When are total concentrations not total? Factors affecting geochemical analytical techniques for measuring element concentrations in soil

Inductively coupled plasma (ICP) following aqua regia digestion and X-ray fluorescence (XRF) are both geochemical techniques used to determine ‘total’ concentrations of elements in soil. The aim of this study is to compare these techniques, identify elements for which inconsistencies occur and investigate why they arise. A study area (∼14,000 km2) with a variety of total concentration controls and a large geochemical dataset (n = 7950) was selected. Principal component analysis determined underlying variance in a dataset composed of both geogenic and anthropogenic elements. Where inconsistencies between the techniques were identified, further numerical and spatial analysis was completed. The techniques are more consistent for elements of geogenic sources and lead, whereas other elements of anthropogenic sources show less consistency within rural samples. XRF is affected by sample matrix, while the form of element affects ICP concentrations. Depending on their use in environmental studies, different outcomes would be expected from the techniques employed, suggesting the choice of analytical technique for geochemical analyses may be more critical than realised.

The taphonomy of Last Glacial–Interglacial Transition (LGIT) distal volcanic ash in small Scottish lakes

An extensive micro-tephrostratigraphic survey of three small lakes in the Scottish Inner Hebrides was conducted encompassing the Last Glacial–Interglacial Transition (LGIT). The lakes are highly contrasting in terms of lake area to catchment ratio, the presence or absence of stream inlets draining the catchment, and in the complexity of the catchment drainage network. A suite of distal Icelandic volcanic ashes was consistently detected in all three lakes, with three, namely Penifiler Tephra, Vedde Ash and Ashik Tephra, being common to all the lakes. These ashes were chosen to examine the taphonomic intercomparability of ash location and concentration among the lakes. Findings reveal that the part played by catchment inlets in determining ash concentration and within-basin location applies to microtephra layers as much as it does in studies of macrotephra layer thickness. The position of ash concentration maxima is also shown to vary significantly for different LGIT periods and may be a consequence of lake-level changes, especially during the early Holocene. High-resolution stratigraphic analysis through the Vedde Ash visible macrotephra at Loch Ashik reveals a high degree of complexity in taphonomic behaviour between the different geochemical components, with possible implications for the correct interpretation of the isochron position. The detection of multiple intact ash isochrons and the taphonomic processes responsible for their deposition should prove useful in future tephrostratigraphic surveys, as well as having applications within other palaeolimnological disciplines.

Use of maternity surveys in improving the care experience – a review of the evidence

The use of surveys and direct feedback from women as a measurement of their maternity experience is seen as a means of stimulating quality improvement. Underpinning the overall rationale behind national maternity surveys is the acknowledgement that there is a need to document women's views of maternity services to inform policymakers with a view to enhancing the delivery of quality care to women. The evidence suggests that using maternity surveys to improve maternity care experience is central to UK health policy. It is also evident that qualitative input from women has the power to highlight mismatches of experience between women and professionals. Trusts are required to look to the future and invest in qualitative methodologies, which elicit rich and detailed information on women's experiences. The aim of this literature review is to critically analyse the use of maternity surveys and their validity in improving the care experienced by users of maternity services.

Tephra from andesitic Shiveluch volcano, Kamchatka, NW Pacific: chronology of explosive eruptions and geochemical fingerprinting of volcanic glass

The ~16-ka-long record of explosive eruptions from Shiveluch volcano (Kamchatka, NW Pacific) is refined using geochemical fingerprinting of tephra and radiocarbon ages. Volcanic glass from 77 prominent Holocene tephras and four Late Glacial tephra packages was analyzed by electron microprobe. Eruption ages were estimated using 113 radiocarbon dates for proximal tephra sequence. These radiocarbon dates were combined with 76 dates for regional Kamchatka marker tephra layers into a single Bayesian framework taking into account the stratigraphic ordering within and between the sites. As a result, we report ~1,700 high-quality glass analyses from Late Glacial–Holocene Shiveluch eruptions of known ages. These define the magmatic evolution of the volcano and provide a reference for correlations with distal fall deposits. Shiveluch tephras represent two major types of magmas, which have been feeding the volcano during the Late Glacial–Holocene time: Baidarny basaltic andesites and Young Shiveluch andesites. Baidarny tephras erupted mostly during the Late Glacial time (~16–12.8 ka BP) but persisted into the Holocene as subordinate admixture to the prevailing Young Shiveluch andesitic tephras (~12.7 ka BP–present). Baidarny basaltic andesite tephras have trachyandesite and trachydacite (SiO₂ < 71.5 wt%) glasses. The Young Shiveluch andesite tephras have rhyolitic glasses (SiO₂ > 71.5 wt%). Strongly calc-alkaline medium-K characteristics of Shiveluch volcanic glasses along with moderate Cl, CaO and low P₂O₅ contents permit reliable discrimination of Shiveluch tephras from the majority of other large Holocene tephras of Kamchatka. The Young Shiveluch glasses exhibit wave-like variations in SiO₂ contents through time that may reflect alternating periods of high and low frequency/volume of magma supply to deep magma reservoirs beneath the volcano. The compositional variability of Shiveluch glass allows geochemical fingerprinting of individual Shiveluch tephra layers which along with age estimates facilitates their use as a dating tool in paleovolcanological, paleoseismological, paleoenvironmental and archeological studies. Electronic tables accompanying this work offer a tool for statistical correlation of unknown tephras with proximal Shiveluch units taking into account sectors of actual tephra dispersal, eruption size and expected age. Several examples illustrate the effectiveness of the new database. The data are used to assign a few previously enigmatic wide-spread tephras to particular Shiveluch eruptions. Our finding of Shiveluch tephras in sediment cores in the Bering Sea at a distance of ~600 km from the source permits re-assessment of the maximum dispersal distances for Shiveluch tephras and provides links between terrestrial and marine paleoenvironmental records.

The inclusion of open-ended questions on quantitative surveys of children: Dealing with unanticipated responses relating to child abuse and neglect

Web surveys have been shown to be a viable, and relatively inexpensive, method of data collection with children. For this reason, the Kids’ Life and Times (KLT) was developed as an annual online survey of 10 and 11 year old children. Each year, approximately 4,000 children participate in the survey. Throughout the six years that KLT has been running, a range of questions has been asked that are both policy-relevant and important to the lives of children. Given the method employed by the survey, no extremely sensitive questions that might cause the children distress are included. The majority of questions on KLT are closed yielding quantitative data that are analysed statistically; however, one regular open-ended question is included at the end of KLT each year so that the children can suggest questions that they think should be asked on the survey the following year. While most of the responses are innocuous, each year a small minority of children suggest questions on child abuse and neglect. This paper reports the responses to this question and reflects on how researchers can, and should, deal with this issue from both a methodological and an ethical perspective.

Vaccination and All Cause Child Mortality 1985-2011: Global Evidence from the Demographic and Health Surveys

Based on models with calibrated parameters for infection, case fatality rates, and vaccine efficacy, basic childhood vaccinations have been estimated to be highly cost effective. We estimate the association of vaccination with mortality directly from survey data. Using 149 cross-sectional Demographic and Health Surveys, we determine the relationship between vaccination coverage and under five mortality at the survey cluster level. Our data include approximately one million children in 68,490 clusters in 62 countries. We consider the childhood measles, Bacille Calmette-Guérin (BCG), Diphtheria-Pertussis-Tetanus (DPT), Polio, and maternal tetanus vaccinations. Using modified Poisson regression to estimate the relative risk of child mortality in each cluster, we also adjust for selection bias caused by the vaccination status of dead children not being reported. Childhood vaccination, and in particular measles and tetanus vaccination, is associated with substantial reductions in childhood mortality. We estimate that children in clusters with complete vaccination coverage have relative risk of mortality 0.73 (95% Confidence Interval: 0.68, 0.77) that of children in a cluster with no vaccination. While widely used, basic vaccines still have coverage rates well below 100% in many countries, and our results emphasize the effectiveness of increasing their coverage rates in order to reduce child mortality.

The single component geochemical map: Fact or fiction?

Single component geochemical maps are the most basic representation of spatial elemental distributions and commonly used in environmental and exploration geochemistry. However, the compositional nature of geochemical data imposes several limitations on how the data should be presented. The problems relate to the constant sum problem (closure), and the inherently multivariate relative information conveyed by compositional data. Well known is, for instance, the tendency of all heavy metals to show lower values in soils with significant contributions of diluting elements (e.g., the quartz dilution effect); or the contrary effect, apparent enrichment in many elements due to removal of potassium during weathering. The validity of classical single component maps is thus investigated, and reasonable alternatives that honour the compositional character of geochemical concentrations are presented. The first recommended such method relies on knowledge-driven log-ratios, chosen to highlight certain geochemical relations or to filter known artefacts (e.g. dilution with SiO2 or volatiles). This is similar to the classical normalisation approach to a single element. The second approach uses the (so called) log-contrasts, that employ suitable statistical methods (such as classification techniques, regression analysis, principal component analysis, clustering of variables, etc.) to extract potentially interesting geochemical summaries. The caution from this work is that if a compositional approach is not used, it becomes difficult to guarantee that any identified pattern, trend or anomaly is not an artefact of the constant sum constraint. In summary the authors recommend a chain of enquiry that involves searching for the appropriate statistical method that can answer the required geological or geochemical question whilst maintaining the integrity of the compositional nature of the data. The required log-ratio transformations should be applied followed by the chosen statistical method. Interpreting the results may require a closer working relationship between statisticians, data analysts and geochemists.