Characterisation of the tetrahalophosphonium cations PBrnI4 − n+ (0 ≤ n ≤ 4) by 31P MAS NMR, IR and Raman spectroscopy and the crystal structures of PI4+AlCl4−, PI4+AlBr4− and PI4+GaI4−

The novel tetrahalophosphonium salts PBr4+AsF6−, PI4+AlCl4− and PI4+EBr4− (E = Al, Ga) have been synthesised. A variety of solid complexes containing PBr4+ (e.g. PBr4+AsF6−, PBr4+AlBr4− PBr4+GaBr4−), PI4+ (e.g. PI4+AlCl4−, PI4+AlBr4−, PI4+GaBr4−) or the mixed species PBrnI4 − n+ (0 ≤ n ≤ 4, containing AlBr4−, GaBr4−, AsF6− or SbF6−) have been studied by solid-state 31P MAS NMR and vibrational spectroscopy. The influence of the counter-ion on the chemical shift and the vibrational frequencies are discussed. The crystal structures of PI4+AlCl4−, PI4+AlBr4− and PI4+GaI4− are reported. Evidence for the existence of the hitherto unknown mixed bromoiodophosphonium cations PBr3I+, PBr2I2+ and PBrI3+ has been confirmed by spin–orbit corrected density functional calculations of isotropic 31P chemical shifts for PBrnI4 − n+

Changes in Received Pronunciation: Diachronic Case Studies

This paper sets out to investigate changes and individual irregularities in the Received Pronunciation of a number of individuals over time and to compare them with the changes noted in contemporary RP in the literature. The aim of the study is to ascertain whether accent change affects individuals during their lifetimes or is only brought about by new generations of speakers accepting different pronunciations as the norm and effectively speaking with a different accent to older generations within their social circle. The variations/changes looked for were: CLOTH transfer, CURE lowering, GOAT allophony, R-sandhi, and T-voicing. The procedure of the study was to identify the presence or absence of these features in the speech of certain individuals in recordings made over a period of at least 35 years. The individuals studied were: Her Majesty Queen Elizabeth II, Baroness Thatcher, Sir David Attenborough and David Dimbleby. The results of these comparisons suggest that individual speakers are not greatly affected by changes in pronunciation taking place around them and generally stay with the preferred pronunciation of their youth. There are, however, cases where a general uncertainty amongst speakers of the accent, here found in CURE lowering, does influence the speech of individuals over time

Reduced admixture of North Atlantic Deep Water to the deep central South Pacific during the last two glacial periods

Key Points: • Little deep water circulation changes in the past 240,000 years in the central South Pacific • Reduced North Atlantic Deep Water admixture during glacials to the Southern Ocean • South Pacific lithogenic material mainly sourced from SE Australia and South New Zealand The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific basin are exchanged. Here we reconstruct the deep-water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for εNd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water (NADW) to CDW during cold stages. The absolute values and amplitudes of the benthic δ13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific

Migration and household demography in Nang Rong, Thailand

This work investigates various facets of migration and household demography in Thailand, a developing country that has been experiencing a shift from a rural subsistence economy to an urban industrial base. The setting is Nang Rong, a rural agrarian district located in Buriram province in the Northeast. At one time a frontier region, the district has been undergoing tremendous social, economic, and demographic transformations in the last three decades. The first analytical portion of the work deals with care for children of absent migrant parents. I develop a model of total childcare, whereby someone other than a biological parent assumes total parental responsibility in the parents' absence. I describe a process whereby a mutually-beneficial intergenerational household division of labor develops in which the older generation cares for the children of absent migrant parents, who provide for economic needs of their origin households. Next, using help with harvesting rice as an illustration of the profound changes that occur during the industrial transition, I examine intergenerational relations between young out-migrants and their parents. I find that migrants are more likely to help with the rice harvest if their origin household owns securely titled land, and if the migrant has lower human capital endowments. Results suggest that intergenerational relations between parents and children are becoming more instrumental, which is related to a household strategy predicated on individual self-interest and bargaining. The final analytical chapter deals with the effect of remittances on household division, a demographic process that is understudied in rural developing contexts. Results suggest that remittance money sent by other household members (especially women, who perhaps are siblings of those who eventually move) is used to finance a household split. This is potentially related to the effect that remittances have on alleviating credit constraints, which makes it possible for families and households to fund costs (such as home construction) associated with movement into an independent household. Remittance effects are particularly associated with a later stage in the Thai household life cycle whereby a young couple moves out of the household of the wife's family into an independent nuclear household

Migrant Remittances and Skipped Generation Households: Investigating the Exchange Motive Using Evidence from Nang Rong, Thailand

Using data from the Nang Rong projects social survey (N=6,801 households) and qualitative data from semi-structured interviews, I examine the relationship between migrant remittances and the skipped generation household structure. I find that the skipped generation household is a significant determinant of in-kind remittances and the amount of remittances received by the household. Surprisingly, although qualitative data suggest that grandparents living in skipped generation households provide childcare for the children of absent migrants, quantitative evidence reveals that these households receive lower remittance amounts than other households. This suggests that although an exchange motivation may be overlooked in the remittance literature, it does not apply to migrant remittances as it does in the broader literature on inter vivos intergenerational transfers.Yeshttps://us.sagepub.com/en-us/nam/manuscript-submission-guideline

Southern Ocean deep convection as a driver of Antarctic warming events

Simulations with a free-running coupled climate model show that heat release associated with Southern Ocean deep convection variability can drive centennial-scale Antarctic temperature variations of up to 2.0 °C. The mechanism involves three steps: Preconditioning: heat accumulates at depth in the Southern Ocean; Convection onset: wind and/or sea-ice changes tip the buoyantly unstable system into the convective state; Antarctic warming: fast sea-ice–albedo feedbacks (on annual–decadal timescales) and slow Southern Ocean frontal and sea-surface temperature adjustments to convective heat release (on multidecadal–century timescales) drive an increase in atmospheric heat and moisture transport toward Antarctica. We discuss the potential of this mechanism to help drive and amplify climate variability as observed in Antarctic ice-core records

Marriage counterfactuals in Japan: Variation by gender, marital status, and time

Background: This paper takes a unique perspective on the debate surrounding the deinstitutionalization of marriage. Rather than examining how diversification of family behaviors (external context) relates to marriage, it considers how perceptions of marriage dimensions (the internal context) vary across relevant stakeholders. Objective: We ask whether perceived consequences of marriage differ for people who married vs. people who never married and men vs. women and over time. Methods: Based on data from the 1994 National Survey on Work and Family Life in Japan and the 2000 and 2009 National Survey of Family and Economic Conditions (NSFEC) in Japan (N = 8,467) we use unique measures of perceived consequences of marriage ("marriage counterfactuals") to examine social, economic, psychological, and personal dimensions (i.e., respect, living standard, emotional security, freedom, and overall satisfaction). Results: Ordinal regression results reveal that marital perceptions worsened over time (in terms of living standard and freedom), consistent with worsening economic conditions. We also find that people who have never been married tend to view marriage more favorably than their married counterparts (especially freedom and respect), while men view marriage consequences (except for living standard) more favorably than women. Conclusions: Despite more negative change over time in perceptions of marriage among people who never married than people who have married, the traditional breadwinner-homemaker model of marriage continues to be important and influential in Japan, and cultural beliefs regarding traditional marriage persist in spite of structural changes. Contribution: Research and theory on family change should pay more attention to the internal marriage context more fully than they have in the past

Farming Systems and Rural Out-Migration in Nang Rong, Thailand, and Chitwan Valley, Nepal: Farming Systems and Rural Out-Migration

Using data from two post-frontier rural settings, Nang Rong, Thailand (N=2,538) and Chitwan Valley, Nepal (N=876), this paper examines agricultural push factors determining the outmigration of young people age 15 to 19. We focus on different dimensions of migration, including distance and duration. Our study examines a wide array of agricultural determinants, each with its own potential effect on migration. These determinants include land tenure, crop portfolios, animal husbandry activities, and use of farm inputs. We link these proximal causes to two underlying mechanisms: risk and amenities. We examine these determinants using separate models across settings. Our results indicate that agricultural factors are significant determinants of migration in both contexts. However, different factors operate in different settings, indicating the importance of contextual variation in explaining the manner in which risks and amenities influence agricultural determinants of migration

Zircon effect alone insufficient to generate seawater Nd-Hf isotope relationships

[1] Many studies have suggested that continental weathering inputs have controlled the dissolved oceanic budget of hafnium (Hf). However, whether the offset of seawater Nd‐Hf isotope compositions from the terrestrial array can be fully generated by incongruent weathering of continental rocks (the zircon effect) is still not well constrained. In recent years, an increasing amount of combined U‐Pb ages and Hf‐isotopic compositions of riverine detrital zircons have been published. Here a new model of the Nd‐Hf isotopic compositions of the weathered zircon‐free part of the upper continental crust is presented, which is based on published Hf isotope compositions and formation ages of modern riverine detrital zircons combined with Nd isotopic compositions of rocks from the upper continental crust. Our model results indicate that the Nd‐Hf isotopic composition of the weathered zircon‐free part of the upper continental crust is not consistent with the seawater isotopic compositions. This suggests that the elevated seawater Hf isotope compositions for given Nd isotope compositions cannot be fully explained by incongruent zircon weathering of the continents, which is also supported by a recent study demonstrating incongruent weathering of other minerals than zircon