The Lower Pliocene lacustrine sediments of the Sakarya and Porsuk Formations in the Sivrihisar and Yunusemre-Biçer regions consist of claystone, argillaceous carbonate, carbonate, and evaporites. No detailed studies of paleoclimatic conditions have been performed previously. The present study aimed to determine the depositional environment and paleoclimatic conditions for the formation of these economically important sepiolite/palygorskite/carbonate/evaporite deposits based on detailed mineralogical, geochemical, and isotopic studies. Samples from various lacustrine sediments were examined using polarized-light microscopy, X-ray diffraction, scanning electron microscopy, and chemical and isotopic analysis methods. Dolomites are predominantly of micrite, which is partly recrystallized to dolomicrosparite/dolosparite close to desiccation fractures. The presence of ostracods and dacycladecean algae in the carbonates reflects a restricted depositional environment. The formation of sepiolite and palygorskite fibers, either as cement between/enclosing dolomite and/or as calcite crystals, reflects occasional changes in physicochemical conditions provided by fluctuations in the lake-water level and influx of groundwater in relation to climatic changes during and after dolomite precipitation. The positive correlations of ΣREE with Al2O3, Nb, high-field-strength elements, and transition elements are due to alteration of feldspar and hornblende in the volcanic units. The high values of Ba and Sr relative to Cr, Co, Ni, and V also indicate that felsic rather than ophiolitic rocks were the parent material. The crossplot of whole-rock SiO2vs. Al2O3+K2O+Na2O and V/Cr ratio suggests deposition of carbonate-dolomitic sepiolite-sepiolitic dolomite under arid climate and oxic conditions, whereas the Ni/Co and V/(V+Ni) ratios of the sediments indicate deposition of organic-bearing sepiolite/palygorskite under anoxic-dysoxic conditions. An enrichment in δ13C and δ18O values of dolomite with respect to calcite is probably due to differences in mineral fractionations. The δ34S and δ18O values and 87Sr/86Sr isotope ratios for gypsum suggest an intensely evaporitic lacustrine environment fed by an older marine evaporitic source. The Si, Al, Mg, Ca, and enhanced TOT/C required for periodic precipitation of organic-rich brown sepiolite/palygorskite characterize deposition in a swampy environment, while dolomitic sepiolite and sepiolitic dolomite formed in ponds by partial drying of the main alkaline lake.

The scientific community and most mainstream agriculturalists typically design fertilizer recommendations to provide a ‘sufficient level of available nutrients’ to meet the annual N, P and K requirements of common field crops. Soil balancing is another approach to managing soil fertility that focuses on the levels of Ca, Mg and K to achieve a desired base cation saturation ratio (BCSR). Soil balancing is believed to be practiced frequently by organic and other alternative farmers but is viewed skeptically by conventional agricultural scientists due to a lack of support for the idea in the published scientific literature. This study represents a pioneering effort to collect systematic data on the extent of soil balancing, how it is practiced and the types of outcomes reported by organic farmers. Our survey of over 850 farmers who grow certified organic corn in Indiana, Michigan, Ohio and Pennsylvania found that over half report using a soil-balancing approach based on BCSR. Their practice of soil balancing frequently includes more than management of base cations, but also uses a wide range of soil amendment products (such as purchased organic NPK fertilizers, micronutrients, microbial stimulants and soil inoculants) other than those applied specifically for cation balance. Farms that rely on vegetable and dairy production for most of their income, and Amish farmers who rely on horses for fieldwork, were more likely to report using a soil-balancing program. Self-described soil balancers perceived positive agronomic outcomes from the use of a BCSR program, including improvements in soil physical and biological properties and improved crop health and quality. Although farmers in our study report extensive use and positive perceived outcomes from soil-balancing methods, the scientific research literature has been unable to reproduce evidence that manipulating soil base cation levels has any systematic effect on crop yield. Future research could consider the interacting effects of BCSR with other field management practices to more closely approximate the actual practices of farmers.

Portuguese gypsum deposits utilized by the cement industry were characterized mineralogically, chemically and technologically for possible application in dermocosmetics. The deposits studied (Loulé, Óbidos and Soure) correspond to small outcrops in diapiric anticline areas. In principle, they represent gypsites which are white, and generally of higher quality for traditional applications (e.g. white cement), or greyish, and generally not adequate for cements and mortars. The analytical methods used to characterize the materials were wet sieving and X-ray sedimentation, X-ray diffraction, X-ray fluorescence spectrometry and assessment of abrasiveness, plasticity, texturometrics (adhesivity and firmness), oil absorption and cooling rate. The Óbidos gypsum displayed greater mineralogical and chemical quality (almost pure calcium sulfate) and had a finer grain size (<63 μm), whereas Loulé and Soure gypsums contain mineralogical impurities (mainly quartz). The Óbidos gypsum shows good characteristics in general for application in dermocosmetics because of its absorption, plasticity, adhesivity, firmness and low abrasiveness.

Siliceous-sulphate rock coatings were observed at Zhenzhu Spring, an acid sulphate hot spring in the Tengchong volcanic field, China. These rock coatings are mainly formed of gypsum and amorphous silica. Some alum-(K), voltaite, α-quartz and muscovite were also found. Four different laminae are developed in the rock coatings: gypsum layer, tight siliceous layer, tabular siliceous layer and siliceous debris layer. The gypsum layer is located at the top of the rock coatings, while other siliceous layers appear below the gypsum layer. Geochemical modelling of the fluids was performed to identify the mechanisms responsible for the formation of gypsum and amorphous silica. The results indicated that the occurrence of gypsum is related to the acid-fog deposition and amorphous silica mainly originates from spring water. Fog deposition provided the rock coatings with abundant SO42− and Ca, and the subsequent complete evaporation of the condensed fluids produced gypsum. Seasonal climate change (especially variation in rainfall) determines the fluctuations of capillary action and dissolution. Rainfall events in the wet season led to periods of non-precipitating gypsum and promoted the capillary rise of the spring water. Slightly diluted capillary water (a small amount of rainwater) covered the rock coatings, formed a tight siliceous layer on the rock-coating surface and/or filled the pores among the gypsum crystals forming many tabular siliceous aggregates. Heavy rainfall (high dilution), however, resulted in non-precipitating amorphous silica and accelerated the gypsum dissolution, leaving tabular pores around tabular siliceous aggregates and forming a tabular siliceous layer.

The dehydration of pure and waste gypsums has been examined using in situ synchrotron angledispersive X-ray diffraction. Pure gypsum was studied under a number of defined environments; various industrial waste gypsums were also studied under a common standard environment. It is found that the dehydration of gypsum to anhydrite proceeds via the hemihydrate and γ-anhydrite phases and the interplay and behaviour of these phases has been determined by full structural ‘Rietveld’ refinement. In the study of the pure gypsum system, the hemihydrate structure is shown to be preserved as water is lost. A ‘zero-water hemihydrate’ is observed before refinement in the higher symmetry γ-anhydrite cell is possible. The waste gypsum materials studied showed significant differences in the temperatures at which key transformation events occurred; these observations raise implications concerning the re-use of by-product gypsum materials. Finally, high temperature data are re-examined in the search for a variation of the anhydrite structure.

Arsenic is a very common by-product of the processing of Cu, Au and polymetallic ores worldwide, where the ore is roasted (calcined) to remove volatile elements. In southwest England, a diverse range of As-mineral species occur as efflorescent secondary mineral growths on historic calciner buildings. Gypsum occurs as abundant dendritic growths comprising either interlocking blades or tabular crystals. Ca-arsenate minerals are locally very abundant as white colloform masses. Positively identified Ca arsenates include pharmacolite, weilite and haidingerite. Other secondary minerals include arsenolite, scorodite, bukovskyite and an As-bearing potassium alum, together with a wide variety of unidentified minerals, including an Al-As-S phase and As-rich F-bearing phases. Gypsum contains As concentrations up to ~7 wt.%. Efflorescent growth at sites exposed to the prevailing weather systems is less abundant than at sheltered sites. This is interpreted as being due to ‘pressure washing’ of exposed sites by driving rain. Successive concentric growths of gypsum and Ca arsenate on masonry are interpreted as being the result of seasonal crystallization.

Understanding both current and historicalmining and mineralprocessing methods is criticalin the evaluation of the potential impact on the modern environment. In particular, due to the abundance of As-bearing minerals in a wide range of ore types, many buildings worldwide are potentially significantly contaminated with As even though few are directly related to As production or handling. Characterizing the secondary As mineralspecies present at mine and mineralprocessing sites is critical in understanding the potentialheal th risk these sites might pose.

Gypsum evaporites are forming under desiccating conditions in relict cave passages in Mynydd Llangattwg, south Wales. Sulphur isotope compositions of these sulphates indicate that oxidation of diagenetic pyrite in the overlying Millstone Grit is the source of sulphate solutions, rather than dissolution of evaporitic sulphate in the limestones.

Gypsum crystals were grown at 25, 35, and 45 °C from solutions containing different ionic impurities (Mg2+, Na+, Cd2+). Curved gypsum crystals formed from the solutions enriched in magnesium or cadmium, whereas, in the presence of sodium, gypsum always grew undeformed. The mechanism of the curvature is described and an interpretation based on crystallographic considerations is given. Curvature is the result of impurity incorporation followed by crack formation and mechanical twinning which releases the internal stresses.

A new experimental determination of the stability relationships for the dehydration of gypsum to the hemihydrate mineral bassanite at elevated temperature and pressure is described. The experimental method used depends on the observation of very small changes in pressure on the onset of reaction due to the potential volume change in the reaction. The technique yields P-T data of very high precision for this dehydration reaction, and the method is likely to be of use for other reactions. The experimental P-T results have been compared with those calculated from existing thermodynamic data for this reaction.

The structure of the high-temperature form of CaSeO4, formed by dehydration of the gyspum-type structure dihydrate is presented. The material is equivalent to that described previously as a P212121 form, but is however, a monazite with unit cell a = 6.85661(16) Å, b = 7.04962(15) Å, c = 6.68817(15) Å and β = 104.2675(21)° in space group P121/n1. Also presented is evidence for two intermediate trigonal and pseudo-trigonal phases related to the structurally similar minerals rhabdophane, bassanite, and γ-CaSO4. This result permits closer comparisons between intermediate-temperature structures of the selenate with related sulphates, and orthophosphates with a view to extending structural stability via synthesis of solid-solutions.

Results are reported here of an investigation into the effects of three carboxylic acid additives (tartaric, maleic and citric acids) on the precipitation of calcium sulfate phases. Precipitation reactions were followed at pH 7 in the pure CaSO4 system and in experiments with 0–20 ppm carboxylic acids added using in situ UV-VIS spectrophotometry (turbidity). The solid products were characterized in terms of their mineralogical composition, using X-ray diffraction, during and at the end of each reaction, and in terms of their morphological features, by scanning electron microscopy. All additives increased the time needed for turbidity to develop (induction time, start of precipitation) and the comparison between additive and additive-free experiments showed that, at equivalent concentrations, citric acid performed far better than the other two carboxylic acids. In all cases bassanite precipitated first and with time it transformed to gypsum. The addition of citrate stabilized bassanite and changed the final gypsum habit from typical needle-like crystals in the pure CaSO4 system to plates in the citrate-additive experiments.

The dehydration of gypsum CaSO4.2H2O has been studied, at negligible water vapour pressure, by in situ infrared (IR) spectroscopy and by thermogravimetry to determine whether intermediate phases (CaSO4.nH2O) exist, other than the hemihydrate with n=0.5, and also to compare the mechanism of the dehydration process when measured by two techniques with very different correlation lengths. Thermogravimetry shows an apparently continuous water loss with an activation energy of 90.3 kJ.mol−1, with no changes in the activation energy as a function of the degree of dehydration. IR spectroscopy on the other hand, clearly shows the existence of three discrete phases, gypsum CaSO4.2H2O, hemihydrate CaSO4.0.5H2O and γ-CaSO4, with nucleation of each successive phase as dehydration proceeds. There is no evidence to suggest the presence of phases with any intermediate water content.

Gypsum (CaSO4·2H2O) and brushite (CaHPO4·2H2O) are minerals with similar structures, despite not being isostructural. They both belong to the monoclinic system, but crystallize in different space groups. It is known that, to some extent, phosphate and sulphate groups can substitute for each other within the structure of these minerals. In the present work, the dehydration behaviour of experimentally produced Ca(SO4,HPO4)·2H2O solid solutions is assessed from thermogravimetrical (TG and DTG) and differential scanning calorimetry (DSC) analyses. For the applied experimental conditions it was not possible to obtain homogenous precipitates with compositions within 0.27 < XBr < 0.53, where XBr is the brushite mole fraction. The results reveal that the dehydration behaviour of solid solutions with compositions within the 0 < XBr < 0.27 interval tend to approach the dehydration process of pure gypsum. On the other hand, solid solutions with compositions within 0.53 < XBr < 1 involve higher dehydration temperatures than the brushite end-member, in a two-step process.

There is increasing evidence that Mars may have once been a habitable environment. Gypsum is targeted in the search for Martian biosignatures because it can host extensive cryptoendolithic communities in extreme terrestrial environments and is widespread on Mars. In this study the viability of using different spectroscopy-based techniques to identify the presence of gypsum endolithic communities was investigated by analysing various cryptoendoliths collected from the Lake St. Martin impact crater (LSM), a Mars analogue site found in Manitoba, Canada. Concurrently, the cryptoendolithic microbial community structure present was also analysed to aid in assigning spectroscopic features to microbial community members. Two main morphologies of endolithic communities were collected from gypsum deposits at LSM: true cryptoendolithic communities and annular deposits on partially buried boulders and cobbles <1 cm below the soil surface. Endolithic communities were found to be visibly present only in gypsum with a high degree of translucency and could occur as deep as 3 cm below the exterior surface. The bacterial community was dominated by a phylum (Chloroflexi) that has not been previously observed in gypsum endoliths. The exterior surfaces of gypsum boulders and cobbles are devoid of spectroscopic features attributable to organic molecules and detectable by reflectance, Raman, or ultraviolet-induced fluorescence spectroscopies. However, exposed interior surfaces show unique endolithic signatures detectable by each spectroscopic technique. This indicates that cryptoendolithic communities can be detected via spectroscopy-based techniques, provided they are either partially or fully exposed and enough photon–target interactions occur to enable detection.

In this paper we present a high temperature heating device, working under defined environmental conditions, for a Siemens D500 Bragg–Brentano powder diffractometer. The powder sample is prepared in a flat mould on a metal block consisting either of copper or of platinum depending on the temperature range selected for investigations. Although the heating cell can be used separately under ambient conditions up to sample temperatures of 1000 °C, it is possible to work under defined environmental conditions in the temperature range between 20 and 200 °C and up to a water vapour pressure of 1000 mbar. For that purpose a special cover for the in situ control of temperature and water vapour pressure has been constructed. It is important to note that the three sample conditions (sample temperature, gas temperature, and gas humidity) can be adjusted separately by the user. Current studies have shown that the described X-ray heating device is a powerful tool to study dehydration reactions in the frame of fundamental research as well as to understand industrially relevant processes concerning dehydration reactions and their mechanisms.

During the ongoing excavations in the palace of the famous Qatna complex, the excavators noted patches of brown staining on the floor of a high status tomb. Chemical extraction revealed the presence of brominated derivatives of indigo and indirubin, and more detailed characterisation showed that it likely came from Hexaplex trunculus. In short, this was none other than the renowned Tyrian or Royal Purple mentioned by Pliny, which was to have such an influential career colouring the clothing of the powerful. Furthermore, it was associated in the tomb with ghosts of high quality textiles preserved in gypsum.

In previous work, a platform was developed for testing computer-vision algorithms for robotic planetary exploration. This platform consisted of a digital video camera connected to a wearable computer for real-time processing of images at geological and astrobiological field sites. The real-time processing included image segmentation and the generation of interest points based upon uncommonness in the segmentation maps. Also in previous work, this platform for testing computer-vision algorithms has been ported to a more ergonomic alternative platform, consisting of a phone camera connected via the Global System for Mobile Communications (GSM) network to a remote-server computer. The wearable-computer platform has been tested at geological and astrobiological field sites in Spain (Rivas Vaciamadrid and Riba de Santiuste), and the phone camera has been tested at a geological field site in Malta. In this work, we (i) apply a Hopfield neural-network algorithm for novelty detection based upon colour, (ii) integrate a field-capable digital microscope on the wearable computer platform, (iii) test this novelty detection with the digital microscope at Rivas Vaciamadrid, (iv) develop a Bluetooth communication mode for the phone-camera platform, in order to allow access to a mobile processing computer at the field sites, and (v) test the novelty detection on the Bluetooth-enabled phone camera connected to a netbook computer at the Mars Desert Research Station in Utah. This systems engineering and field testing have together allowed us to develop a real-time computer-vision system that is capable, for example, of identifying lichens as novel within a series of images acquired in semi-arid desert environments. We acquired sequences of images of geologic outcrops in Utah and Spain consisting of various rock types and colours to test this algorithm. The algorithm robustly recognized previously observed units by their colour, while requiring only a single image or a few images to learn colours as familiar, demonstrating its fast learning capability.