Magnetic properties of surface sediments as proxies of recent anthropogenic pollution in the Anllóns riverbed (NW Spain)

A study of surface sediments from the Anllóns riverbed (northwestern Spain) was conducted to assess the use of their magnetic properties as proxies of recent trace element contamination (i.e., As, Zn, Pb, Cr, Ni and Cu). Thermomagnetic curves, hysteresis parameters, specific magnetic susceptibility χ, frequency-dependent magnetic susceptibility κ _FD%, magnetic remanence and saturation isothermal remanent magnetization ratios (i.e., S and SIRM/χ) reveal the presence of mostly fine-grained magnetite and maghemite in these samples. The Tomlinson Pollution Load Index (PLI), as well as the magnetic parameters χ, κ _FD%, SIRM/χ and S-ratios, vary more or less in agreement to each other when they are sequentially arranged throughout a 30-km-long transect that goes from the town of Carballo to the river mouth in Ponteceso. From that profile, it is possible to identify an anomaly of χ that lies between two small peaks of the PLI and seems to define a contaminated area probably linked to a diffuse low-impact source of pollution. There is also a conspicuous peak of the PLI that is likely associated to a nearby gold mine. The variations of the κ _FD%’s along the transect are the ones that best reflect the changes in the PLI values, regardless of the level of contamination. This result suggests that adsorption is the main mechanism of trace elements removal by Fe oxides in these samples. Direct signal analyses, used to decompose the isothermal remanent magnetization curves, reveal the presence of four magnetic fractions, with varying relative concentrations all over the profile, namely single-domain magnetite, close to the superparamagnetic threshold (SD/SP) and/or maghemite (\(\log B_{1/2}\) ca 1.2), single-domain magnetite (\(\log B_{1/2}\) ca 2), hematite (\(\log B_{1/2}\) ca 2.5) and goethite (\(\log B_{1/2}\) ca 3.5). Integrating all the available information, it was sketched out a likely sequence of events that included magnetic minerals neoformation in parent soils, their subsequent chemical transformations and the contamination episodes that affected the region.     

Allochthonous versus autochthonous naturally occurring organic matter in the Anllóns river bed sediments (Spain)

Despite of the importance of the aquatic ecosystems as organic matter pools within the global carbon cycle, specific studies in river sediments are still insufficient. This study was carried out in an Atlantic basin where nine sites were selected in the lowest middle stretch of the River. The analyses include total organic carbon, C/N ratios, humus composition (humic, fulvic and humin), A2/A4 and A4/A6 ratios, biologically active organic matter (BAOM), water soluble organic matter (WSOC) and coloured water soluble organic carbon (CWSOC). The results suggested a predominance of allochthonous sources to the organic matter, highly influenced by the land uses together with the river hydrodynamics, namely urban and forest at sites 1, 2 and 9, and agricultural at sites 7 and 8. The 38% of the total organic matter was humic and fulvic acids. The biologically active organic matter, which may act as a proxy of microbial activity, showed a mean value of 0.9% of the total organic matter, showing the lowest values at sites with the highest organic matter total, soluble or coloured. This coloured organic matter represented an average of 3.60% of the total organic matter, and showed the highest visible light absorption at those sites more affected by human activities, close to centres of population (1, 2 and 9). This coloured fraction showed also a high degree of photostability. C/N ratios were less effective to discriminate between allochthonous or autochthonous sources, whereas A4/A6 ratios were effective to estimate variations of autochthonous sources, as it measures the variations of phytopigments of the river bed sediments.     

Analysis of the degree of contamination and evolution in the last 100 years of the composition of the bed sediments of the Anllóns Basin

In this study, five cores of the Anllóns River bed sediments were analyzed in order to evaluate the downcore and downstream variations in their chemical composition. The first step was the evaluation of the metal distribution in the bulk (<2 mm) and fine fractions (<63 μm). The analysis revealed that most of the metals followed the same trend in both fractions, although the fine fraction presented usually higher concentrations. However, the concentration of both fractions tended to equalize with increasing contamination. No general increase was observed in the metal concentrations toward the surface which could be attributed to recent anthropogenic contributions. Instead, the distributions were homogeneous or peaked at various depths downcore. The most important historical feature was observed at the mouth of the river, at 96-cm depth, corresponding to the end of the eighteenth century. Upcore increased metal concentrations in parallel with increased fine fraction occurred from this depth, which were attributed to a bridge construction and consequent changes in sediment dynamics. As the metal concentrations can be influenced by variations in texture or other sediment characteristics, the second step was to evaluate the efficiency of several normalized indexes in the assessment of the degree of contamination, by calculating the enrichment factor (EF), the geoaccumulation index (I _GEO) and the pollution load index (PLI). The EFs obtained were <10, thus revealing little anthropogenic inputs to the basin. The I _GEO produced higher values when compared with the EFs. Instead of absolute EF or I _GEO absolute values, the use of cumulative probability plots allowed identifying more accurately potential outliers indicating contamination. Only one population was identified for Zn and Pb, with a reduced number of outliers at the highest concentrations for Pb. As shown, a more complex plot with the outliers identified at C4 and C5. Finally, the PLI allowed determining the absence of a significant contamination in the bed sediments. The bioavailable and non-geogenic fractions contribute up to a 90% of the total concentrations in the case of As and Cu, and showed similar (dissimilar) profiles in comparison with total metals. Also, the quality guidelines were surpassed, so the high solubility of As, Zn, Pb and Ni in the sediments revealed the need to monitor the bed sediment quality of the Anllóns River.     

Distribution and Abundance of Arsenic in the Soils and Sediments of O‘ahu,Hawai‘i

Lack of high-spatial-resolution soil and sediment arsenic data for Hawai‘i has generated substantial disagreement between researchers and regulators regarding the magnitude of natural levels of arsenic in Hawai‘i and rendered difficult the defining of areas of anthropogenically elevated arsenic. Our earlier research into the occurrence of arsenic in terrestrial and marine environments revealed widely disparate concentrations of arsenic with no apparent spatial pattern. To better understand the distribution and abundance of arsenic in soils and sediments of O‘ahu, we collected an additional 64 samples at locations chosen to represent different environments with varying degrees of human impact. We found surface arsenic values that ranged from 0.28 to 740 ppm with a median concentration of 8.1 ppm, which is above the global median of 5 ppm and US soil median of 5.2 ppm. Higher concentrations of arsenic (up to 913 ppm) were encountered at depth in soil cores. The median arsenic in streambed sediments from one of our earlier studies of 6.1 ppm was comparable to the conterminous US median of 6.3 ppm; however, we encountered arsenic concentrations as high as 43.9 ppm (median = 8.60 ppm, n = 75) in marine sediments in recent work off the leeward coast of O‘ahu. Overall, arsenic in the soils and sediments of O‘ahu is elevated relative to world and national values, but there still is no readily discernible pattern in the distribution of arsenic to explain these elevated values.     

Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería,SE Spain)

In the old mining area of Rodalquilar, mine wastes, soil and sediments were characterized and the results revealed high concentration of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments. The contaminant of greatest environmental concern is As. The mean concentration in the tailings was 679.9, and 345 mg/kg in the sediments of Playazo creek. The groundwater samples from the alluvial aquifer showed high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb and Zn and very high concentration of chloride and sulfate, which were above the concentration defined in the European standards for drinking water. The presence of As in groundwater may be caused by the oxidation of arsenian pyrite, the possible As desorption from goethite and ferrihydrite and the jarosite dissolution. Groundwater concentrations of Cd, Fe, Mn, and possibly Cu, were associated with low values of Eh, indicating the possible dissolution of oxy-hydroxides of Fe and Mn. The mobility of metals in the column experiments show the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in significant concentrations but below the detected values in groundwater. However, As, Cd, Sb, Se Pb and Au, are generally mobilized in concentrations above the detected values in groundwater. The possible mass transfer processes that could explain the presence of the contaminants in the aquifer and the leachates was simulated with the PHREEQC numerical code and revealed the possible dissolution of the following mineral phases: jarosite, natrojarosite, arsenian pyrite, alunite, chlorite, kaolinite and calcite.     

A Study on the Dissolution Kinetics of Basalt—Water Interaction under Different pH Conditions I：Release of Elements and pH Neutralization Effect

Experimental research on the chemical weathering of alkaline-olivine basalt from Huangyi Mountain,Kuandain County,Liaoning.Province and olivine basalt from Dayangke,Mingxi County,Fujian Province has shown that the acidity of the solution tends to become neutral regardless of what the acidity of the starting solution would be during basalt0-water interaction.We call this phenome-non“pH neutralized Effect”.The dissolved species in the solution were determined and unreacted and reacted sample-surface chemical components involved or uninvolved in reaction were analyzed using X-ray photoelectron spectroscopy(XPS).The results revealed two different mechanisms of dissolution of basalt in acidic and basic solutions.     

Stratigraphy and ecostratigraphic distribution of foraminiferal morphogroups from the Upper Jurassic of the Makar’yev section (Unzha River,Volga River basin)

Investigation of the Upper Callovian to Lower Kimmeridgian microfossils from the Makar’yev reference section (Unzha River, East European Platform) has been carried out. The section is characterized by ammonite debris and abundant associations of benthic and planktic foraminifers. It is a perfect object for stratigraphic and paleoecological researches. The biostratigraphic distribution of foraminifers from the Makar’yev section allows one to identify standard foraminifera zones of the East European Platform, as well as to upgrade some of them. The analysis of vertical and lateral ammonites and foraminiferal distribution, completed with litho stratigraphy, has precised the stratigraphic volume and position of boundaries of several lithological units.An improved stratigraphic scheme for the Kostroma area of the Moscow Depression is proposed. Analysis of the composition, structure, and dynamic changes of the foraminiferal assemblages has been performed. The morphofunctional analysis of foraminiferal genera has for the first time identified how foraminiferal morphogroups differing in their life style and feeding strategy varied with short-term paleoenvironmental changes. These morphogroup changes allow establishing four ecostratigraphic levels. These paleoecological data have been calibrated along with geochemical factors. They have shown a crisis of foraminiferal association during the Late Oxfordian and Early Kimmeridgian. A similar crisis has also been discovered in the north of Siberia, which may be an argument for its global distribution. The analysis of the taxonomic composition and the density of foraminiferal associations, in parallel with the structure of the association, has revealed a succession of transgressive and regressive events during the Late Callovian-Early Kimmeridgian. It allows the typification of each assemblage in relation with each event and underlines the occurrence of second-order sea-level fluctuations (middle part of the Middle Oxfordian and the earliest Kimmeridgian).     

Impact of agricultural activity and geologic controls on groundwater quality of the alluvial aquifer of the Guadalquivir River (province of Jaén,Spain): a case study

The alluvial aquifer of the Alto Guadalquivir River is one of the most important shallow aquifers in Jaén, Spain. It is located in the central-eastern part of the province, and its groundwater resources are used mainly for crop irrigation in an agriculture-dominated area. Hydrochemical and water-quality data obtained through a 2-year sampling (2004–2006) and analysis program indicate that nitrate pollution is a serious problem affecting groundwater due to the use of nitrogen (N)-fertilizers in agriculture. During the study, 231 water samples were collected from wells and springs to determine water chemistry and the extent of nitrate pollution. The concentration of nitrate in groundwater ranged from 1.25 to 320.88 mg/l. Considerable seasonal fluctuations in groundwater quality were observed as a consequence of agricultural practices and other factors such as annual rainfall distribution and the Guadalquivir River flow regime. The chemical composition of the water is not only influenced by agricultural practices, but also by interaction with the alluvial sediments. The dissolution of evaporites accounts for part of the Na⁺, K⁺, Cl⁻, SO₄ ²⁻, Mg²⁺, and Ca²⁺, but other processes, such as calcite precipitation and dedolomitization, also contribute to groundwater chemistry.     

Mineralogical and geochemical characterization of the Riópar non-sulfide Zn-(Fe-Pb) deposits (Prebetic Zone,SE Spain)

The present paper reports the first detailed petrological and geochemical study of non-sulfide Zn–(FePb) deposits in the Riópar area (Prebetic Zone of the Mesozoic Betic Basin, SE Spain), constraining the origin and evolution of ore-forming fluids. In Riópar both sulfide and non-sulfide Zn–(FePb) (“calamine”) ores are hosted in hydrothermally dolomitized Lower Cretaceous limestones. The hypogene sulfides comprise sphalerite, marcasite and minor galena. Calamine ores consist of Zn-carbonates (smithsonite and scarce hydrozincite), associated with abundant Fe-(hydr)oxides (goethite and hematite) and minor Pb-carbonates (cerussite). Three smithsonite types have been recognized: i) Sm-I consists of brown anhedral microcrystalline aggregates as encrustations replacing sphalerite; ii) Sm-II refers to brownish subhedral aggregates of rugged appearance related with Fe oxi-hydroxides in the surface crystals, which replace extensively sphalerite; and iii) Sm-III smithsonite appears as coarse grayish botryoidal aggregates in microkarstic cavities and porosity. Hydrozincite is scarce and appears as milky white botryoidal encrustations in cavities replacing smithsonite. Also, two types of cerussite have been identified: i) Cer-I cerussite consists of fine crystals replacing galena along cleavage planes and crystal surfaces; and ii) Cer-II conforms fine botryoidal crystals found infill porosity. Calcite and thin gypsum encrustations were also recognized. The field and petrographic observations of the Riópar non-sulfide Zn–(FePb) revealed two successive stages of supergene ore formation under meteoric fluid processes: i) “gossan” and “red calamine” formation in the uppermost parts of the ore with deposition of Fe-(hydr)oxides and Zn- and Pb-carbonates (Sm-I, Sm-II and Cer-I), occurring as direct replacements of ZnPb sulfides; and ii) “gray calamine” ore formation with deposition of Sm-III, Cer-II and hydrozincite infilling microkarst cavities and porosity. The stable isotope variation of Riópar smithsonite is very similar to those obtained in other calamine-ore deposits around the world. Their CO isotope data (δ¹⁸O: + 27.8 to + 29.6‰ V-SMOW; δ¹³C: − 6.3 to + 0.4‰ V-PDB), puts constrains on: i) the oxidizing fluid type, which was of meteoric origin with temperatures of 12 to 19 °C, suggesting a supergene weathering process for the calamine-ore formation under a temperate climate; and ii) the carbon source, that resulted from mixing between two CO₂ components derived from: the dissolution of host-dolomite (¹³C-enriched source) and vegetation decomposition (¹³C-depleted component).     

New data on the composition and age of the Ust’-Emuneret flora from the Enmyvaam River basin (Central Chukotka)

The Ust’-Emuneret floristic assemblage from the Emuneret Formation developed in the Enmyvaam River basin (Okhotsk-Chukotka volcanogenic belt) is described. The age of flora-bearing deposits is debatable, being previously determined in the interval of the Cenomanian to Campanian. According to the new data, the assemblage includes 57 species of fossil plants with dominant angiosperms, subdominant conifers, and subordinate ferns, liverworts, ginkgoaleans, and czekanowskialeans. The Ust’-Emuneret flora is characterized by the presence of advanced forms among different plant groups, which occur in Santonian-Campanian and younger floras of northeastern Russia, and by the presence of relict ginkgoaleans and czekanowskialeans. The flora is compared with other floras from neighboring regions, which provides grounds for the inference on its most probable Late Santonian age (probably, including the Early Santonian and initial Campanian).     

First representative of the genus Helius Lepeletier and Serville, 1828 (Diptera,Limoniidae) from the Lower Cretaceous Álava amber (Spain)

Helius alavensis sp. nov., one of the oldest representative of the genus Helius Lepeletier and Serville, 1828 (Diptera: Limoniidae), is described from the Álava amber (Lower Cretaceous, upper Albian), northern Spain. This is the first representative of the subfamily Limoniinae and of the genus Helius described from this fossil resin.     

The effects of pH on the adsorption of mercury on laterite from Guizhou Province, China

1 Introduction Because clay minerals have the characteristics ofadsorption, ion exchange capability and expandingcapacity, they are highly capable of adsorbing allkinds of pollutants in waters, thus making soilspossess self-purification functions. Clay m…     

The Combined Effect of Tibetan Plateau Uplift and Glacial-Interglacial Cycles on the Quaternary Evolution of the East Asian Monsoon: Evidence from South China Sea Sediments

The siliciclastic sediments of the uppermost section of 185 mcd(meters composite depth) from ODP Site 1146 on the northern continental slope of the South China Sea(SCS) were partitioned according to their sources using end-member modeling on grain-size data. The goal was to evaluate the evolution of the East Asian monsoon over the past 2 million years. The siliciclastic sediments were described as hybrids of four end-members, EM1, EM2, EM3, and EM4, with modal grain sizes of 8–22 μm, 2–8 μm, 31–125 μm, and 4–11 μm, respectively. EM1 and EM3 are interpreted as eolian dust and EM2 and EM4 as fluvial mud. The ratio of eolian dust to fluvial mud((EM1+EM3)/(EM2+EM4)) is regarded as an indicator of the East Asian monsoon. The variation in this ratio not only shows periodical oscillations consistent with oxygen isotope stages, but also exhibits a phased increasing trend corresponding with the phased uplifts of the Tibetan Plateau, indicating that the evolution of the East Asian Monsoon was controlled not only by glacial-interglacial cycles, but also by the phased uplifts of the Tibetan Plateau during the Quaternary.     

Mobilization of Ag,heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería,SE Spain)

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg^–1), Ba (mean 2.5%), Fe (mean 114,000 mg kg^–1), Sb (mean 342.5 mg kg^–1), Pb (mean 1,229.8 mg kg^–1), Zn (mean 493 mg kg^–1), Mn (mean 4,321.1 mg kg^–1), Cd (mean 1.2 mg kg^–1) and Eu (mean 4.0 mg kg^–1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)₃, which controls the solubility of Eu in the pH–Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.     

Geochemical Constraints of Sediments on the Provenance, Depositional Environment and Tectonic Setting of the Songliao Prototype Basin

The geochemistry of sediments is primarily controlled by their provenances, and different tectonic settings have distinctive provenance characteristics and sedimentary processes. So, it is possible to discriminate provenances, depositional environments and tectonic settings in the development of a sedimentary basin with the geochemistry of the clastic rocks. The analytical results of the present paper demonstrate that sediments in the Songliao prototype basin are enriched in silica (SiO2=66.48-80.51 %), and their ΣREE are 30-130 dmes of that of chondrite with remarkable Eu anomalies. In discriminating diagrams of Eu/Eu vs eeeeeREE and (La/Yb)N vs ΣREE, most samples locate above the line Eu/ Eu=l, on the right of the line Eu/Eu/ΣREE=1 and under the line La/Yb)N/eeeeeREE=1/8, which indicates that the depositional environment of sediments in the basin was oxidizing. In addition, variations of MgO, TiO2, A12O3, FeO+Fe2O3, Na2O and CaO vs SiO2 reflect a tendency of increasing mineral maturity of sediments     

Monitoring study of the mine pond reclamation of Mina Concepción, Iberian Pyrite Belt (Spain)

Mining of massive (Cu, Pb and Zn) sulphide bodies in the Iberian Pyrite Belt (SW Spain) has generated a great number of abandoned waste deposits such as mine ponds. These represent large accumulations of reactive minerals and subsequently, emission sources of trace elements and formation of acid drainage. Even if they have been restored, monitoring studies are required to evaluate the corrective effects and how they may change over time. This work presents the results of a monitoring study carried out at Mine Concepción mine pond, based on mineralogical (XRD), geochemical (INAA, X-ray fluorescence, ICP-MS) and geophysical (electrical resistivity tomography) techniques. In it, a series of relevant parameters have been well delimited, such as the infilling thickness and its variation and, the position, geometry and absence of water leakages through the base of the mine pond. Additionally, the existence of an internal, remnant flow of acid waters that tends to come out through the pond dyke has been identified. Chemistry of these waters indicates that oxidation processes affecting the Mina Concepción mine tailings are generating acid drainage waters which could potentially release substantial amounts of trace elements to the river Odiel. Thus, giving that not complete sealing is accomplished by the restoration capping and rainfall water infiltrates into the pond materials, at least the sealing of the dyke through which leakages occur should be revised.     

Lithology,Biostratigraphy, and Geochronology of the Late Pleistocene–Holocene Sediments on the Coast of Onega Bay of the White Sea

Doklady Earth Sciences - This paper reports on the lithological, micropaleontological, and chronometric data (radiocarbon dating) for one of the areas of the White Sea coast. The sedimentary...     

C, О, S,and Sr Isotope Geochemistry and Chemostratigraphy of Ordovician Sediments in the Moyero River Section,Northern Siberian Platform

The ⁸⁷Sr/⁸⁶Sr ratio in gypsum and limestones of the Ordovician section of the Moyero River decreases from the bottom upward from 0.7091?0.7095 in the Irbukli Formation (Nyaian Regional Stage, ~Lower Ordovician Tremadocian Stage) to 0.7080 in the upper part of the Dzherom Formation (Dolborian Regional Stage, ~Upper Ordovician Katian Stage), which is well consistent with biostratigraphic subdivision of the section and existing concept concerning the strontium isotope evolution of the World Ocean. The most characteristic feature of the carbon isotope curve is decrease of δ¹³С values in carbonates from weakly positive values (0.5…1.1‰) in the Irbukli Formation (Nyaian Regional Stage) to sharply negative values (–5.4...–5.8‰) in the middle part of the Kochakan Formation (top of the Kimaian Regional Stage, ~end of the Dapingian–base of the Darriwilian Stage). Increase of δ¹⁸О from 20?22‰ to 26?28‰, the negative correlation of δ¹³С and δ¹⁸О, and decrease of δ³⁴S in gypsum from 30?32‰ to 22?24‰ in this interval indicate that the ¹³С depletion of carbonates was not related to the sulfate reduction and oxidation of organic matter during diagenesis and that the negative δ¹³С excursion was of primary nature. The presence of negative δ¹³С anomalies at this stratigraphic level in Ordovician sections of the South and North America (Buggish et al., 2003; Edwards and Saltzman, 2014; McLaughlin et al., 2016) indicates the global or subglobal distribution of this event, which was possibly related to the emergence of the oldest ground vegetation. Against the general decrease of δ¹³С, the lower part of the section reveals three low-amplitude (1?2‰) positive excursions, the position of which in general confirms the existing correlation scheme of the Moyero River section with the international scale. The upper part of the section is characterized by the alternation of low-δ¹³С intervals (from–2 to–3‰) and brief positive excursions with amplitude of 0.5?1.3‰. The positive δ¹³С excursion terminating the Ordovician section of the Moyero River correlates with the δ¹³С excursion in the middle Katian Stage, while the δ¹³С excursion in the lower part of the Baksian Regional Stage correlates with the excursion marking the Katian–Sandbian boundary.     

Characterization of indoor and outdoor atmospheric pollutants impacting architectural monuments: the case of San Jerónimo Monastery (Granada, Spain)

Indoor and outdoor concentrations of atmospheric gaseous pollutants as well as composition, size, and morphology of particulate matter have been investigated at the monastery of San Jerónimo in Granada (Southern Spain). Complementary micro- and nano-analytical techniques were applied; elemental and mineralogical composition and morphological characteristics of particulate matter were investigated combining electron probe microanalysis at the single particle level, and bulk aerosol samples were analyzed using energy-dispersive X-ray fluorescence, X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analyzer and transmission electron microscopy (TEM). Microclimatic conditions at the monastery were monitored, and gas concentrations were assessed by means of diffusion tubes subsequently analyzed with ion chromatography. Results revealed high abundances of soil dust particles (aluminosilicates, calcite, dolomite, quartz), salt aerosols (chlorides, sulfates and ammonium-rich salts), and NO₂ and SO₂ both outdoors and indoors. Amorphous black carbon particles had surprisingly high abundances for Granada, a non-industrialized city. The composition of indoor particles corresponds to severe weathering affecting the construction materials and artworks inside the church; moreover their composition promotes a feedback process that intensifies the deterioration. Chemical reactions between chloride-rich salts and pigments from paintings were confirmed by TEM analyses. Indoors, blackening of surface decorative materials is fostered by particle re-suspension due to cleaning habits in the monastery (i.e. dusting). This is the first air quality study performed in a monument in the city of Granada with the aim of developing a strategy for preventive conservation.     

Sulfur and lead isotope systematics: Implications for the genesis of the Riópar Zn-(Fe-Pb) carbonate-hosted deposit (Prebetic Zone,SE Spain)

The Zn-(Fe-Pb) deposits of the Riópar area (Prebetic Zone, SE Spain) are hosted by dolostones that replace Berriasian to Valanginian (Upper Jurassic-Lower Cretaceous) limestones. Mineralization consists of hypogene sphalerite, marcasite and galena, and supergene calamine zones. The hypogene ores are associated with a saddle dolomite gangue. The ore bodies occur as discordant and stratiform lenses, ore-cemented breccias, cm- to mm-wide veins and veinlets, disseminations and stylolite porosity filling within the host dolomites. The main ore controls include stratigraphy and/or lithology, tectonics (faults, fractures and breccias) and availability of metals and sulfur. The morphologies and epigenetic character of the hypogene ore bodies are consistent with the classification of this mineralization as a Mississippi Valley-type (MVT) deposit. The Ga/Ge geothermometer in sphalerite yielded a temperature range of 194–252 °C, which represents the temperature of the source region of the ore solution. This value is comparable to the temperature obtained in the ore deposition site, 159 ± 15 °C from the Δ³⁴S geothermometer in sphalerite galena pairs. This similitude points to a hydrothermal fluid that did not cool down significantly during flow from the fluid reservoir area to the precipitation site. δ³⁴S values of base-metal sulfides (−7.5 to +3.5‰) are consistent with thermochemical reduction of Triassic sulfate (seawater and/or derived from dissolution of evaporites) by interaction with organic compounds (e.g., hydrocarbons, methane), which reduced sulfate to sulfide in the deposition site. The lead isotope ratios (²⁰⁶Pb/²⁰⁴Pb = 18.736–18.762; ²⁰⁷Pb/²⁰⁴Pb = 15.629–15.660; ²⁰⁸Pb/²⁰⁴Pb = 38.496–38.595) of galena suggest that Pb, and probably other metals as Zn, is derived from continental crustal rocks. On the other hand, these relations points to a unique metal source probably derived from the Paleozoic basement rocks. The relationship between bedding-parallel stylolites, dolomitization, sulfide precipitation and Alpine tectonic affecting the MVT ore, suggests a relative timing range for the mineralization in the Riópar area of 95–20 Ma (Upper Cretaceous-Tertiary). The sulfide mineralization and the associated dolomitization are thus explained by the contribution of two fluids that mixed in different proportions during dolomitization and mineralization: i) a fluid probably derived from Cretaceous seawater saturating Mesozoic sediments (Fluid A), characterized by being dilute and initially low temperature, which should have contained organic rich compounds in the ore deposition site (e.g., hydrocarbons and CH₄ dissolved gas); and ii) a high salinity hydrothermal brine (Fluid B) rich in both metals and sulfate, circulated through the Paleozoic basement. During the pre-ore dolomitizing stage the fluid phase was dominated by the diluted fluid (Fluid A > Fluid B), whereas in a later fluid pulse, the proportion of the high salinity fluid increased (Fluid A < Fluid B) which allowed sulfide precipitation. MVT exploration in the Prebetic Zone should focus towards the SW of the Riópar mines, in the vicinity of the Alto Guadalquivir-San Jorge fault.