Lability of Pb in soil: effects of soil properties and contaminant source

Environmental Context: There is growing concern that lead (Pb) in the environment may cause adverse health effects in human populations. We investigated the combined use of isotopic abundance and isotopic dilution to show how the origins of soil Pb and soil characteristics affect lability. Soil pH and soil Pb content are the dominant controls on Pb lability; the lability of recent petrol-derived Pb is similar to that of other sources in urban soils but greater than geogenic Pb in rural roadside topsoils. Lability of lead (Pb) in soils is influenced by both soil properties and source(s) of contamination. We investigated factors controlling Pb lability in soils from (i) land adjacent to a major rural road, (ii) a sewage processing farm and (iii) an archive of the geochemical survey of London. We measured isotopically exchangeable Pb (E-values; PbE), phase fractionation of Pb by a sequential extraction procedure (SEP) and inferred source apportionment from measured Pb isotopic ratios. Isotopic ratios (206Pb/207Pb and 208Pb/207Pb) of total soil Pb fell on a mixing line between those of petrol and UK coal or Pb ore. The main determinant of the isotopically exchangeable Pb fraction (%E-value) was soil pH: %E-values decreased with increasing pH. In rural roadside topsoils and there was also evidence that, petrol-derived Pb remained more labile (35%) than Pb from soil parent material (27%). However, in biosolid-amended and London soils %E-values were low (c. 25%), covered a restricted range, and showed no clear evidence of source-dependent lability

Why do we need a theory and metrics of technology upgrading?

This paper discusses why we need theory and metrics of technology upgrading. It critically reviews the existing approaches to technology upgrading and motivates build-up of theoretically relevant but empirically grounded middle level conceptual and statistical framework which could illuminate a type of challenges relevant for economies at different income levels. It conceptualizes technology upgrading as three dimensional processes composed of intensity and different types of technology upgrading through various types of innovation and technology activities; broadening of technology upgrading through different forms of technology and knowledge diversification, and interaction with global economy through knowledge import, adoption and exchange. We consider this to be necessary first step towards theory and metrics of technology upgrading and generation of more relevant composite indicator of technology upgrading

Does the Millennium Challenge Corporation reinforce capitalist power structures or empower citizens?

In development practice, how does ‘mutual benefit’ accrue, and to whom? China criticises America for perpetuating capitalist power relations and claims it can seek a new geo-political order based on South-South cooperation. Meanwhile, there has been an extraordinary shift of emphasis toward the private sector as a driver of development, but this shift is attracting increasing criticism. The Millennium Challenge Corporation (MCC) - the only development agency to grow in influence under the Trump administration - is evaluated in the light of these two key themes. Neither China nor the private sector are successful in achieving ‘mutual benefit’ for ordinary citizens – both replicate existing power inequalities. As with the rise of both China and the private sector, the MCC also enmeshes developing countries further into the existing neoliberal capitalist structures. However, the advantages of the agency should not be dismissed outright, as its Ruling Justly and Investing in People indicators can enhance the capacity of citizens to challenge these power structures themselves

Effect of crustal stress state on magmatic stalling and ascent: case study from Puyehue-Cordón Caulle, Chile

The Southern Volcanic Zone (SVZ) in Chile is an active continental arc with a complex history of volcanism, where a range of magmatic compositions have been erupted in a variety of styles. In the Central SVZ, both monogenetic and polygenetic volcanoes exist, in close proximity to the Liquiñe-Ofqui Fault System (LOFS), but with variable local stress states. Previous studies have inferred varying crustal storage timescales, controlled by the orientation of volcanic centres relative to the N-S striking LOFS and σHMax in this region. To assess the relationship between volcanism and crustal stress states affected by large-scale tectonic structures and edifice controls, we present whole rock geochemical data, to ensure consistency in source dynamics and crustal processing, mineral-specific compositional data, thermobarometry, and Fe–Mg diffusion modelling in olivine crystals from mafic lavas, to assess ascent timescales, from the stratovolcanic edifice of Puyehue-Cordón Caulle and proximal small eruptive centres. Textural observations highlight differences in crystal maturation timescales between centres in inferred compression, transpression, and extension, yet source melting dynamics remain constant. Only samples from the stratovolcanic edifice (in regional compression) preserve extensive zonation in olivine macrocrysts; these textures are generally absent from proximal small eruptive centres in transtension or extension. The zonation in olivines from stratovolcanic lavas yields timescales on the order of a few days to a few weeks, suggesting that even in environments which inhibit ascent, timescales between unrest and eruption of mafic magmas may be short. Significantly, high-resolution compositional profiles from olivine grains in the studied samples record evidence for post-eruptive growth and diffusion, highlighting the importance of careful interpretation of diffusion timescales from zoned minerals in more slowly cooled lavas when compared with tephra samples

Stable isotopic composition of fossil mammal teeth and environmental change in southwestern South Africa during the Pliocene and Pleistocene

The past 5 million years mark a global change from the warmer, more stable climate of the Pliocene to the initiation of glacial-interglacial cycles during the Pleistocene. Marine core sediment records located off the coast of southwestern Africa indicate aridification and intensified upwelling in the Benguela Current over the Pliocene and Pleistocene. However, few terrestrial records document environmental change in southwestern Africa over this time interval. Here we synthesize new and published carbon and oxygen isotope data of the teeth from large mammals (>6 kg) at Langebaanweg (~5 million years ago, Ma), Elandsfontein (1.0 – 0.6 Ma), and Hoedjiespunt (0.35 – 0.20 Ma), to evaluate environmental change in southwestern Africa between the Pliocene and Pleistocene. The majority of browsing and grazing herbivores from these sites yield enamel 13 C values within the range expected for animals with a pure C3 diet, however some taxa have enamel 13C values that suggest the presence of small amounts C4 grasses at times during the Pleistocene. Considering that significant amounts of C4 grasses require a warm growing season, these results indicate that the winter rainfall zone, characteristic of the region today, could have been in place for the past 5 million years. The average 18O value of the herbivore teeth increases ~4.4‰ between Langebaanweg and Elandsfontein for all taxa except suids. This increase may solely be a function of a change in hydrology between the fluvial system at Langebaanweg and the spring-fed environments at Elandsfontein, or a combination of factors that include depositional context, regional circulation and global climate. However, an increase in regional aridity or global cooling between the early Pliocene and mid-Pleistocene cannot explain the entire increase in enamel 18O values. Spring-fed environments like those at Elandsfontein may have 75 provided critical resources for mammalian fauna in the mid-Pleistocene within an increasingly arid southwestern Africa ecosystem

Dexamphetamine boosts naming treatment effects in chronic aphasia

To date, minimal research has investigated the effect of combining dexamphetamine with standard naming therapy after stroke. The present study used a double-blind, placebo-controlled, multiple baseline, crossover design with two individuals in the chronic stage of stroke recovery. Each individual attended two 4-week blocks of naming therapy (two to three treatment sessions per week). Dexamphetamine (10 mg) was administered at the start of each session during one therapy block, while a placebo was administered during the other therapy block. Therapy progress on treated and untreated items was assessed by a confrontation naming task during and after each therapy block. Both individuals showed greater progress in therapy and maintenance of therapy gains when behavioral treatment was combined with dexamphetamine rather than placebo, although this gain was only statistically significant in one individual. There was no significant improvement on a control task (nonword reading) in either individual. The results provide preliminary evidence that dexamphetamine paired with combined semantic and phonological therapy may be beneficial for the treatment of naming disorders in chronic aphasia

Optimisation of a current generation ICP-QMS and benchmarking against MC-ICP-MS spectrometry for the determination of lead isotope ratios in environmental samples

© 2018 The Royal Society of Chemistry. Novel ANOVA methodology was used to benchmark ICP-QMS against MC-ICP-MS for Pb isotope ratios, demonstrating "fitness-for-purpose" in environmental source apportionment. The precision and accuracy of lead (Pb) isotope measurements obtained from quadrupole-based mass spectrometers (ICP-QMS) are considered to be limited by a number of factors originating in different components of the instruments. In this study, experimental and instrumental protocols were optimised for determining lead isotope ratios in urban soil digests. Experimental measures included individual dilution of all samples and isotopic standards (SRM-981, NIST) to a single Pb concentration intended to produce an intensity which was high enough to negate blanks and interferences but low enough to ensure the detector operated only in pulse counting mode. Instrumental protocols included batch dead time correction, optimisation of dwell time and the number of scans employed and correction of mass discrimination by sequential application of both internal ( 203 Tl/ 205 Tl ratio) and external (SRM-981, NIST) standards. This optimised methodology was benchmarked against multi-collector mass spectrometer (MC-ICP-MS) measurements of Pb isotope ratios using replicate digest solutions of the same soil; but after these had been subjected to Pb separation using an ion-exchange procedure. On the assumption that MC-ICP-MS measurements are more accurate, small additive and multiplicative differences were observed in only the 4 th decimal place. ANOVA was used to compare the precisions of the two techniques demonstrating equal precisions c. 0.08% for 207 Pb/ 206 Pb, suggesting a sample heterogeneity limitation. By contrast, for 207 Pb/ 204 Pb, the worst-case ratio, ICP-QMS had a 10-fold poorer precision, despite negligible interference from 204 Hg, implying an instrumental limitation. The study concludes that ICP-QMS can provide valuable source apportionment information for most Pb isotope ratios but further efforts should focus on improving assay of the 207 Pb/ 204 Pb ratio

Recommendations to facilitate the ideal fit note: are they achievable in practice?

Background: Although the UK fit note has been broadly welcomed as a tool to facilitate return to work, difficulties and uncertainties have resulted in wide variation in its use. Agreement on what constitutes the ‘ideal’ fit note from the perspective of all stakeholders is needed to inform best practice. A recent Delphi study conducted by the authors reached consensus on 67 recommendations for best practice in fit note use for employed patients. However, such recommendations are not necessarily followed in practice. The purpose of this study was therefore to investigate the perceived achievability of implementing these Delphi recommendations with a further reference panel of stakeholders. Methods: Potential participants were identified by the research team and study steering group. These included representatives of employers, government departments, trades unions, patient organisations, general and medical practitioners and occupational health organisations who were believed to have the knowledge and experience to comment on the recommendations. The consensus Delphi statements were presented to the participants on-line. Participants were invited to comment on whether the recommendations were achievable, and what might hinder or facilitate their use in practice. Free text comments were combined with comments made in the Delphi study that referred to issues of feasibility or practicality. These were synthesised and analysed thematically. Results: Twelve individuals representing a range of stakeholder groups participated. Many of the recommendations were considered achievable, such as improved format and use of the electronic fit note, completion of all fields, better application and revision of guidance and education in fit note use. However a number of obstacles to implementation were identified. These included: legislation governing the fit note and GP contracts; the costs and complexity of IT systems and software; the limitations of the GP consultation; unclear roles and responsibilities for the funding and delivery of education, guidance and training for all stakeholders, and the evaluation of practice. Conclusions: This study demonstrated that although many recommendations for the ideal fit note are considered achievable, there are considerable financial, legal, organisational and professional obstacles to be overcome in order for the recommendations to be implemented successfully

Immobilisation of chromium in magnesium carbonate minerals

Hexavalent chromium (Cr6+) is a toxic carcinogenic pollutant that might be released by the mining and processing of ultramafic rocks and nickel laterites and which requires permanent removal from the contaminated biosphere. Ultramafic material can also serve as a feedstock for the sequestration of CO2 resulting from the growth of new minerals, raising the intriguing proposition of integrated sequestration of both pollutants, CO2 and chromium, into magnesium carbonates. Such a synergistic process downstream of ore recovery and mineral processing could be an elegant proposition for more sustainable utilisation and management of the Earth's resources. We have therefore carried out an experimental and microanalytical study to investigate potentially suitable carbonate minerals. Uptake of chromium in carbonate phases was determined, followed by identification of the crystalline phases and characterisation of the local structural environment around the incorporated chromium centres. The results suggest that neither nesquehonite nor hydromagnesite have the structural capacity to incorporate Cr6+ or Cr3+ significantly at room temperature. We therefore propose that further research into this technology should focus on laboratory assessments of other phases, such as layered double hyroxides, that have a natural structural capacity to uptake both chromium and CO2

Dopamine and semantic activation: An investigation of masked direct and indirect priming

To investigate the effects of dopamine on the dynamics of semantic activation, 39 healthy volunteers were randomly assigned to ingest either a placebo (n = 24) or a levodopa (it = 16) capsule. Participants then performed a lexical decision task that implemented a masked priming paradigm. Direct and indirect semantic priming was measured across stimulus onset asynchronies (SOAs) of 250, 500 and 1200 ms. The results revealed significant direct and indirect semantic priming effects for the placebo group at SOAs of 250 ms and 500 ms, but no significant direct or indirect priming effects at the 1200 ms SOA. In contrast, the levodopa group showed significant direct and indirect semantic priming effects at the 250 ms SOA, while no significant direct or indirect priming effects were evident at the SOAs of 500 ins or 1200 ms. These results suggest that dopamine has a role in modulating both automatic and attentional aspects of semantic activation according to a specific time course. The implications of these results for current theories of dopaminergic modulation of semantic activation are discussed