The influence of different ions in the formation of Al(OH)3 polymorphs has been studied experimentally by promoting stoichiometric reactions between the aluminum salts (AlCl3, Al(NO3)3, Al2(SO4)3) and bases (NaOH, KOH, NH4OH). In all cases the polymorphs obtained were a mixture of gibbsite, bayerite and nordstrandite or pseudoboehmite with the exception of the reaction between KOH, or NH4OH and Al2(SO4)3 which produced amorphous gels. Ageing of these gels at ambient temperature and pressure for 180 days or at 60°C for 20 days resulted in crystalline structure. Specifically, pseudoboehmite was crystallized from the reaction between Al2(SO4)3 and NH4OH. Significantly, of all ions present in solution in the present experiment, only the sulphate ones were observed to have a marked influence in the precipitation of Al oxyhydroxides.

Kainite, KMg(SO4)Cl⋅2.75H2O, is one of the most common hydrated sulfate minerals, and it plays an important role as a source of potassium. However, its properties and structure have, to date, been insufficiently studied. In our present work, kainite was investigated using multiple techniques, including single-crystal and powder X-ray diffraction, thermogravimetry, differential scanning calorimetry (DSC), and infrared spectroscopy (IR). The mineral is monoclinic, C2/m, a = 19.6742(2), b = 16.18240(10), c = 9.49140(10) Å, β = 94.8840(10)°, V = 3010.86(5) Å3 and Z = 16. The structure was refined to R1 = 0.0230 for 3080 unique observed reflections with |Fo| ≥ 4σF. The complex hydrogen bonding system for kainite is described for the first time. The structure of kainite contains seven symmetrically independent sites occupied by water molecules, six of which are strongly bonded to Mg2+ cations while the seventh resides in the framework cavities. The acceptors of the hydrogen bonds are either chloride anions, neighbouring water molecules or oxygens atoms of sulfate groups. A bifurcated hydrogen bond was described for one of the water molecules. Based on the analysis of the crystal structure, we have confirmed and propose the correct formula for kainite as KMg(SO4)Cl⋅2.75H2O. The thermal studies of kainite in the temperature range of –150°C to +600°C indicate its stability to 190°C. The decomposition products are K2Mg2(SO4)3, KCl and K2SO4. The thermal expansion was calculated, which for kainite has a character typical for monoclinic crystals and similar to the compressibility tensor described earlier.

We report the crystal structures of eight new synthetic multinary Rb–Cu sulfates representing four new structure types: δ-Rb2Cu(SO4)2, γ-RbNaCu(SO4)2, γ-RbKCu(SO4)2, Rb2Cu2(SO4)3, Rb2Cu2(SO4)3(H2O), β-Rb2Cu(SO4)Cl2, β-Rb4Cu4O2(SO4)4⋅(Cu0.83Rb0.17Cl) and Rb2Cu5O(SO4)5. The determination of their crystal structures significantly expands the family of anhydrous copper sulfates. Some of the anhydrous rubidium copper sulfates obtained turned out to be isostructural to known compounds and minerals. Rb2Cu5O(SO4)5 is isostructural to cesiodymite, CsKCu5O(SO4)5 and cryptochalcite, K2Cu5O(SO4)5. Rb2Cu2(SO4)3 also shows an example of crystallisation in the already known structure type first observed for synthetic K2Cu2(SO4)3. ‘Hydrolangbeinite’, Rb2Cu2(SO4)3(H2O), was formed as a result of a minor hydration of the initial mixture of reagents.

The minerals and synthetic framework compounds of the A2Cu(SO4)2 series demonstrate a vivid example of morphotropism with the formation of structural types depending on the size of the cations residing in the cavities of the [Cu(SO4)2]2– open framework. To date, five types (α, β, γ, δ and ε) can be distinguished. We propose to call this series of compounds ‘saranchinaite-type’, as the stoichiometry A2Cu(SO4)2 was first encountered during the discovery and description of saranchinaite, Na2Cu(SO4)2.

The discovery of β-Rb2Cu(SO4)Cl2, a new monoclinic polymorph of chlorothionite, seems to be of particular interest considering the recently discovered interesting magnetic properties of synthetic K2Cu(SO4)X2 (X = Cl and Br) and Na2Cu(SO4)Cl2.

In these new structural architectures, a number of features have been revealed that were seldom observed previously. The first is the bidentate coordination of the sulfate tetrahedron via edge-sharing with the Cu2+-centred coordination polyhedron. Until recently, such coordination was known only for the chlorothionite structure. The second is formation of ‘high-coordinate’ CuO7 polyhedra. The structures of the new compounds suggest that such coordination is not in fact so uncommon, at least among anhydrous alkali copper sulfates. All of the described features clearly indicate the importance of further systematic studies of anhydrous copper-sulfate systems. Their exploration, particularly of the new copper-oxide substructures with new coordination environments, is highly likely to lead to new potentially interesting magnetic properties due to the unusual arrangements of magnetically active Cu2+ cations.

In addition to experimental details on the synthesis of rubidium analogues of anhydrous potassium and sodium sulfates, this work also provides an analysis and a brief review of the geochemistry of rubidium in volcanic environments.

Hydration processes of primary anhydrous minerals as well as dehydration of the hydrated phases are relevant not only for answering geochemical and petrological questions, but are also interesting in the context of the theory of the ‘Evolution of minerals’. Our study of the evolution of anhydrous exhalative sulfates in hydration and dehydration processes has demonstrated the complexity of the processes for a number of minerals from the active high-temperature fumaroles of Tolbachik volcano (chalcocyanite Cu(SO4), dolerophanite Cu2O(SO4), alumoklyuchevskite K3Cu3AlO2(SO4)4 and itelmenite Na2CuMg2(SO4)4). Hydration and dehydration experiments were carried out for all four minerals using powder X-ray diffraction. A typical structural characteristic of several anhydrous copper sulfate minerals of fumarolic origin is the presence of oxygen-centred OCu4 tetrahedra. These are absent in the structures of all known hydrated minerals or synthetic compounds of the class under consideration. Hydration of minerals initially containing O2– anions as part of oxocomplexes, proceeds with sequential formation of a large series of hydroxysalts. On the contrary, hydration of itelmenite with its relatively complex ‘initial’ structure, but without additional oxygen atoms that are strong Lewis bases, results in formation of simpler hydrates. The lower the temperature and the larger the excess of water, the stronger the tendency of the cations to adopt higher hydration numbers thus outcompeting the sulfate anions as ligands. Ultimately, the water molecules completely expel the bridging sulfate anions from the metal coordination sphere yielding relatively simple fully hydrated structures.

A new mineral glikinite, ideally Zn3O(SO4)2, was found in high-temperature exhalative mineral assemblages in the Arsenatnaya fumarole, Second scoria cone of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Glikinite is associated closely with langbeinite, lammerite-β, bradaczekite, euchlorine, anhydrite, chalcocyanite and tenorite. It is monoclinic, P21/m, a = 7.298(18), b = 6.588(11), c = 7.840(12) Å, β = 117.15(3)°, V = 335.4(11) Å3 and R1 = 0.046. The eight strongest lines of the powder X-ray diffraction pattern [d in Å (I) (hkl)] are: 6.969(56)(00$\bar{1}$), 3.942(52)(101), 3.483(100)(00$\bar{2}$), 3.294(49)(020), 2.936(43)(120), 2.534(63)(201), 2.501(63)(20$\bar{3}$) and 2.395(86)(02$\bar{2}$). The chemical composition determined by electron-microprobe analysis is (wt.%): ZnO 42.47, CuO 19.50, SO3 39.96, total 101.93. The empirical formula calculated on the basis of O = 9 apfu is Zn2.07Cu0.97S1.98O9 and the simplified formula is Zn3O(SO4)2. Glikinite is a Zn,Cu analogue of synthetic Zn3O(SO4)2. The crystal structure of glikinite is based on OZn4 tetrahedra sharing common corners, thus forming [Zn3O]4+ chains. Sulfate groups interconnect [Zn3O]4+ chains into a 3D framework.

Exhalative mineral assemblages from fumaroles of Tolbachik volcano are very rich in anhydrous sulfate minerals of alkali and transition metals. Koryakite, ideally NaKMg2Al2(SO4)6, was found in the Yadovitaya fumarole of the Second scoria cone of the North Breach of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Koryakite occurs as a product of fumarolic activity and closely associates with euchlorine and langbeinite. Koryakite is trigonal, R$\bar{3}$, a = 8.1124(11), c = 22.704(7) Å and V = 1294.0(5) Å3. The chemical composition determined by electron-microprobe analysis is (wt.%): Na2O 4.27, K2O 5.85, ZnO 0.31, СaO 0.31, CuO 0.76, MgO 10.15, Al2O3 11.47, Fe2O3 2.73, SO3 64.33 and SiO2 0.13, total 100.31. The empirical formula calculated on the basis of 24 O apfu is Na1.03K0.93(Mg1.89Cu0.07Ca0.04Zn0.03)Σ2.03(Al1.68Fe3+0.26)Σ1.94(S6.02Si0.02)Σ6.04O24. No natural or synthetic chemical analogues of koryakite are known to date. The topology of the [M2+2M3+2(SO4)6]2– heteropolyhedral framework in koryakite is very similar to the one in millosevichite, Al2(SO4)3 and mikasaite, Fe3+2(SO4)3. Replacement of part of the trivalent cations in the [M3+2(SO4)3]0 framework by divalent cations gives the framework a negative charge for koryakite and allows the incorporation of the alkali species in the channels. This structural mechanism is reminiscent of the concept of stuffed derivative structures. Koryakite is also structurally related to synthetic NaMgFe3+(SO4)3 and to the broader family of NASICON-related phases.

A new mineral majzlanite, ideally K2Na(ZnNa)Ca(SO4)4, was found in high-temperature exhalative mineral assemblages in the Yadovitaya fumarole, Second scoria cone of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Majzlanite is associated closely with langbeinite and K-bearing thénardite. Majzlanite is grey with a bluish tint, has a white streak and vitreous lustre. The mineral is soluble in warm water. Majzlanite is monoclinic, C2/c, a = 16.007(2), b = 9.5239(11), c = 9.1182(10) Å, β = 94.828(7)°, V = 1385.2(3) Å3 and Z = 16. The eight strongest lines of the X-ray powder diffraction pattern are [d, Å (I, %)(hkl)]: 3.3721(40)($\bar{3}$12), 3.1473(56)($\bar{4}$02), 3.1062(65)($\bar{2}$22), 2.9495(50)($\bar{1}$31), 2.8736(100)($\bar{1}$13), 2.8350(70)(421), 2.8031(45)(511) and 2.6162(41)($\bar{5}$12). The following structural formula was obtained: K2Na(Zn0.88Na0.60Cu0.36Mg0.16)(Ca0.76Na0.24)(S0.98Al0.015Si0.005O4)4. The chemical composition determined by electron-microprobe analysis is (wt.%): Na2O 9.73, K2O 15.27, ZnO 11.20, CaO 7.03, CuO 4.26, MgO 1.07, Al2O3 0.47, SO3 51.34, SiO2 0.12, total 100.49. The empirical formula calculated on the basis of 16 O apfu is K1.99Na1.93Zn0.84Ca0.77Cu0.33Mg0.16(S3.94Al0.06Si0.01)O16 and the simplified formula is K2Na(Zn,Na,Cu,Mg)Σ2(Ca,Na)(SO4)4. No natural or synthetic compounds directly chemically and/or structurally related to majzlanite are known to date. The topology of the heteropolyhedral framework in majzlanite is complex. An interesting feature of the structure of majzlanite is an edge-sharing of ZnO6 octahedra with SO4 tetrahedra.

The NASA 2020 Mars mission is a Curiosity-type rover whose objective is to improve the knowledge of the geological and climatic evolution of Mars and to collect rock samples for return to Earth. The new rover has a payload of seven instruments including the SuperCam instrument which consists of four tools including a Raman spectrometer. This Raman device will be non-destructive and will analyse the surface remotely in order to determine the mineralogy of rocks and, by extent, to detect and quantify major elements such as sulfur. Sulfur has been detected as sulfate (Ca,Mg,Fe-sulfates) in sedimentary rocks. This element is difficult to quantify using the laser ablation tool of the ChemCam instrument on-board the Curiosity rover.

We propose a Raman calibration to constrain the sulfur abundance in polymineralic mixtures. We acquired Raman signatures on binary and ternary mechanical mixtures containing Ca and Mg sulfates, mixed with natural silicate minerals supposed to be relevant to basaltic-sedimentary rocks at the surface of Mars: olivine, clinopyroxene, orthopyroxene and plagioclase. Using the Voigt function to process the Raman spectra from samples extracted from our mixtures allows us to calculate the initial proportions of our preparations of Ca and Mg sulfates. From these simulations, calibration equations have been provided allowing us to determine sulfate proportions (CaSO4 and MgSO4) in a mixture with basaltic minerals. With the presented calibration, S can be quantified at a lower limit of 0.7 wt.% in Martian soil.

Markhininite, ideally TlBi(SO4)2, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Markhininite occurs as white pseudohexagonal plates associated with shcherbinaite, pauflerite, bobjonesite, karpovite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Markhininite is triclinic, P, a = 7.378(3), b = 10.657(3), c = 10.657(3) Å , α = 61.31(3), β = 70.964(7), γ = 70.964(7)º, V = 680.2(4) Å3, Z = 4 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 68/4.264/111, 100/3.441/113, 35/3.350/222, 24/3.125/122, 23/3.054/202, 45/2.717/022, 20/2.217/331, 34/2.114/204. Chemical composition determined by electron microprobe analysis is (wt.%): Tl2O 35.41, Bi2O3 38.91, SO3 25.19, total 99.51. The empirical formula based on 8 O a.p.f.u. is Tl1.04Bi1.05S1.97O8. The simplified formula is TlBi(SO4)2, which requires Tl2O 35.08, Bi2O3 38.48, SO3 26.44, total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.055 on the basis of 1425 independent observed reflections. The structure contains four Tl+ and two Bi3+ sites in holodirected symmetrical coordination. BiO8 tetragonal antiprisms and SO4 tetrahedra in markhininite share common O atoms to produce [Bi(SO4)2]– layers of the yavapaiite type. The layers are parallel to (111) and linked together through interlayer Tl+ cations. The mineral is named in honour of Professor Yevgeniy Konstantinovich Markhinin (b. 1926), Institute of Volcanology, Russian Academy of Sciences, Kamchatka peninsula, Russia, in recognition of his contributions to volcanology. Markhininite is the first oxysalt compound that contains both Tl and Bi in an ordered crystal structure.

The stabilities of antierite, Cu3SO4(OH)4, and a synthetic compound whose stoichiometry is here established as Cu3SO4(OH)4.2H2O, have been determined at 5°C intervals between 10°C and 45°C using solution methods. The results of the experiments show that antlerite is stable with respect to the compound Cu3SO4(OH)4.2H2O only at temperatures above 30°C Below 30°C a change in the relative stabilities of these two basic copper(II) sulfates occurs, and the compound Cu3SO4(OH)4.2H2O, although unknown at present as a mineral, instead, is stable. Under these conditions, it does not react to give antlerite if kept in contact with water. Once isolated from its mother liquor, however, the dihydrate undergoes rapid dehydration to yield antlerite. Thermodynamic quantities for the two phases have been derived from equilibrium measurements. At 298.2K, values of AfG° for the compounds Cu3SO4(OH)4.2H2O(s ) and antlerite are −1919.6(14) and −1445.0(10) kJ mol−1, respectively. The results have been used to construct stability field diagrams for the system CuO—H2O–SO3 at 25°C and at 35°C These diagrams have been used to illustrate the chemical conditions under which the two compounds might be expected to form in the oxidised zones of cupriferous base metal orebodies.

Karpovite, ideally Tl2VO(SO4)2(H2O), was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Karpovite occurs as bundles of white, needle-like crystals associated with shcherbinaite, pauflerite, bobjonesite, markhininite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Karpovite is monoclinic, P21, a = 4.6524(4), b = 11.0757(9), c = 9.3876(7) Å , β = 98.353(2)º, V = 478.60(7) Å3, Z = 2 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 64/4.289/012, 81/4.253/110, 38/3.683/111, 47/3.557/022, 100/3.438/21, 52/2.982/013, 59/2.945/112, 54/2.354/132. The chemical composition determined by the electron microprobe analysis is (wt.%) Tl2O 61.43, VO2 11.53, SO3 23.55, H2O 2.61, total 99.12. The empirical formula (calculated on the basis of 10 O a.p.f.u.) is Tl2.00V0.96S2.03O9(H2O). The simplified formula of karpovite is Tl2VO(SO4)2(H2O), which requires Tl2O 61.93, VO2 12.09, SO3 23.34, H2O 2.62 total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.026 for 4196 independent observed reflections. The structure contains two symmetrically independent Tl+ sites, one V4+ site and two S6+ sites. VO5H2O octahedra and SO4 tetrahedra link together by sharing corners to form kröhnkite-type stripes parallel to the a axis with their planes oriented parallel to (021) and (02). Tl+ cations are located between the chains, linked into a three-dimensional structure. The new mineral is named in honour of Professor Gennadii Alexandrovich Karpov (b. 1938), volcanologist at the Institute of Volcanology, Russian Academy of Sciences, Petropavlovsk-Kamchatskii, Kamchatka Peninsula, Russia.

This study describes the occurrences of sulfate minerals in mines of the Czech part of the Upper Silesian Basin. This mineralization originates from the oxidation of Fe disulfides contained in the coal matrix and enclosing sediments. The oxidation occurs in the presence of formational brines and chemotrophic bacteria. The brines have a pH between 6.3 and 8.5 and total solute content of up to 300 g/l. They are rich in Na, Ca, K, Mg, Ba and Sr and Cl– is the major anion. The minerals of the pickeringite–halotrichite series with coexisting magnesiocopiapite are formed primarily in drier places and areas where the water is only slightly mineralized. In more humid places where the brines are more concentrated, a diverse assemblage of up to 20 different sulfates are found (e.g. natrojarosite, sideronatrite, metasideronatrite, tamarugite, magnesiocopiapite, bílinite, starkeyite, blödite, rozenite and siderotil). These sulfates are accompanied by halite, sulfur, goethite and a number of phases of uncertain identity, such as sulfates containing Sr and REE. This is an example of mineral paragenesis formed by weathering in a saline evaporite environment, which is extremely rare in Europe but is found in arid regions elsewhere (e.g. in the Atacama Desert in Chile).

The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerization of coordination polyhedra of higher bond valence. A mathematical hierarchy is an ordered set of elements where the ordering reflects a natural hierarchical relation between (or arrangement of) the elements. Here, I review the structure hierarchies for the borate, uranyl oxide, phosphate, sulfate, beryllate and oxide-centred Cu, Pb and Hg minerals (plus synthetics where appropriate). Structure hierarchies have two functions: (1) they serve to organize our knowledge of minerals (crystal structures) in a coherent manner; (2) if the basis of the classification involves factors that are related to the mechanistic details of the stability and behaviour of minerals, then the physical, chemical and paragenetic characteristics of minerals should arise as natural consequences of their crystal structures and the interaction of those structures with the environment in which they occur. We may justify the structure hierarchy hypothesis by considering a hypothetical structure-building process whereby higher bond-valence polyhedra polymerize to form the structural unit. The clusters constituting the FBBs (fundamental building blocks) may polymerize to form the following types of structural unit: (1) isolated polyhedra; (2) clusters; (3) chains and ribbons; (4) sheets; and (5) frameworks. The major advantage of this approach to structure hierarchy is the fact that the hypothetical structure-building process outlined above resembles (our ideas of) crystallization from an aqueous solution, whereby complexes in aqueous and hydrothermal solutions condense to form crystal structures, or fragments of linked polyhedra in a magma condense to form a crystal. Although our knowledge of these processes is rather vague from a mechanistic perspective, the foundations of the structure hypothesis give us a framework within which to think about the processes of crystallization and dissolution.

Itelmenite, ideally Na2CuMg2(SO4)4, was found in a fumarole of the Naboko scoria cone of the Tolbachik volcano Fissure Eruption (2012–2013), Kamchatka Peninsula, Russia. Itelmenite occurs as irregularly shaped grains as well as microcrystalline masses associated with anhydrite, saranchinaite, hermannjahnite, euchlorine, thénardite, aphthitalite and hematite. Itelmenite is orthorhombic, Pbca, a = 9.568(2) Å, b = 8.790(2) Å, c = 28.715(8) Å, V = 2415.0(11) Å3 and Z = 4 (from single-crystal diffraction data). The nine strongest lines of the powder X-ray diffraction pattern are [d(I)(hkl)]: 7.9614(41)(102), 7.1803(32)(004), 5.9122(64)(112), 3.8455(87)(122), 3.6292(52)(214), 3.3931(62)(215), 3.0003(44)(027), 2.9388(100)(312) and 2.4975(56)(230). The chemical composition determined by the electron-microprobe analysis is (wt.%): Na2O 10.77, K2O 0.20, MgO 11.10, CuO 15.38, ZnO 5.61, SO3 56.42, total 99.48. The empirical formula based on O = 32 apfu is (Na3.93K0.05)Σ3.98Mg3.12(Cu2.19Zn0.78)Σ2.97S7.97O32. The simplified formula is Na2CuMg2(SO4)4 taking into account structural data. The crystal structure was solved by direct methods and refined to an agreement index R1 = 0.034 on the basis of 1855 independent observed reflections. The structure of itelmenite is based on a unique type of [A2+3(SO4)4]2– (A = Mg, Cu and Zn) heteropolyhedral framework with voids filled by Na+ cations.

The new mineral saranchinaite, ideally Na2Cu(SO4)2, was found in sublimates of the Saranchinaitovaya fumarole, Naboko Scoria Cone, Tolbachik volcano, Kamchatka, Russia. Its discovery and study has enabled the characterization of the thermal decomposition of kröhnkite and provided an insight into the high-temperature behaviour of other kröhnkite-type materials. Saranchinaite is monoclinic, P21, a = 9.0109(5), b = 15.6355(8), c = 10.1507(5) Å, β = 107.079(2)°, V = 1367.06(12) Å3, Z = 8 and R1 = 0.03. Saranchinaite is a unique mineral in that two of its four independent Cu sites display a very unusual Cu2+ coordination environment with two weak Cu–O bonds of ~2.9–3.0 Å, resulting in [4+1+2] CuO7 polyhedra. Each of the Cu-centred polyhedra shares common corners with SO4 tetrahedra resulting in a [Cu4(SO4)8]8– framework with a complex channel system occupied by Na atoms. Saranchinaite is sensitive to moisture and transforms into kröhnkite within one week when exposed to open air at 87% relative humidity and 25°C. High-temperature X-ray diffraction studies were performed for both kröhnkite (from La Vendida mine, Antofagasta Region, Chile) and saranchinaite. During thermal expansion kröhnkite retains its strongly anisotropic character up to its full dehydration and the formation of saranchinaite at ~200°C, which then transforms back into kröhnkite after exposure to open air. The thermal expansion of saranchinaite is more complex than that of kröhnkite. Saranchinaite is stable up to 475°C with subsequent decomposition into tenorite CuO, thénardite Na2SO4 and unidentified phases.

Bioavailability studies are vital to assess the potential impact of bioactive compounds on human health. Although conjugated phenolic metabolites derived from colonic metabolism have been identified in the urine, the quantification and appearance of these compounds in plasma is less well studied. In this regard, it is important to further assess their potential biological activity in vivo. To address this gap, a cross-over intervention study with a mixed fruit purée (blueberry, blackberry, raspberry, strawberry tree fruit and Portuguese crowberry) and a standard polyphenol-free meal was conducted in thirteen volunteers (ten females and three males), who received each test meal once, and plasma metabolites were identified by HPLC–MS/MS. Sulfated compounds were chemically synthesised and used as standards to facilitate quantification. Gallic and caffeic acid conjugates were absorbed rapidly, reaching a maximum concentration between 1 and 2 h. The concentrations of sulfated metabolites resulting from the colonic degradation of more complex polyphenols increased in plasma from 4 h, and pyrogallol sulfate and catechol sulfate reached concentrations ranging from 5 to 20 μm at 6 h. In conclusion, phenolic sulfates reached high concentrations in plasma, as opposed to their undetected parent compounds. These compounds have potential use as biomarkers of polyphenol intake, and their biological activities need to be considered.

We interpret recent spectral data of Mars collected by the Mars Exploration Rovers to contain substantial evidence of sulfate minerals and aqueous processes. We present visible/near-infrared (VNIR), mid-IR and Mössbauer spectra of several iron sulfate minerals and two acid mine drainage (AMD) samples collected from the Iron Mountain site and compare these combined data with the recent spectra of Mars. We suggest that the sulfates on Mars are produced via aqueous oxidation of sulfides known to be present on Mars from Martian meteorites. The sulfate-rich rock outcrops observed in Meridiani Planum may have formed in an acidic environment similar to AMD environments on Earth. Because microorganisms are typically involved in the oxidation of sulfides to sulfates in terrestrial AMD sites, sulfate-rich rock outcrops on Mars may be a good location to search for evidence of life on that planet. Whether or not life evolved on Mars, following the trail of sulfate minerals is likely to lead to aqueous processes and chemical weathering. Our results imply that sulfate minerals formed in Martian soils via chemical weathering, perhaps over very long time periods, and that sulfate minerals precipitated following aqueous oxidation of sulfides to form the outcrop rocks at Meridiani Planum.

Phenolic tsetse attractants in host urine were shown to form gradually from proattractants identified as a mixture of glucuronates and sulphates. The breakdown of proattractants is predominantly due to microbial activity. Of the eight bacteria isolated from buffalo urine three have demonstrated varying ability to give rise to free phenols the formation of which was monitored by observing the build-up of 4-cresol by means of gas chromatography. These observations may provide a useful biotechnological model for controlled release of these semiochemicals in the field.