Contribution of interstitial OH groups to the incorporation of water in forsterite

Water incorporation in forsterite samples synthesized under low to medium silica-activity conditions mostly occurs via a substitutional mechanism in which a Si vacancy is compensated by four protons. Corresponding IR absorption spectra display a cluster of narrow and weakly anharmonic OH-stretching bands at wavenumbers above 3,500 cm^?1. However, this diagnostic spectrum is often superimposed to one broader absorption band, rarely two, displaying pronounced temperature-dependent properties and tentatively assigned to H atoms in interstitial position (Ingrin et al. in Phys Chem Miner 40:499–510, 2013). Here, we investigate the structural and vibrational properties of selected interstitial H-bearing defects in forsterite using a first-principles modeling approach. We show that the broad bands discussed by Ingrin et al. (Phys Chem Miner 40:499–510, 2013) are most likely related to interstitial OH groups in the vacant octahedral sites alternating with the M2 sites along the c axis of the forsterite structure. The corresponding OH defects lead to the formation of fivefold coordinated Si species. Their peculiar thermal properties stem from the vibrational phase relaxation due to the anharmonic coupling of the high-energy local OH-stretching mode with a low-energy vibrational mode. This “exchange mode” corresponds to the hindered longitudinal translation of the OH group. These results suggest that at high pressure, hydrogen incorporation in forsterite is dominated by coexisting interstitial OH groups and (4H)_Si defects.     

Extraterrestrial water in micrometeorites and cosmic spherules from Antarctica: An ion microprobe study

Abstract— The D/H ratios and water contents were measured by ion microprobe analysis in 52 individual Antarctic micrometeorites (AMMs) and 10 Antarctic cosmic spherules (ACSs) containing nuggets of iron hydroxide (COPS phase). In AMMs, δD values vary from ?366 to +249%‰ and water contents lie between 0.4-3.7 wt%. The COPS nuggets in cosmic spherules have high water contents (2 to 8 wt%) and exhibit δD values from ?144 to +167%‰, which is indicative of an extraterrestrial origin of their constituent water. The silicate portion of ACSs also contain extraterrestrial H equivalent to ～0.l to 1.2 wt% water. Deuterium-exchange experiments were performed with isotopically spiked water. These experiments demonstrate that water in mineral phases of AMMs and ACSs is indigenous and does not result from contamination during residence in Antarctic ice. The frequency distribution of D/H ratios in AMMs allows us to further narrow the relationship between AMMs and carbonaceous chondrites to CM and CI chondrites but contrasts with that of stratospheric interplanetary dust particles (IDPs) of similar sizes (from ?10 to 50 μm). The relatively narrow range of D/H ratios measured in AMMs as well as in ACSs (which are more resistant and thus less susceptible to collection biases) suggests that D-rich IDP-like particles are very rare in our AMMs collections. This indicates that these D-rich grains might constitute a minor fraction of the micrometeorite flux in the interplanetary medium and that possible collection biases in Antarctica would not be responsible for their strong depletion in the AMMs collections.     

Influence of Continental Sources on Oceanic Air Composition at the Eastern Edge of the North Atlantic Ocean, TOR 1992–1995

The atmospheric concentrations of O3, NMHCs, PAN and NOx were measured at the TOR station in Porspoder (Brittany, France) from 1992 to 1995. The results from April 1992 to December 1994 are reported here. In order to study the behaviour of trace gases in the air masses coming from the Atlantic Ocean, the origin of these air masses was characterised by the analysis of the five-day back-trajectories reaching 950 mbar at Porspoder. Three kinds of oceanic air masses are considered, depending on their origin: North Atlantic northern and southern latitudes and North American continent. It appears that the oceanic high-latitude troposphere was strongly influenced by continental emissions, which in turn impacted the median latitude troposphere during polar outflow events. A greater accumulation of anthropogenic compounds in the Arctic sector was calculated and may be at the origin of the high oxidant levels measured in spring in this same sector. The influence of north American emissions on the European coast was also studied and seems to reach a maximum in spring. Long-range transport of long- lived species was observed throughout the year, but evidence for winter transport of more reactive species, such as ethene, is also shown. Meteorological parameters and local photochemistry appear to play an important role in the distribution of the pollutants over the North Atlantic Ocean throughout the year. Further investigations are needed to give more complete information about the origin, formation and destruction of the secondary pollutants.     

Age gap between the intrusion of gneissose granitoids and regional high‐temperature metamorphism in the Ryoke belt (Mikawa area), central Japan

The relationships between the intrusion of gneissose granitoids and the attainment of regional high‐T conditions recorded in metamorphic rocks from the Ryoke belt of the Mikawa area, central Japan, are explored. Seven gneissose granitoid samples (tonalite, granodiorite, granite) were collected from three distinct plutonic bodies that are mapped as the so‐called “Older Ryoke granitoids.” Based on bulk‐rock compositions and U–Pb zircon ages obtained by laser ablation inductively coupled plasma mass spectrometry, the analyzed granitoids can be separated into two groups. Gneissose granitoids from the northern part of the area give weighted mean ²⁰⁶Pb/²³⁸U ages of 99 ±1 Ma (two samples) and 95 ±1 Ma (one sample), whereas those from the southern part yield 81 ±1 Ma (two samples) and 78–77 ±1 Ma (two samples). Regional comparisons allow correlation of the northern granitoids (99–95 Ma) with the Kiyosaki granodiorite, and mostly with the Kamihara tonalite found to the east. The southern granitoids are tentatively renamed as “78–75 Ma (Hbl)?Bt granite” and “81–75 Ma Hbl?Bt tonalite” (Hbl, hornblende; Bt, biotite). and seem to be broadly coeval members of the same magmatic suite. With respect to available age data, no gneissose granitoid from the Mikawa area shows a U–Pb zircon age which matches that of high‐T metamorphism (ca 87 Ma). The southern gneissose granitoids (81–75 Ma), although they occur in the highest‐grade metamorphic zone, do not seem to represent the heat source which produced the metamorphic field gradient with a low dP/dT slope.     

CM carbonaceous chondrite falls and their terrestrial alteration

The CM carbonaceous chondrites provide unique insights into the composition of the protoplanetary disk, and the accretion and geological history of their parent C‐complex asteroid(s). Of the hundreds of CMs that are available for study, the majority are finds and so may have been compromised by terrestrial weathering. Nineteen falls have been recovered between 1838 and 2020, and there is a hint of two temporal clusters: 1930–1942 and 2009–2020. Falls are considered preferable to finds to study because they should be near pristine, and here this assumption is tested by investigating their susceptibility to alteration before recovery and during curation. CMs falling on the land surface are prone to contamination by organic compounds from soil and vegetation. Where exposed to liquid water prior to collection, minerals including oldhamite can be dissolved and most fluid mobile elements leached. Within days of recovery, CMs adsorb water from the atmosphere and are commonly contaminated by airborne hydrocarbons. Interaction with atmospheric water and oxygen during curation over year to decadal timescales can produce Fe‐oxyhydroxides from Fe,Ni metal and gypsum from indigenous gypsum and oldhamite. Relationships between the petrologic (sub)types of pre‐1970 falls and their terrestrial age could be due to extensive but cryptic alteration during curation, but are more likely a sampling bias. The terrestrial history of a CM fall, including circumstances of its collection and conditions of its curation, must be taken into account before it is used to infer processes on C‐complex parent bodies such as Ryugu and Bennu.     

Evolution of new regional development interventions in New Zealand: An analysis of the first year of the Provincial Growth Fund

Regional development has evolved in response to shifting local and global priorities. These shifts have transformed both the way we think about regions, their role and how that shapes the outcomes and benefits that might occur from engaging in regional development. Key debates centre around the ability (or desirability) of regional development interventions to unsettle path dependence and “lock‐in” created by past approaches and to create opportunities for alternative development futures and to provide choices between sectoral‐based investments to support economic activity in contrast to a more place‐based approach to regional development. This paper overviews the dynamic nature of regional development to offer reasons for its recent resurgence by highlighting the key debates about the purpose and function of regions and what regional development can or should do. We then discuss the New Zealand context specifically and use the first year of Provincial Growth Fund investments to reflect on how the processes, objectives and goals reflect particular interpretations of the meaning and purpose of regional development. We conclude that a strong adherence to a growth imperative has the potential to reinforce path dependencies at the expense of alternative development pathways.     

New Zealand's small town transition: The experience of demographic and economic change and place based responses

A significant percentage of the smaller urban centres around the world are losing people which raises questions regarding the appropriate responses to this challenge. Responses from the state have generally been muted, and as a result, concepts of new localism and new regionalism are useful for understanding the role played by place‐based leadership and partnerships between local businesses, community groups and individuals. Key within this space is the role of endogenous responses anchored on local social capital and resilience. This paper overviews key themes in the literature before examining statistical evidence of small town growth, stabilisation or decline in New Zealand. This leads into an examination of how three small towns in the country are responding to demographic and economic change. The cases illustrate the importance of local‐led responses to the debilitating effects of change and the degree to which place based development can be critical in the context of coping with change in small towns. The paper further argues that “right‐sizing” to a new economic and demographic reality may be the appropriate focus of local attention.