Mg/Ca ratios in freshwater microbial carbonates: Thermodynamic, kinetic and vital effects

The ratio of magnesium to calcium (Mg/Ca) in carbonate minerals in an abiotic setting is conventionally assumed to be predominantly controlled by (Mg/Ca)solution and a temperature dependant partition coefficient. This temperature dependence suggests that both marine (e.g. foraminiferal calcite and corals) and freshwater (e.g. speleothems and surface freshwater deposits, “tufas”) carbonate deposits may be important archives of palaeotemperature data. However, there is considerable uncertainty in all these settings. In surface freshwater deposits this uncertainty is focussed on the influence of microbial biofilms. Biogenic or “vital” effects may arise from microbial metabolic activity and/or the presence of extracellular polymeric substances (EPS). This study addresses this key question for the first time, via a series of unique through-flow microcosm and agitated flask experiments where freshwater calcite was precipitated under controlled conditions. These experiments reveal there is no strong relationship between (Mg/Ca)calcite and temperature, so the assumption of thermodynamic fractionation is not viable. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments (where the solution is only moderately supersaturated) is controlled by biofilm growth rate, but occurs even when light is excluded indicating that photosynthetic influences are not critical. Our results thus suggest the apparent kinetic fractionation arises from the electrochemical activity of EPS molecules, and are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal EPS) speleothems

Synthesis and antibacterial effects of cobalt–cellulose magnetic nanocomposites

© The Royal Society of Chemistry. Green synthesis is employed to prepare cobalt/cellulose nanocomposites with cubic (α-cobalt) cobalt as a main component with antibacterial and magnetic properties. An in situ reduction of aqueous solutions of cobalt ions on a model cellulose substrate surface using hydrogen gas affords spherical, cellulose-stabilised cobalt nanoclusters with magnetic properties and an average diameter of 7 nm that are distributed evenly over the surface of the cellulose fibres. These cobalt/cellulose nanocomposites exhibit good antibacterial action against opportunistic pathogens both Gram-positive (S. aureus) and Gram-negative (E. coli, A. baumannii and P. aeruginosa), with zones of inhibition up to 15 mm, thereby encouraging the deployment of these advanced materials for the treatment of wastewater or within medical dressings. This method of preparation is compared with the analogous in situ reduction of cobalt ions on a cellulose surface using sodium borohydride as reducing agent

Evaporative Mass Loss Measurement as a Quality Control Tool for Quality Assurance in the Manufacture of Inks Suitable for High Speed (≥60 m/min) Printing

In any manufacturing environment, it is always important to be able to embrace a culture of traceability of any non-conformed product. For the case of ink manufacture, operator confusion, leading to the mixing-up of solvents, or connecting the incorrect solvent drum to solvent lines, can lead to disastrous consequences that are not trivial for a quality control/quality assurance team to unravel. Accordingly, simple methods for assessing whether the correct solvents were added in the correct ratios to products empower this QA/QC requirement. In this paper, we examine the use of a trivial measurement of evaporative mass loss as a protocol for validating the conformance of manufactured ink to specification. Inspired by the transport-limit that occurs at ultramicroelectrodes in electrochemistry, we develop theory to analyse evaporation rate measurements, and illustrate how vaporisation at the liquid | gas interface is dominated by a diffusion anisotropy, owing to natural convection for organic solvents, manufactured resins and commercialised inks that have been used, inter alia, for the underground transport tickets in the cities of London and Paris. We further demonstrate that the use of incorrect solvents is readily seen through evaporation rate transients, thereby enabling this measurement for human factor mitigation during the ink manufacture process

Linking mineralisation process and sedimentary product in terrestrial carbonates using a solution thermodynamic approach

Determining the processes which generate terrestrial carbonate deposits (tufas, travertines and to a lesser extent associated chemical sediments such as calcretes and speleothems) is a long-standing problem. Precipitation of mineral products from solution reflects a complex combination of biological, equilibrium and kinetic processes, and the different morphologies of carbonate sediment produced by different processes have yet to be clearly demarked. Building on the groundbreaking work of previous authors, we propose that the underlying control on the processes leading to the deposition of these products can be most parsimoniously understood from the thermodynamic properties of their source solutions. Here, we report initial observations of the differences in product generated from spring and lake systems spanning a range of temperature–supersaturation space. We find that at high supersaturation, biological influences are masked by high rates of physico-chemical precipitation, and sedimentary products from these settings infrequently exhibit classic "biomediated" fabrics such as clotted micrite. Likewise, at high temperature (>40 °C) exclusion of vascular plants and complex/diverse biofilms can significantly inhibit the magnitude of biomediated precipitation, again impeding the likelihood of encountering the "bio-type" fabrics. <br></br> Conversely, despite the clear division in product between extensive tufa facies associations and less spatially extensive deposits such as oncoid beds, no clear division can be identified between these systems in temperature–supersaturation space. We reiterate the conclusion of previous authors, which demonstrate that this division cannot be made on the basis of physico-chemical characteristics of the solution alone. We further provide a new case study of this division from two adjacent systems in the UK, where tufa-like deposition continuous on a metre scale is happening at a site with lower supersaturation than other sites exhibiting only discontinuous (oncoidal) deposition. However, a strong microbiological division is demonstrated between these sites on the basis of suspended bacterial cell distribution, which reach a prominent maximum where tufa-like deposits are forming. <br></br> We conclude that at high supersaturation, the thermodynamic properties of solutions provide a highly satisfactory means of linking process and product, raising the opportunity of identifying water characteristics from sedimentological/petrological characteristics of ancient deposits. At low supersaturation, we recommend that future research focuses on geomicrobiological processes rather than the more traditional, inorganic solution chemistry approach dominant in the past

Electrochemical immunoassay for the detection of stress biomarkers

A rapid electrochemical immunoassay method was developed to detect and measure stress biomarkers (cortisol and cortisone) in two biological samples (Zebrafish whole-body and artificial saliva). This methodology utilizes an immunoassay approach taking advantage of the lock and key mechanism that is related to the antibody-antigen interaction depending on the reliable immobilization of the antibody labelled with ferrocene tags (Ab-Fc) on a modified tin-doped indium oxide (ITO) electrode using electrochemical instrumentation to build a POC platform. The limit of detection (LOD) obtained for this biosensor was 1.03 pg ml−1 for cortisol and 0.68 pg ml−1 for cortisone, respectively. The correlation coefficient was 0.9852 and 0.9841 for cortisol and cortisone, respectively with a linear concentration from (0-50 ng ml−1) which covers the standard levels of stress hormones in both selected biological samples. The incubation time was investigated and 30 min was found to be the optimum incubation time. This time would be acceptable for the POC system as total process time can be determined within 35 min

Interaction of temperature, salinity and extracellular polymeric substances controls trace element incorporation into tufa calcite

The influence of extracellular polymeric substances on carbonate mineral growth in natural settings remains one of the most poorly understood contributors to the growth of non-marine carbonate sediments. The influences of these materials are complicated by their association with living cells creating local microenvironments via metabolism and enzyme production, and by our uncertainty about the extracellular polymeric substances materials themselves. Different mixtures of extracellular polymeric substance molecules may behave in different ways, and differences in the local physical environment may alter how the mixtures influence mineral formation, and even result in different patterns of polymerization. Here, the influence of extracellular polymeric substances on calcite precipitation rate and Mg/Cacalcite in the absence of cells is investigated using extracts of extracellular polymeric substances from temperate fluvial tufa biofilm. The influence is complex, with the concentration of extracellular polymeric substances in solution altering deposition rate and trace element incorporation. Moreover, the results show interaction of the presence/absence of extracellular polymeric substances and both temperature and salinity. However, despite extracting extracellular polymeric substances from the same parent sample, a uniform influence was not found in these experiments, implying that the mixture is sufficiently variable within a sample for microenvironments within the biofilm to either promote or inhibit mineralization. As sedimentologists, we can no longer take the view that extracellular polymeric substances are a bystander material, or that they have a single set of coherent and predictable or intuitive influences. Rather, the emphasis must be on investigating the specific mixtures present in nature, and their complex and dynamic interaction with both mineral surfaces and hydrochemical conditions

Effects of O2, Ar, and H2 gases on the field-emission properties of single-walled and multiwalled carbon nanotubes

In this article, the authors compare the effects of O2, Ar, and H2 gases on the field-emission (FE) properties of single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs)

Synthesis and antimicrobial effects of highly dispersed, cellulose-stabilized silver/cellulose nanocomposites

Small, spherical silver nanoclusters were synthesised on the surface of paper as a model cellulosic fibre substrate by a standard chemical reduction method. The concentration of the silver nanoclusters on the substrate surface is roughly proportional to the initial silver salt concentration. However, there is a noticeable degree of nanocluster aggregation to larger agglomerates. The addition of small amounts of α-cellulose, carboxymethyl cellulose or aminocellulose during the synthesis of the silver/cellulose nanocomposites suppresses this aggregation and significantly increases the concentration of the silver nanoclusters on the surface of the fibres of cellulose. These small, surface-stabilised silver nanoclusters, with the desired size and morphology, deposited from aqueous solutions on the surface of cellulosic cotton fibres, show enhanced antibacterial activity against MRSA compared to that of the corresponding silver/cotton nanocomposites prepared in the absence of a cellulosic surface stabiliser