Penciclovir solubility in Eudragit films: a comparison of X-ray, thermal, microscopic and release rate techniques

The solubility of penciclovir (C10N5O3H17) in a novel film formulation designed for the treatment of cold sores was determined using X-ray, thermal, microscopic and release rate techniques. Solubilities of 0.15–0.23, 0.44, 0.53 and 0.42% (w/w) resulted for each procedure. Linear calibration lines were achieved for experimentally and theoretically determined differential scanning calorimetry (DSC) and X-ray powder diffractometry (XRPD) data. Intra- and inter-batch data precision values were determined; intra values were more precise. Microscopy was additionally useful for examining crystal shape, size distribution and homogeneity of drug distribution within the film. Whereas DSC also determined melting point, XRPD identified polymorphs and release data provided relevant kinetics.

Artisanal gold mining at the margins of mineral resource governance : a case from Tanzania

This article discusses the character of mineral resource governance at the margins of the state in Tanzania and the way artisanal gold miners are incorporated into mineral sector transformation. The landscape of mineral resource exploitation has changed dramatically over the past 20 years: processes of economic liberalisation have heralded massive foreign investment in large-scale gold mining, while also stimulating artisanal activities. Against this background, the article shows how artisanal gold miners are affected by contradictory processes: some have become integrated with state institutions and legal processes, while others, the large majority, are either further excluded or incorporated in ways that exacerbate insecurity and exploitation, underpinned by socio-economic inequalities. These processes are compounded by the actions of large-scale and medium-scale gold mining companies and by poor local governance. It is open to debate whether this will bring improved integration and welfare for artisanal mining communities or new forms of exclusion, although evidence suggests the latter.

How will organic carbon stocks in mineral soils evolve under future climate? Global projections using RothC for a range of climate change scenarios

We use a soil carbon (C) model (RothC), driven by a range of climate models for a range of climate scenarios to examine the impacts of future climate on global soil organic carbon (SOC) stocks. The results suggest an overall global increase in SOC stocks by 2100 under all scenarios, but with a different extent of increase among the climate model and emissions scenarios. The impacts of projected land use changes are also simulated, but have relatively minor impacts at the global scale. Whether soils gain or lose SOC depends upon the balance between C inputs and decomposition. Changes in net primary production (NPP) change C inputs to the soil, whilst decomposition usually increases under warmer temperatures, but can also be slowed by decreased soil moisture. Underlying the global trend of increasing SOC under future climate is a complex pattern of regional SOC change. SOC losses are projected to occur in northern latitudes where higher SOC decomposition rates due to higher temperatures are not balanced by increased NPP, whereas in tropical regions, NPP increases override losses due to higher SOC decomposition. The spatial heterogeneity in the response of SOC to changing climate shows how delicately balanced the competing gain and loss processes are, with subtle changes in temperature, moisture, soil type and land use, interacting to determine whether SOC increases or decreases in the future. Our results suggest that we should stop looking for a single answer regarding whether SOC stocks will increase or decrease under future climate, since there is no single answer. Instead, we should focus on improving our prediction of the factors that determine the size and direction of change, and the land management practices that can be implemented to protect and enhance SOC stocks.

Cyclodextrin-mediated enhancement of riboflavin solubility and corneal permeability

Cyclodextrins are water-soluble cyclic oligosaccharides consisting of six, seven, and eight α-(1,4)-linked glucopyranose subunits. This study reports the use of different cyclodextrins in eye drop formulations to improve the aqueous solubility and corneal permeability of riboflavin. Riboflavin is a poorly soluble drug with a solubility up to 0.08 mg mL–1 in deionized water. It is used as a drug topically administered to the eye to mediate UV-induced corneal cross-linking in the treatment of keratoconus. Aqueous solutions of β-cyclodextrin (10–30 mg mL–1) can enhance the solubility of riboflavin up to 0.12–0.19 mg mL–1, whereas the higher concentration of α-cyclodextrin (100 mg mL–1) achieved a lower level of enhancement of 0.11 mg mL–1. The other oligosaccharides were found to be inefficient for this purpose. In vitro diffusion experiments performed with fresh and cryopreserved bovine cornea have demonstrated that β-cyclodextrin enhances riboflavin permeability. The mechanism of this enhancement was examined through microscopic histological analysis of the cornea and is discussed in this paper.

Effects of acid sulphate on DOC release in mineral soils: the influence of SO42−retention and Al release

Dissolved organic carbon (DOC) in acid-sensitive upland waters is dominated by allochthonous inputs from organic-rich soils, yet inter-site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH-related retention of DOC in O horizon soils was influenced by acid-base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 μeq l−1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH-DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 μeq l−1), with the greatest decreases occurring in soils with very small % base saturation (BS, <3%) and/or large capacity for sulphate (SO42−) retention (up to 35% of added SO42−). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid-base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However,superimposed on this is the capacity of mineral soils to sorb DOC and SO42−, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO42−.

Effects of phytate and minerals on the bioavailability of oxalate from food

Phytate and mineral cations are both considered as important dietary factors for inhibiting the crystallisation of calcium oxalate kidney stones in susceptible individuals. In this paper, the phytate and mineral composition of whole bran cereals (wheat, barley and oat) and legumes were determined together with their soluble and insoluble oxalate concentrations in order to investigate the effects on oxalate solubility. The oat bran sample had the highest soluble oxalate concentration at 79 ± 1.3 mg/100 g, while total and soluble oxalate concentrations in the food samples studied range from 33 to 199 mg/100 g and 14 to 79 mg/100 g, respectively. The phytate concentration was in the range from 227 to 4393 mg/100 g and the concentrations of cations were in the range 54–70 mg/100 g for calcium, 75–398 mg/100 g for magnesium, 244–1529 mg/100 g for potassium and 4–11 mg/100 g for iron. Soluble oxalate concentration did not increase in proportion to total oxalate, and the phytate concentration in all foods was sufficient to contribute to an increase in soluble oxalate concentration by binding calcium.

Phylogenetic variation in the shoot mineral concentration of angiosperms

The calcium (Ca) concentration of plant shoot tissues varies systematically between angiosperm orders. The phylogenetic variation in the shoot concentration of other mineral nutrients has not yet been described at an ordinal level. The aims of this study were (1) to quantify the shoot mineral concentration of different angiosperm orders, (2) to partition the phylogenetic variation in shoot mineral concentration between and within orders, (3) to determine if the shoot concentration of different minerals are correlated across angiosperm species, and (4) to compare experimental data with published ecological survey data on 81 species sampled from their natural habitats. Species, selected pro rata from different angiosperm orders, were grown in a hydroponic system under a constant external nutrient regime. Shoots of 117 species were sampled during vegetative growth. Significant variation in shoot carbon (C), calcium (Ca), potassium (K), and magnesium (Mg) concentration occurred between angiosperm orders. There was no evidence for systematic differences in shoot phosphorus (P) or organic-nitrogen (N) concentration between orders. At a species level, there were strong positive correlations between shoot Ca and Mg concentration, between shoot P and organic-N concentration, and between shoot K concentration and shoot fresh weight:dry weight ratio. Shoot C and cation concentration correlated negatively at a species level. Species within the Poales and the Caryophyllales had distinct shoot mineralogies in both the designed experiment and in the ecological survey.

Relationships between yield and mineral concentrations in potato tubers

There is concern that modern cultivars and/or agronomic practices have resulted in reduced concentrations of mineral elements essential to human nutrition in edible crops. Increased yields are often associated with reduced concentrations of mineral elements in produce, and a number of recent studies have indicated that, when grown under identical conditions, the concentrations of several mineral elements are lower in genotypes yielding more grain or shoot biomass than in older, lower-yielding genotypes. Potato is a significant crop, grown worldwide, yet few studies have investigated whether increasing yields, through agronomy or breeding, affects the concentrations of mineral elements in tubers. This article examines the hypothesis that increasing yields, either by the application of mineral fertilizers and/or by growing higher-yielding varieties, leads to decreased concentrations of mineral elements in tubers. It reports that the application of fertilizers influences tuber elemental composition in a complex manner, presumably as a consequence of soil chemistry and interactions between mineral elements within the plant, that considerable variation exists between potato genotypes in the concentrations of mineral elements in their tubers, and that, like in other crops, higher-yielding genotypes occasionally have lower concentrations of some mineral elements in their edible tissues than lower-yielding genotypes.

Mg/Ca partitioning between aqueous solution and aragonite mineral: a molecular dynamics study

We have calculated the concentrations of Mg in the bulk and surfaces of aragonite CaCO3 in equilibrium with aqueous solution, based on molecular dynamics simulations and grand-canonical statistical mechanics. Mg is incorporated in the surfaces, in particular in the (001) terraces, rather than in the bulk of aragonite particles. However, the total Mg content in the bulk and surface of aragonite particles was found to be too small to account for the measured Mg/Ca ratios in corals. We therefore argue that most Mg in corals is either highly metastable in the aragonite lattice, or is located outside the aragonite phase of the coral skeleton, and we discuss the implications of this finding for Mg/Ca paleothermometry.

Vertical distribution and radiative effects of mineral dust and biomass burning aerosol over West Africa during DABEX

This paper presents measurements of the vertical distribution of aerosol extinction coefficient over West Africa during the Dust and Biomass-burning Aerosol Experiment (DABEX)/African Monsoon Multidisciplinary Analysis dry season Special Observing Period Zero (AMMA-SOP0). In situ aircraft measurements from the UK FAAM aircraft have been compared with two ground-based lidars (POLIS and ARM MPL) and an airborne lidar on an ultralight aircraft. In general, mineral dust was observed at low altitudes (up to 2 km), and a mixture of biomass burning aerosol and dust was observed at altitudes of 2–5 km. The study exposes difficulties associated with spatial and temporal variability when intercomparing aircraft and ground measurements. Averaging over many profiles provided a better means of assessing consistent errors and biases associated with in situ sampling instruments and retrievals of lidar ratios. Shortwave radiative transfer calculations and a 3-year simulation with the HadGEM2-A climate model show that the radiative effect of biomass burning aerosol was somewhat sensitive to the vertical distribution of aerosol. In particular, when the observed low-level dust layer was included in the model, the absorption of solar radiation by the biomass burning aerosols increased by 10%. We conclude that this absorption enhancement was caused by the dust reflecting solar radiation up into the biomass burning aerosol layer. This result illustrates that the radiative forcing of anthropogenic absorbing aerosol can be sensitive to the presence of natural aerosol species.

Sensitivity of direct radiative forcing by mineral dust to particle characteristics

Airborne dust affects the Earth's energy balance — an impact that is measured in terms of the implied change in net radiation (or radiative forcing, in W m-2) at the top of the atmosphere. There remains considerable uncertainty in the magnitude and sign of direct forcing by airborne dust under current climate. Much of this uncertainty stems from simplified assumptions about mineral dust-particle size, composition and shape, which are applied in remote sensing retrievals of dust characteristics and dust-cycle models. Improved estimates of direct radiative forcing by dust will require improved characterization of the spatial variability in particle characteristics to provide reliable information dust optical properties. This includes constraints on: (1) particle-size distribution, including discrimination of particle subpopulations and quantification of the amount of dust in the sub-10 µm to <0.1 µm mass fraction; (2) particle composition, specifically the abundance of iron oxides, and whether particles consist of single or multi-mineral grains; (3) particle shape, including degree of sphericity and surface roughness, as a function of size and mineralogy; and (4) the degree to which dust particles are aggregated together. The use of techniques that measure the size, composition and shape of individual particles will provide a better basis for optical modelling.

Bile salt composition is secondary to bile salt concentration in determining hydrocortisone and progesterone solubility in intestinal mimetic fluids.

Simulated intestinal fluids (SIFs) used to assay the solubility of orally administered drugs are typically based on a single bile salt; sodium taurocholate (STC). The aim of this study was to develop mimetic intestinal fluids with a closer similarity to physiological fluids than those reported to date by developing a mixed bile salt (MBS) system (STC, sodium glycodeoxycholate, sodium deoxycholate; 60:39:1) with different concentrations of lecithin, the preponderant intestinal phospholipid. Hydrocortisone and progesterone were used as model drugs to evaluate systematically the influence of SIF composition on solubility. Increasing total bile salt concentration from 0 to 30 mM increased hydrocortisone and progesterone solubility by 2- and ∼25-fold, respectively. Accordingly, higher solubilities were measured in the fed-state compared to the fasted-state SIFs. Progesterone showed the greatest increases in solubility in STC and MBS systems (2-7-fold) compared to hydrocortisone (no significant change; P>0.05) as lecithin concentration was increased. Overall, MBS systems gave similar solubility profiles to STC. In conclusion, the addenda of MBS and lecithin were found to be secondary to the influence of BS concentration. These data provide a foundation for the design of more bio-similar media for pivotal decision-guiding assays in drug development and quality control settings.

Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.