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Synthetic, relatively well-crystallized aluminum-substituted maghemite samples, γ-(Aly·Fe1−y)2O3, with y = 0, 0.032, 0.058, 0.084, 0.106 and 0.151 have been studied by X-ray diffraction and zero-field Mössbauer spectroscopy in the range 8 K to 475 K, and also with an external field of 60 kOe at 4.2 K and 275 K. It was found that there are two different converging models for fitting the zero-field spectra of the maghemites with a superposition of two Lorentzian-shaped sextets, both resulting in inconsistent values for the hyperfine fields (Hhf) and/or the center shifts (δ) of the tetrahedral (A) and octahedral (B) ferric ions. From the applied-field measurements it is concluded that there is a constant difference of 0.12 ± 0.01 mm/s between δB and δA, regardless of the Al content. For the Al-free sample the center shifts are found as: δA = 0.370 mm/s and δB = 0.491 mm/s at 4.2 K and δA = 0.233 mm/s and δB = 0.357 mm/s at 275 K (relative to metallic iron), with an estimated error of 0.005 mm/s. Both δA and δB are observed to decrease with increasing Al concentration. The effective hyperfine fields for the non-substituted maghemite sample are: Heff,A = 575 kOe and Heff,B = 471 kOe at 4.2 K and Heff,A = 562 kOe and Heff,B = 449 kOe at 275 K, with an error of 1 kOe. The B-site hyperfine field remains approximately constant with Al substitution, while for the A site a slight decrease with increasing Al content was observed.
Synthetic aluminum-substituted maghemite samples, γ-(Fe1-xAlx)2O3, have been prepared by thermal decomposition of Al-lepidocrocite (γ-Fe1-xAlxOOH), with × = 0, 0.04, 0.06, 0.14 and 0.18. The particles are needle-shaped and the mean crystallite diameter along the [311] crystallographic direction was found to be between 2.0 and 5.0 nm. Mössbauer spectra were collected at 6 K and from 80 K up to 475 K at steps of 25 K. In a wide range of temperatures the spectra of the non-substituted sample consist of a superposition of a broad sextet and a superparamagnetic doublet, whereas for the Al-maghemites this range is much smaller. From the temperature variation of the fractional doublet area two different parameters were defined: the temperature corresponding to a 50/50 doublet-sextet spectrum (T1/2), and the temperature below which the doublet ceases to exist (T0). These two parameters (T1/2 and T0) decrease from 390 K and 92 K (Al-free sample), to 118 K and 64 K (4 mole % Al) and to 100 K and 48 K (18 mole % Al), respectively. The average hyperfine fields at 6 K undergo a steep drop in going from the Al-free sample (Hhf = 506 kOe) to the sample with 4 mole % Al (Hhf = 498 kOe), but for higher substitutions the effect is much smaller. The A- and B-site quadrupole splittings, obtained from the data between 220 K and 475 K, were found as: ΔEQ,A = 0.86 ± 0.04 mm/s and ΔEQ,B = 0.65 ± 0.04 mm/s for the 4 mole % Al sample. The characteristic Mössbauer temperature, determined from the temperature dependence of the average isomer shift, was found to be in the range of 500–600 K.
In a previous paper, we used powder X-ray diffraction and changes in magnetic susceptibility to argue the importance of pedogenic maghemite to soils and the efficacy of the chemical extractant citrate-bicarbonate-dithionite (CBD) to preferentially remove pedogenic maghemite from soil samples while not removing coarse-grained magnetite. Although X-ray diffraction provides strong support for this contention, Mössbauer spectroscopy is the method of choice for determining the oxidation state of iron in minerals and for inferring mineralogy of the iron oxide phases. Our objective in this work was to seek confirming evidence of the importance of maghemite as a pedogenic mineral and the usefulness of the CBD procedure in separating pedogenic maghemite from lithogenic magnetite. We present Mössbauer data on magnetic fractions from pre- and post-CBD treated soil samples. Six of the 10 samples had only maghemite as the sextet component and after CBD treatment, four lost between 96 and 100% of the magnetic susceptibility. Two samples were interpreted as highly oxidized magnetite or a mixture of magnetite and maghemite. We cannot distinguish between these with Mössbauer spectroscopy. In the remaining two samples, iron existed as hematite, ilmenite, magnetite and minor (<10%) amounts of maghemite. Our results provide additional support for pedogenic maghemite in soils and for the preferential removal of maghemite by the CBD procedure.
The central and associated county or district chambers of agriculture have attracted little attention from historians. Their origins have been attributed to the perceived lack of a national coordinating body for agriculture highlighted by the 1865–7 cattle plague. This article based on the records of the Shropshire Chamber of Agriculture, newspapers and printed histories reconsiders their role. Members were initially drawn from landowning society and larger tenant farmers, although membership widened with the growth of rival organisations. Activities included lectures, talks and debates on agricultural subjects, visits to farms, factories and the county agricultural college and farm institute, dinners and social occasions at which those interested in agriculture could meet. By foregrounding the people and politics of the chambers of agriculture, it is argued they need to be incorporated more fully into the historiography of agricultural and rural politics of Britain during the nineteenth and early twentieth centuries.
Animal hoarding is considered to be an under-reported problem, which affects the welfare of both people and animals. Few published studies on animal hoarding are available in the scientific literature, particularly outside North America. The present study was designed to obtain data on animal hoarding in Spain, with a particular focus on animal welfare issues. Data were obtained retrospectively from 24 case reports of animal hoarding involving a total of 1,218 dogs and cats and 27 hoarders. All cases were the result of legal intervention by a Spanish humane society during the period from 2002 to 2011. Hoarders could be characterised as elderly, socially isolated men and women who tended to hoard only one species (dog or cat). Most cases presented a chronic course of more than five years of animal hoarding. The average number of animals per case was 50, with most animals being dogs. In 75% of cases the animals showed indications of poor welfare, including poor body condition, and the presence of wounds, parasitic and infectious illnesses. Amongst the hoarded animals aggression and social fear were the most commonly reported behaviours. To the authors’ knowledge, this is the first report on animal hoarding in Spain and one of the first in Europe. Further studies are needed to fully elucidate the epidemiology, cross-cultural differences and aetiology of this under-recognised public health and welfare problem. More research might help to find efficient protocols to assist in the resolution and prevention of this kind of problem.
We summarize some of the past year's most important findings within climate change-related research. New research has improved our understanding of Earth's sensitivity to carbon dioxide, finds that permafrost thaw could release more carbon emissions than expected and that the uptake of carbon in tropical ecosystems is weakening. Adverse impacts on human society include increasing water shortages and impacts on mental health. Options for solutions emerge from rethinking economic models, rights-based litigation, strengthened governance systems and a new social contract. The disruption caused by COVID-19 could be seized as an opportunity for positive change, directing economic stimulus towards sustainable investments.
Technical summary
A synthesis is made of ten fields within climate science where there have been significant advances since mid-2019, through an expert elicitation process with broad disciplinary scope. Findings include: (1) a better understanding of equilibrium climate sensitivity; (2) abrupt thaw as an accelerator of carbon release from permafrost; (3) changes to global and regional land carbon sinks; (4) impacts of climate change on water crises, including equity perspectives; (5) adverse effects on mental health from climate change; (6) immediate effects on climate of the COVID-19 pandemic and requirements for recovery packages to deliver on the Paris Agreement; (7) suggested long-term changes to governance and a social contract to address climate change, learning from the current pandemic, (8) updated positive cost–benefit ratio and new perspectives on the potential for green growth in the short- and long-term perspective; (9) urban electrification as a strategy to move towards low-carbon energy systems and (10) rights-based litigation as an increasingly important method to address climate change, with recent clarifications on the legal standing and representation of future generations.
Social media summary
Stronger permafrost thaw, COVID-19 effects and growing mental health impacts among highlights of latest climate science.
Further research is still needed to demonstrate the benefits of animal-assisted therapy (AAT) for specific participant profiles, such as children with behavioural disorders.
Objectives
We wanted to find out if AAT could be considered an efficient therapeutic strategy for the treatment of children with behavioural disorders.
Aims
We wanted to study the effects of a preestablished AAT program on the behaviour of children with emotional and behavioural issues in 6 different reception centres for children under government guardianship.
Methods
Forty-five children (12 to 17 years old) with emotional and behavioural issues participated in a 14-session AAT program. Behavioural measures were those routinely scored as part of therapy; an observational report of 3 different problematic behaviours (such as impulsivity, lack of social skills or lack of personal recognition) was made twice a week for each child (with a score of frequency and intensity). A pre- and post-treatment “global behaviour score” was calculated for each child, as an average value of the 3 problematic behaviours measured during the month pre-treatment and the month post-treatment.
Results
The 45 participants attended, on average, 72.8% of AAT sessions. Independent behaviour scores differed between the pre- and post-intervention evaluations (n = 135 behaviours) (Wilcoxon test; P < 0.0001). Based on the global behaviour score for each child (n = 45), significant change was found between pre- and post-intervention evaluations (Wilcoxon test; P = 0.0011).
Conclusions
Our results suggest AAT could be a beneficial intervention for children with behavioural issues in terms of program adherence and behaviour improvement.
Disclosure of interest
The authors have not supplied their declaration of competing interest.
Animal hoarding is considered an under-reported problem, which affects the welfare of both people and animals. Few reports on animal hoarding are available in scientific literature, particularly outside North America.
Objectives
We designed a study to analyse cases of animal hoarding in Catalonia.
Aims
We wanted to expose the presence and consequences of this disorder in our area and to check for cross-cultural similarities with previous studies in other countries.
Methods
Data was obtained retrospectively from 23 case reports of animal hoarding in Catalonia collected by city councils and the Catalonian police from 1992 to 2015.
Results
Thirty-three people (20 women and 13 men) and 1521 animals, mainly dogs and cats, were involved. Most cases (n = 13) involved a sole animal hoarder. Most cases (n = 14) were chronic (lasting longer than 5 years). Object hoarding co-morbidity was found in most cases (n = 17). All hoarders were over 40-years-old, with half of them aged over 65. Only in 4 cases was an intervention by the healthcare system reported. Most of the hoarders (9 out of 13) actively opposed animal removal. In more than 50% of cases, the hoarder's personal care, health and financial situation were precarious. No awareness of the impaired welfare of the animals was found in most cases.
Conclusions
To the author's knowledge, this is the first study on animal hoarding in Catalonia and one of the few available in Europe. Our results are aligned with previous research, adding evidence of cross-cultural common elements of animal hoarding.
Disclosure of interest
The authors have not supplied their declaration of competing interest.
Obtaining geochemical profiles using X-ray fluorescent (XRF) techniques has become a standard procedure in many sediment core studies. The resulting datasets are not only important tools for palaeoclimatic and palaeoceanographic reconstructions, but also for stratigraphic correlation. The International Ocean Discovery Program (IODP) has therefore recently introduced shipboard application of a handheld XRF device, making geochemical data directly available to the science party. In all XRF scanning techniques, the physical properties of wet core halves cause substantial analytical deviations. In order to obtain estimates of element concentrations (e.g. for quantitative analyses of fluxes or mass-balance calculations), a calibration of the scanning data is required. We test whether results from the handheld XRF analysis on discrete samples are suitable for calibrating scanning data. Log-ratios with Ca as a common denominator were calculated. The comparison between the handheld device and conventional measurements show that the latter provide high-quality data describing Al, Si, K, Ca, Ti, Mn, Fe, Zn, Rb and Sr content (R2 compared with conventional measurements: ln(Al/Ca) = 0.99, ln(Si/Ca) = 0.98, ln(K/Ca) = 0.99, ln(Ti/Ca) = 0.99, ln(Mn/Ca) = 0.99, ln(Fe/Ca) = 0.99, ln(Zn/Ca) = 0.99 and ln(Sr/Ca) = 0.99). Our results imply that discrete measurements using the shipboard handheld analyser are suitable for the calibration of XRF scanning data. Our test was performed on downcore sediments from IODP Expedition 355 that display a wide variety of lithologies of both terrestrial and marine origin. The implication is that our findings are valid on a general scale and that shipboard handheld XRF analysis on discrete samples should be used for calibrating XRF scanning data.
H2D+ and D2H+ are important chemical tracers of prestellar cores due to their pure rotational spectra that can be excited at the ~20 K temperature of these environments. The use of these molecules as probes of prestellar cores requires understanding the chemistry that forms and destroys these molecules. Of the eight key reactions that have been identified (Albertssonet al. 2013), five are thought to be well understood. The remaining three are the isotope exchange reactions of atomic D with H
$${ + \over 3}$$
, H2D+, and D2H+. Semi-classical results differ from the classical Langevin calculations by an order of magnitude (Moyano et al. 2004). To resolve this discrepancy, we have carried out laboratory measurements for these three reactions. Absolute cross sections were measured using a dual-source, merged fast-beams apparatus for relative collision energies between ~10 meV to ~10 eV (Hillenbrand et al. 2019). A semi-empirical model was developed incorporating high level quantum mechanical ab initio calculations for the zero-point-energy-corrected potential energy barrier in order to generate thermal rate coefficients for astrochemical models. Based on our studies, we find that these three reactions proceed too slowly at prestellar core temperatures to play a significant role in the deuteration of H
$${ + \over 3}$$
isotopologues.
Eleven Oxisols with high clay contents, 2.6–59.7 wt.% Fe2O3, and containing hematite, goethite, magnetite and maghemite, from São Paulo, Minas Gerais and Goiás, Brazil, were studied for the purpose of microwave remote sensing applications in the 0.3 to 300 GHz range. Of special interest are: the pseudosand effect caused by Fe-oxide cementation of clusters of soil particles; the mineralogy; and whether the soil magnetic susceptibility affected by ferromagnetic magnetite and maghemite interferes with microwave propagation. Quantitative mineralogical analyses were conducted using X-ray diffraction with Rietveld refinement. Visible, near infrared and short wave infrared spectroscopic analyses were used to characterize the samples qualitatively for comparison with published spectral radiometry results. Quartz (3–88%), hematite (2–36%) and gibbsite (1–40%) occurred in all soils, whereas kaolinite (2–70%) and anatase (2–13%) occurred in nine samples. Ilmenite (1–8%) was found in eight soils and goethite (2–39%) in seven. Of the ferromagnetic minerals, maghemite occurred in seven soils (1–13%) and three contained magnetite (<2%). These results will be applied to the interpretation of the effect of Fe oxides, particularly the ferromagnetic oxides, on microwave interaction with high-Fe soils, with ultimate application to the monitoring of soil water content by microwave remote sensing.
We investigate self-similar sign-changing solutions to the thin-film equation, ht = −(|h|nhxxx)x, on the semi-infinite domain x ≥ 0 with zero-pressure-type boundary conditions h = hxx = 0 imposed at the origin. In particular, we identify classes of first- and second-kind compactly supported self-similar solutions (with a free-boundary x = s(t) = Ltβ) and consider how these solutions depend on the mobility exponent n; multiple solutions can exist with the same number of sign changes. For n = 0, we also construct first-kind self-similar solutions on the entire half-line x ≥ 0 and show that they act as limiting cases for sequences of compactly supported solutions in the limit of infinitely many sign changes. In addition, at n = 1, we highlight accumulation point-like behaviour of sign-changes local to the moving interface x = s(t). We conclude with a numerical investigation of solutions to the full time-dependent partial differential equation (based on a non-local regularisation of the mobility coefficient) and discuss the computational results in relation to the self-similar solutions.
This paper describes a study of the hydraulic reactions between metakaolin (MK) and air lime using electrochemical impedance spectroscopy (EIS) and nuclear magnetic resonance spectroscopy (NMR). Tests were carried out at 20, 25 and 30°C on lime-MK pastes with 10:1 w/w ratio. Tests over 28 days allowed identification of relevant changes in the EIS signals and characterization of pastes using thermal analysis (TGA/DSC), scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP) and uni-axial compressive tests. Tests over shorter periods of time (up to 42 h) allowed more detailed studies of the hydraulic phases formed at the very beginning of the reactions.
Results of thermal analyses demonstrate formation of hydraulic compounds such as CSH, C4AH13 and C3ASH6 and show their evolution over time. MIP analysis demonstrates changes in pore size distribution related to the formation and trasformation of hydraulic phases. Variations of impedance response with time are shown to be associated with reaction kinetics. Changes in the NMR signal within the first 42 h of reaction are shown to be associated with the dissolution of calcium hydroxide in the pore solution. Overall, this paper demonstrates the importance of NMR in the study of hydraulic reactions in lime based materials and the ability of EIS to detect the formation of hydraulic compounds and the end of the calcium hydroxide dissolution process.
High levels of molecular diversity were identified in mitochondrial cytochrome c oxidase (cox1) gene sequences of Schistosoma turkestanicum from Hungary. These cox1 sequences were all specific to Hungary which contrasted with the low levels of diversity seen in the nuclear internal transcribed spacer region (ITS) sequences, the majority of which were shared between China and Iran isolates. Measures of within and between host molecular variation within S. turkestanicum showed there to be substantial differences in molecular diversity, with cox1 being significantly more diverse than the ITS. Measures of haplotype frequencies revealed that each host contained its own subpopulation of genetically unique parasites with significant levels of differentiation. Pairwise mismatch analysis of cox1 sequences indicated S. turkestanicum populations to have a bimodal pairwise difference distribution and to be stable unlike the ITS sequences, which appeared to have undergone a recent population expansion event. Positive selection was also detected in the cox1 sequences, and biochemical modelling of the resulting protein illustrated significant mutational events causing an alteration to the isoelectric point of the cox1 protein, potentially altering metabolism. The evolutionary signature from the cox1 indicates local adaptation and long establishment of S. turkestanicum in Hungary with continual introgression of nuclear genes from Asian isolates. These processes have led to the occurrence of mito-nuclear discordance in a schistosome population
Impetigo is common in remote Indigenous children of northern Australia, with the primary driver in this context being Streptococcus pyogenes [or group A Streptococcus (GAS)]. To reduce the high burden of impetigo, the transmission dynamics of GAS must be more clearly elucidated. We performed whole genome sequencing on 31 GAS isolates collected in a single community from children in 11 households with ⩾2 GAS-infected children. We aimed to determine whether transmission was occurring principally within households or across the community. The 31 isolates were represented by nine multilocus sequence types and isolates within each sequence type differed from one another by only 0–3 single nucleotide polymorphisms. There was evidence of extensive transmission both within households and across the community. Our findings suggest that strategies to reduce the burden of impetigo in this setting will need to extend beyond individual households, and incorporate multi-faceted, community-wide approaches.
Enclosure disputes have long attracted attention given their perceived political motivations, the importance of custom and customary practices in legitimising action and various forms of protest. Based on research undertaken at local and national record offices and the study of both written records and maps, this paper explores a series of disputes over common land in the wood-pasture countryside of Shropshire, placing them within the wider historiography concerning enclosure riots and popular protest. It complements the existing body of local and regional studies which have provided insight into the national historical context of the enclosure process. Historians need to examine economic and social developments at a local level to ascertain the causation of enclosure protest and the motivation of those involved. This evidence suggests that disputes arose between lords and tenants over the loss of customary rights and also neighbouring manorial lords as a result of ownership or boundary disputes.
This paper describes the system architecture of a newly constructed radio telescope – the Boolardy engineering test array, which is a prototype of the Australian square kilometre array pathfinder telescope. Phased array feed technology is used to form multiple simultaneous beams per antenna, providing astronomers with unprecedented survey speed. The test array described here is a six-antenna interferometer, fitted with prototype signal processing hardware capable of forming at least nine dual-polarisation beams simultaneously, allowing several square degrees to be imaged in a single pointed observation. The main purpose of the test array is to develop beamforming and wide-field calibration methods for use with the full telescope, but it will also be capable of limited early science demonstrations.
The apparatus for X-ray diffraction imaging (XRDI) of 450-mm wafers, is now placed at the ANKA synchrotron radiation source in Karlsruhe, is described in the context of the drive to inspect wafers for plastic deformation or mechanical damage. It is shown that full wafer maps at high resolution can be expected to take a few hours to record. However, we show from experiments on 200-, 300-, and 450-mm wafers that a perimeter-scan on a 450-mm wafer, to pick up edge damage and edge-originated slip sources, can be achieved in just over 10 min. Experiments at the Diamond Light Source, on wafers still in their cassettes, suggest that clean-room conditions may not be necessary for such characterization. We conclude that scaling up of the 300-mm format Jordan Valley tools, together with the existing facility at ANKA, provides satisfactory capability for future XRDI analysis of 450-mm wafers.
The nucleation of dislocations at indents in silicon following rapid thermal annealing (RTA) has been examined by X-ray diffraction imaging (topography). For indentation loads below 200 mN, no slip bands were generated from the indent sites following RTA at 1000 °C under spike conditions. Upon plateau annealing at 1000 °C, slip dislocations were propagated from some indents but not all. Slip was also observed from edge defects not associated with indentation. For 500-mN indentation load, large scale dislocation sources were generated from the indent sites propagating on two of the four {111} slip planes. These dislocations multiplied into macroscopic-scale slip bands. A significant change in morphology was observed in the 60° dislocation segments after the screw segment reached the rear surface of the wafer. Dislocations changed line direction and in some cases appeared to leave the Peierls trough during glide.