrosion currents, were also made over a micro-pipette source containing a concentrated magnesium chloride gel as a source of Mg 2+ and over a current source in the absence of Mg 2+ . From these measurements it was concluded that the potentiometric measurements over corroding surfaces were dominated by the changes in Mg 2+ distributions with small electric potential contributions due to corrosion current.
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