Coexistence of antiferrodistortive and ferroelectric distortions at the PbTiO3_3 (001) surface

The c(2$\times$2) reconstruction of (001) PbTiO$_3$ surfaces is studied by means of first principles calculations for paraelectric (non-polar) and ferroelectric ([001] polarized) films. Analysis of the atomic displacements in the near-surface region shows how the surface modifies the antiferrodistortive (AFD) instability and its interaction with ferroelectric (FE) distortions. The effect of the surface is found to be termination dependent. The AFD instability is suppressed at the TiO$_2$ termination while it is strongly enhanced, relative to the bulk, at the PbO termination resulting in a c(2x2) surface reconstruction which is in excellent agreement with experiments. We find that, in contrast to bulk PbTiO$_3$, in-plane ferroelectricity at the PbO termination does not suppress the AFD instability. The AFD and the in-plane FE distortions are instead concurrently enhanced at the PbO termination. This leads to a novel surface phase with coexisting FE and AFD distortions which is not found in PbTiO$_3$ bulk

Short-term changes in soil pore size distribution : Impact of land use

Changes in land use affect the pore size distribution (PSD) of the soil, and hence important soil functions such as gas exchange, water availability and plant growth. The objective of this study was to investigate potentially damaging and restorative soil management practices on soil pore structure. We quantified the rate of change in PSD six years after changes in land use taking advantage of the Highfield land-use change experiment at Rothamsted Research. This experiment includes short-term soil degradation and restoration scenarios established simultaneously within long-term contrasting treatments that had reached steady-state equilibrium. The land-use change scenarios comprised conversion to grassland of previously arable or bare fallow soil, and conversion of grassland to arable and bare fallow soils. In the laboratory, we exposed intact soil cores (100 cm3) to matric potentials ranging from −10 hPa to -1.5 MPa. Based on equivalent soil mass, the plant available water capacity decreased after conversion from grassland, whereas no change was observed after conversion to grassland. Structural void ratio decreased after termination of grassland and introduction of grassland in bare fallow soil, while no change was seen when changing arable to grassland. Consequently, it was faster to degrade than to restore a complex soil structure. The study illustrates that introducing grassland in degraded soil may result in short term increase in soil density

Soil degradation and recovery – changes in organic matter fractions and structural stability

The combination of concurrent soil degradation and restoration scenarios in a long-term experiment with contrasting treatments under steady-state conditions, similar soil texture and climate make the Highfield land-use change experiment at Rothamsted Research unique. We used soil from this experiment to quantify rates of change in organic matter (OM) fractions and soil structural stability (SSS) six years after the management changed. Soil degradation included the conversion of grassland to arable and bare fallow management, while soil restoration comprised introduction of grassland in arable and bare fallow soil. Soils were tested for clay dispersibility measured on two macro-aggregate sizes (DispClay 1-2 mm and DispClay 8-16 mm) and clay-SOM disintegration (DI, the ratio between clay particles retrieved without and with SOM removal). The SSS tests were related to soil organic carbon (SOC), permanganate oxidizable C (POXC) and hot water-extractable C (HWC). The decrease in SOC after termination of grassland was greater than the increase in SOC when introducing grassland. In contrast, it was faster to restore degraded soil than to degrade grassland soil with respect to SSS at macro-aggregate scale. The effect of management changes was more pronounced for 8-16 mm than 1-2 mm aggregates indicating a larger sensitivity towards tillage-induced breakdown of binding agents in larger aggregates. At microscale, SSS depended on SOC content regardless of management. Soil management affected macroscale structural stability beyond what is revealed from measuring changes in OM fractions, underlining the need to include both bonding and binding mechanisms in the interpretation of changes in SSS induced by management

Direct evidence for ferroelectric polar distortion in ultrathin lead titanate perovskite films

X-ray photoelectron diffraction is used to directly probe the intra-cell polar atomic distortion and tetragonality associated with ferroelectricity in ultrathin epitaxial PbTiO3 films. Our measurements, combined with ab-initio calculations, unambiguously demonstrate non-centro-symmetry in films a few unit cells thick, imply that films as thin as 3 unit cells still preserve a ferroelectric polar distortion, and also show that there is no thick paraelectric dead layer at the surface

Converting loss-on-ignition to organic carbon content in arable topsoil: Pitfalls and proposed procedure

Assessments of changes in soil organic carbon (SOC) stocks depend heavily on reliable SOC concentration values as obtained by automated high-temperature C analysers. However, historical as well as current studies often rely on indirect SOC estimates such as loss-on-ignition (LOI). In this study, we revisit the conversion of LOI to SOC using soil from two long-term agricultural field experiments and one arable field differing in contents of SOC, clay and particles < 20 µm (Fines20). Clay-, silt- and sand-sized fractions were isolated from the arable soil. Samples were analysed for texture, LOI (500 oC for 4 h) and SOC by dry combustion. For a topsoil with 2 g C and 30 g clay 100 g-1 converting LOI to SOC by the conventional factor 0.58 overestimated the SOC stock by 45 Mg C ha-1. The error increased with increasing contents of clay and Fines20. Converting LOI to SOC by a regression model underestimated the SOC stock by 5 Mg C ha-1 at low clay and Fines20 contents and overestimated the SOC stock by 8 Mg C ha-1 at high contents. This was due to losses of structural water from clay minerals. The best model to convert LOI to SOC incorporated clay content. Evaluating this model against an independent data set gave a root mean square error and mean error of 0.295 and 0.125 g C 100 g-1, respectively. To avoid misleading accounts of SOC stocks in agricultural soils, we recommend re-analysis of archived soil samples for SOC using high-temperature dry combustion methods. Where archived samples are not available, accounting for clay content improves conversion of LOI to SOC considerably. The use of the conventional conversion factor 0.58 is antiquated and provides misleading estimates of SOC stocks

Soil organic matter widens the range of water contents for tillage

The effects of soil organic matter on the water contents for tillage were investigated by sampling soils with a uniform texture, but a range of soil organic carbon (SOC) from two long-term field experiments at Highfield in Rothamsted Research, UK and Askov Experimental Station, Denmark. The treatments studied in Highfield were Bare fallow (BF), Continuous arable rotation (A), Ley-arable (LA) and Grass (G); and in Askov: unfertilized (UNF), ½ mineral fertilizer (½ NPK), 1 mineral fertilizer (1NPK), and 1½ animal manure (1½AM). Minimally undisturbed soil cores (100 cm3) were sampled per plot in both locations from 6-10 cm depth to generate water retention data. Soil blocks were also sampled at 6-15 cm depth to determine basic soil properties and to measure soil aggregate strength parameters. The range of soil water contents appropriate for tillage were determined using the water retention and the consistency approaches. SOC content in Highfield was in the order:G>LA=A>BF, and in Askov: 1½ AM>1NPK=½NPK>UNF. Results showed that different long-term management of the silt loam Highfield soil, and fertilization of the sandy loam Askov soil affected the mechanical properties of the soils— for Highfield soil, aggregates from the G treatment were stronger in terms of rupture energy when wet (-100 hPa matric potential) than the BF treatment. As the soil dried (-300 and -1000 hPa matric potentials), soil aggregates from the G treatment were relatively weaker and more elastic than the BF soil. Our study showed, for both Highfield and Askov soils, a strong positive linear increase in the range of water contents for tillage with increasing contents of SOC. This suggests that management practices leading to increased SOC can improve soil workability by increasing the range of water contents for tillage. We recommended using the consistency approach over the water retention approach for determining the range of water contents for tillage because it seems to give realistic estimates of the water contents for tillage

Soil Water Retention: Uni-Modal Models of Pore-Size Distribution Neglect Impacts of Soil Management

Most models describing soil water retention imply a uni-modal pore-size distribution (PSD). The uni-modal model presented by van Genuchten (termed vanG) is widely used although double-exponential models (termed Dex) implying a bi-modal PSD may better reflect reality. We tested the ability of vanG and Dex models to represent water retention in sandy top- and subsoils with different texture, in soil with contrasting management (Highfield), and in soil exposed to different tillage (Flakkebjerg). Soils were subjected to matric potentials from –10 hPa to –1.5 MPa. For all soils, the bi-modal Dex model showed a better fit to water retention data than the uni-modal vanG model. Neither of the models worked well for highly sorted soils. The vanG model gave a poorer fit for topsoils than for subsoils because of a more pronounced bi-modality of the PSD in topsoils caused by larger soil organic carbon (SOC) content and tillage. For Highfield soils, the root mean squared error (RMSE) of the vanG fit increased from long-term bare fallow (low C content, intensive tillage) to permanent grass (high C content, no tillage) reflecting a more distinct bi-modality of the PSD for well-structured soils. We conclude that uni-modal models should be used with great caution when describing effects of texture and management on PSD and that bi-modal models may provide a better fit to PSD

Follow-up of patients with functional bowel symptoms treated with a low FODMAP diet

AIM: To investigate patient-reported outcomes from, and adherence to, a low FODMAP diet among patients suffering from irritable bowel syndrome and inflammatory bowel disease. METHODS: Consecutive patients with irritable bowel syndrome (IBS) or inflammatory bowel disease (IBD) and co-existing IBS fulfilling the ROME. criteria, who previously attended an outpatient clinic for low FODMAP diet (LFD) dietary management and assessment by a gastroenterologist, were invited to participate in a retrospective questionnaire analysis. The questionnaires were sent and returned by regular mail and gathered information on recall of dietary treatment, efficacy, symptoms, adherence, satisfaction, change in disease course and stool type, and quality of life. Before study enrolment all patients had to sign an informed written consent. RESULTS: One hundred and eighty patients were included, 131 (73%) IBS and 49 (27%) IBD patients. Median age was 43 years (range: 18-85) and 147 (82%) were females. Median follow-up time was 16 mo (range: 2-80). Eighty-six percent reported either partial (54%) or full (32%) efficacy with greatest improvement of bloating (82%) and abdominal pain (71%). The proportion of patients with full efficacy tended to be greater in the IBD group than in the IBS group (42% vs 29%, p = 0.08). There was a significant reduction in patients with a chronic continuous disease course in both the IBS group (25%, p < 0.001) and IBD group (23%, p = 0.002) along with a significant increase in patients with a mild indolent disease course of 37% (p < 0.001) and 23% (p = 0.002), respectively. The proportion of patients having normal stools increased with 41% in the IBS group (p < 0.001) and 66% in the IBD group (p < 0.001). One-third of patients adhered to the diet and high adherence was associated with longer duration of dietary course (p < 0.001). Satisfaction with dietary management was seen in 83 (70%) IBS patients and 24 (55%) IBD patients. Eighty-four percent of patients lived on a modified LFD, where some foods rich in FODMAPs were reintroduced, and 16% followed the LFD by the book without deviations. Wheat, dairy products, and onions were the foods most often not reintroduced by patients. CONCLUSION: These data suggest that a diet low in FODMAPs is an efficacious treatment solution in the management of functional bowel symptoms for IBS and IBD patients

Relating soil C and organic matter fractions to structural stability

Soil organic matter (SOM) is important for maintaining soil structural stability (SSS). The influence of soil organic carbon (SOC) and different organic matter components on various SSS measures were quantified. We used a silt loam soil with a wide range of SOC(0.0080-0.0427 kg kg-1 minerals) sampled in spring 2015 from the Highfield Ley-Arable Long-Term Experiment at Rothamsted Research. Four treatments were sampled: Bare fallow, continuous arable rotation, ley-arable rotation, and grass. Soils were tested for clay dispersibility (DispClay), clay-SOM disintegration (DI, the ratio between clay content without and with SOM removal) and dispersion of particles <20 μm. The SSS tests were related to SOC, permanganate oxidizable carbon (POXC), hot water-extractable carbon (HWC), mid-infrared photoacoustic spectroscopy (FTIR-PAS) and mineral fines/SOC ratio. SSS increased with increasing content of SOM components. The relationships between SOM components and SSS followed a broken-stickregression with a change point at ~0.0230 kg SOC kg-1 minerals (clay/SOC~10) coinciding with a change from the tilled treatments to the grass treatment. We found a greater influence of SOC, POXC and HWC on SSS at contents below the change point than above. A stronger linear relation between POXC and DispClay compared to SOC and HWC suggests that POXC was a better predictor of the variation in DispClay. POXC and HWC were less related to DI than SOC. The grass treatment had a very stable structure, shown in all SSS tests, probably due to the absence of tillage and large annual inputs of stabilizing agents. This suggests that a change in management from arable rotation to permanent grass is an effective tool for improving SSS