Environmental implications of fluoride presence in drinking water along the southeastern of El Bajío Guanajuatese, Guanajuato, Mexico: sources and health effects

Chronic exposure from drinking water with naturally high concentrations of fluoride (F⁻) has serious health consequences in several regions across the world including north-central Mexico as Guanajuato State, where the rural population is particularly dependent on untreated groundwater pumped from wells that have natural F- concentrations higher than those allowed by national and international regulations. The contaminated aquifers in the area are usually located in fractured volcanic environment that interacts with sedimentary basins and have a carbonate basement. Few studies focused on identifying the origin and hydrogeochemical processes related to fluoride release and mobilization have been developed, and even fewer that quantify the natural content of F in the geological environment. In this study, an evaluation of fluoride in volcanic rocks collected from 11 sampling sites along the Sierra de Codornices (Guanajuato State, Central Mexico) was carried out. The fluoride content is disseminated in volcanic rocks and the highest contents were obtained in felsic rocks. According to results obtained of a sampling campaign of 32 wells in 2019 their statistical and hydrogeochemical evaluation suggest that F- mobilization in groundwater from Juventino Rosas and Villagran municipalities, is a product of volcanic glass dissolution, a process involved in alkaline desorption occurring on the surfaces of F-containing minerals, and possibly on ion exchange occurring in minerals and some clays or even in deep fluids enriched in F. All these processes may be accelerated by the geothermal characteristics of the groundwater in the study area. The hydrogeochemical results and the epidemiological survey conducted indicate that children and older adults of Praderas de la Venta are at risk of exposure to F- due to the high concentrations ingested over a long period of time, to the toxicity of the element and its ability to accumulate in the bones. Prolonged exposure to high concentrations increases the risk.

Improving the Performance of Mortars Made from Recycled Aggregates by the Addition of Zeolitised Cineritic Tuff

Metropolitan construction and demolition waste (CDW) is currently an important source of recycled materials that, despite having completed their useful life cycle, can be reincorporated into the circular economy process (CEP); however, the recycling process is very selective, and waste material is not always fully satisfactory due to the intrinsic nature of the waste. This work aims to demonstrate and establish how to increase the effectiveness of the construction and demolition waste in more resistant mortars, by mixing it with zeolitised cinerite tuff (ZCT) at varying normalised proportions. To attain the objectives of this research, a series of tests were done: First, a chemical, physical and mineralogical characterisation of the CDW and the ZCT through XRF, XRD, SEM and granulometric methods. Second, a technological test was made to determine the mechanical strength at 7, 28 and 90 days of specimens made with Portland cement (PC) and mixtures of PC/CDW, PC/ZCT, and PC/CDW-ZCT. The results obtained through the characterisation methods showed that the sample of construction and demolition waste consisted of the main phase made of portlandite and tobermorite, and by a secondary phase consisting of quartz, ettringite and calcite; whereas the ZCT has a main phase of mordenite and a secondary phase of smectite (montmorillonite), amorphous materials consisting of devitrified volcanic glass, quartz and plagioclase. Mechanical strength tests established that specimens made with PC/CDW mixtures have very discreet compressive strength values up to 44 MPa at 90 days, whereas specimens made with PC/ZCT mixtures achieved a remarkably high mechanical strength consisting of 68.5 MPa. However, the most interesting conclusion in this research is the good result obtained in mechanical strength of the specimens made up of mixtures of PC/CDW-ZCT, which increased from 52.5 to 62 MPa at 90 days of curing; this fact establishes the positive influence of ZCT on waste in the mortar mixtures, which permits the authors to establish that the objective of the work has been fulfilled. Finally, it can be argued that the results obtained in this research could contribute to more effective use of construction and demolition waste in metropolitan areas.

Recently Discovered Thick Bentonite Bed Hosted by the Lithothamnium Limestones (Badenian) in the Polish Part of the Carpathian Foredeep: The Evidence for Volcanic Origin

In this paper, we discuss the hypothesis on the volcanic origin of the precursor sediments for a thick (0.6 m) clay bed, hosted by the sequence of lithothamnium limestones of the Pińczów Formation. Combined X-ray powder diffraction, imaging methods (optical and electron microscopy), and chemical analysis were used to document the volcanic markers, which were preserved in the rock studied. The results obtained show that the clay bed discussed is bentonite in origin. This bentonite, which can be called Drugnia Rządowa bentonite, is composed almost entirely of montmorillonite with little admixtures of quartz and biotite. A small amount of calcite is present, but only in the top of the bed. Despite that, the bentonite contains nothing but clay material—it is a model example of entirely altered pyroclastic rock, which retains texture originally developed in volcanic glass fragments and reveals the preserved original features of the precursor fallout pyroclastic deposits (rhyolitic in character). The thick bentonite beds, discovered for the first time within the Badenian lithothamnium limestones of the Pińczów Formation, can be considered as a record of a violent, explosive volcanic event related to the closure of the Outer Carpathian basin and the development of the Carpathian Foredeep.

Miocene and Pliocene Silicic Coromandel Volcanic Zone Tephras from ODP Site 1124-C: Petrogenetic Applications and Temporal Evolution

<p>The Coromandel Volcanic Zone (CVZ) was the longest-lived area of volcanism in New Zealand hosting the commencement of large explosive rhyolitic and ignimbrite forming eruptions. The NW trending Coromandel Peninsula is the subaerial remnant of the Miocene-Pliocene CVZ, which is regarded as a tectonic precursor to the Taupo Volcanic Zone (TVZ), currently the most dynamic and voluminous rhyolitic volcanic centre on Earth. This study presents new single glass shard major and trace element geochemical analyses for 72 high-silica volcanic tephra layers recovered from well-dated deep-sea sediments of the SW Pacific Ocean by the Ocean Drilling Program (ODP) Leg 181. ODP Site 1124, ~720 km south and east from the CVZ, penetrated sediments of the Rekohu Drift yielding an unprecedented record of major explosive volcanic eruptions owing to the favourable location and preservation characteristics at this site. This record extends onshore eruptive sequences of CVZ explosive volcanism that are obscured by poor exposure, alteration, and erosion and burial by younger volcanic deposits. Tephra layers recovered from Site 1124 are well-dated through a combination of biostratigraphic and palaeomagnetic methods allowing the temporal geochemical evolution of the CVZ to be reconstructed in relation to changes in the petrogenesis of CVZ arc magmas from ~ 10 to 2 Ma. This thesis establishes major and trace element geochemical "fingerprints" for all Site 1124-C tephras using well-established (wavelength dispersive electron probe microanalysis) and new (laser ablation inductively coupled plasma mass spectrometry) in situ single glass shard microanalytical techniques. Trace element analysis of Site 1124-C glass shards (as small as 20 um) demonstrate that trace element signatures offer a more specific, unequivocal characterisation for distinguishing (and potentially correlating) between tephras with nearly identical major element compositions. The Site 1124-C core contains 72 unaltered Miocene-Pliocene volcanic glass-shard-bearing laminae > 1 cm thick that correspond to 83 or 84 geochemical eruptive units. Revised eruptive frequencies based on the number of geochemical eruptive units identified represent at least one eruption every 99 kyr for the late Miocene and one per 74 kyr for the Pliocene. The frequency of tephra deposition throughout the history of the CVZ has not been constant, rather reflecting pulses of major explosive eruptions resulting in closely clustered groups of tephra separated by periods of reduced activity, relative volcanic quiescence or non-tephra deposition. As more regular activity became prevalent in the Pliocene, it was accompanied by more silicic magma compositions. Rhyolitic volcanic glass shards are characterised by predominantly calc-alkaline and minor high-K enriched major element compositions. Major element compositional variability of the tephras deposited between 10 Ma and 2 Ma reveals magma batches with pre-eruptive compositional gradients implying a broad control by fractional crystallisation. Trace element characterisation of glass shards reveals the role of magmatic processes that are not readily apparent in the relatively homogeneous major element compositions. Multi-element diagrams show prominent negative Sr and Ti anomalies against primitive mantle likely caused by various degrees of plagioclase and titanomagnetite fractional crystallisation in shallow magma chambers. Relative Nb depletion, characteristic of arc volcanism, is moderate in CVZ tephras. HFSEs (e.g. Nb, Zr, Ti) and HREEs (e.g. Yb, Lu) remain immobile during slab fluid flux suggesting they are derived from the mantle wedge. LILE (e.g. Rb, Cs, Ba, Sr) and LREE (e.g. La, Ce) enrichments are consistent with slab fluid contribution. B/La and Li/Y ratios can be used as a proxy for the flux of subducting material to the mantle wedge, they suggest there is a strong influence from this component in the generation of CVZ arc magmas, potentially inducing melting. CVZ tephra show long-term coherent variability in trace element geochemistry. Post ~ 4 Ma tephras display a more consistent, less variable, chemical fingerprint that persists up to and across the CVZ/TVZ transition at ~ 2 Ma. Initiation of TVZ volcanism may have occurred earlier than is presently considered, or CVZ to TVZ volcanism may have occurred without significant changes in magma generation processes.</p>

Miocene and Pliocene Silicic Coromandel Volcanic Zone Tephras from ODP Site 1124-C: Petrogenetic Applications and Temporal Evolution

<p>The Coromandel Volcanic Zone (CVZ) was the longest-lived area of volcanism in New Zealand hosting the commencement of large explosive rhyolitic and ignimbrite forming eruptions. The NW trending Coromandel Peninsula is the subaerial remnant of the Miocene-Pliocene CVZ, which is regarded as a tectonic precursor to the Taupo Volcanic Zone (TVZ), currently the most dynamic and voluminous rhyolitic volcanic centre on Earth. This study presents new single glass shard major and trace element geochemical analyses for 72 high-silica volcanic tephra layers recovered from well-dated deep-sea sediments of the SW Pacific Ocean by the Ocean Drilling Program (ODP) Leg 181. ODP Site 1124, ~720 km south and east from the CVZ, penetrated sediments of the Rekohu Drift yielding an unprecedented record of major explosive volcanic eruptions owing to the favourable location and preservation characteristics at this site. This record extends onshore eruptive sequences of CVZ explosive volcanism that are obscured by poor exposure, alteration, and erosion and burial by younger volcanic deposits. Tephra layers recovered from Site 1124 are well-dated through a combination of biostratigraphic and palaeomagnetic methods allowing the temporal geochemical evolution of the CVZ to be reconstructed in relation to changes in the petrogenesis of CVZ arc magmas from ~ 10 to 2 Ma. This thesis establishes major and trace element geochemical "fingerprints" for all Site 1124-C tephras using well-established (wavelength dispersive electron probe microanalysis) and new (laser ablation inductively coupled plasma mass spectrometry) in situ single glass shard microanalytical techniques. Trace element analysis of Site 1124-C glass shards (as small as 20 um) demonstrate that trace element signatures offer a more specific, unequivocal characterisation for distinguishing (and potentially correlating) between tephras with nearly identical major element compositions. The Site 1124-C core contains 72 unaltered Miocene-Pliocene volcanic glass-shard-bearing laminae > 1 cm thick that correspond to 83 or 84 geochemical eruptive units. Revised eruptive frequencies based on the number of geochemical eruptive units identified represent at least one eruption every 99 kyr for the late Miocene and one per 74 kyr for the Pliocene. The frequency of tephra deposition throughout the history of the CVZ has not been constant, rather reflecting pulses of major explosive eruptions resulting in closely clustered groups of tephra separated by periods of reduced activity, relative volcanic quiescence or non-tephra deposition. As more regular activity became prevalent in the Pliocene, it was accompanied by more silicic magma compositions. Rhyolitic volcanic glass shards are characterised by predominantly calc-alkaline and minor high-K enriched major element compositions. Major element compositional variability of the tephras deposited between 10 Ma and 2 Ma reveals magma batches with pre-eruptive compositional gradients implying a broad control by fractional crystallisation. Trace element characterisation of glass shards reveals the role of magmatic processes that are not readily apparent in the relatively homogeneous major element compositions. Multi-element diagrams show prominent negative Sr and Ti anomalies against primitive mantle likely caused by various degrees of plagioclase and titanomagnetite fractional crystallisation in shallow magma chambers. Relative Nb depletion, characteristic of arc volcanism, is moderate in CVZ tephras. HFSEs (e.g. Nb, Zr, Ti) and HREEs (e.g. Yb, Lu) remain immobile during slab fluid flux suggesting they are derived from the mantle wedge. LILE (e.g. Rb, Cs, Ba, Sr) and LREE (e.g. La, Ce) enrichments are consistent with slab fluid contribution. B/La and Li/Y ratios can be used as a proxy for the flux of subducting material to the mantle wedge, they suggest there is a strong influence from this component in the generation of CVZ arc magmas, potentially inducing melting. CVZ tephra show long-term coherent variability in trace element geochemistry. Post ~ 4 Ma tephras display a more consistent, less variable, chemical fingerprint that persists up to and across the CVZ/TVZ transition at ~ 2 Ma. Initiation of TVZ volcanism may have occurred earlier than is presently considered, or CVZ to TVZ volcanism may have occurred without significant changes in magma generation processes.</p>

Integration of Geological, Geochemical, Mineralogical and Remote Sensing Data for Studying Zeolite Deposits of Al-Ahyuq-Taiz, Yemen

Zeolite deposits crop out at Al-Ahyuq area, and lies at about 89 km southwest of Taiz city. It is one of the most important zeolite localities in Yemen. The study area is covered by the Yemen volcanic group. X-Ray Diffraction (XRD) analyses showed that clinoptilolite is the major type of Al-Ahyuq zeolites with high purity. Chemical analysis shows that the studied zeolitic tuff samples have silica content ranging from 63.10 wt% - 71.1wt% with an average 68.69 wt%, Fe2O3 [as total iron] with an average 2.38wt%, MgO with an average 0.44 wt% and TiO2 with an average 0.17wt%. These chemical properties of Al-Ahyuq zeolite deposits are with low impurities content such as CaO and MgO, compared to those deposits found in other countries around the world. The chemical and mineralogical studies support that the zeolite minerals of the Al-Ahyuq area formed by subaerial hydrothermal alteration of the parent volcanic glass. The ASTER bands as false colour composite (1-R, 2-G, 3-B), and band ratios 3/9 and 4/6 highlighted area of zeolite deposits dominated as bright pixels. The band ratio combination 4/6-R, 2/1-G and 3/2-B is effective in mapping of Al-Ahyuq zeolitic tuffs. Spectra after being resampled to ASTER VNIR+SWIR bands of the study area comparing with the USGS library spectra of zeolite – clinoptilolite shows almost identical and confirmed that clinoptilolite is the major of zeolite deposits in Al-Ahyuq area. Chemical and mineralogical investigation of the Al-Ahyuq zeolite (clinoptilolite) deposits recommends many important agricultural, environmental, and industrial applications. Keyword: Zeolitic tuff; clinoptilolite; XDR; XRFS; ASTER data; band ratio

The Identification and Analysis of Gas-Related Volcanic Features within Chang’e-5 Landing Region

Chang’e-5 (CE-5) successfully landed on the young basalts area in the northeastern Oceanus Procellarum on 1 December 2020. Recent studies on the CE-5 landing area have shown that the lack of gas-related volcanic morphology indicates that the volatile elements captured in the interior of the Moon within late-stage magma is relatively low. Typical lunar gas-related volcanic features include dark mantle deposits, volcanic pits, irregular mare patches and so on. Based on orbital images, topography, and spectral data obtained from multiple missions restricted by the morphologic and compositional characteristics of typical volcanic explosive features, this study investigated the morphological characteristics of the volcanic features in detail and found that there are three dark mantle deposits (DMDs) near the source area of Rima Mairan that have unusually low albedo and abnormally high titanium and iron content than those of the surrounding material. Combined with M3 spectral analysis, it is shown that DMDs contain some volcanic glass components, which indicates a gas-rich explosive eruption process. In addition to DMDs, irregular mare patches (IMPs) and a volcanic depression/pit have been recognized in this area, both of which indicate a history of gas-related volcanic eruptions. Based on this study and combined with past studies, we determined the volcanic history in the source area of Rima Mairan, including both effusive and explosive volcanic activities.

Effects of a Natural Mordenite as Pozzolan Material in the Evolution of Mortar Settings

This paper shows the results of a study focused on the evolution and properties of mortars made with a mixture of portland cement (PC) and natural mordenite (Mor). To begin, samples of mordenite, cement and sand were studied with X-ray diffraction (XRD), X-ray fluorescence (XRF) and granulometric analysis (GA). Next, mortars with a ratio of 75% PC and 25% mordenite were prepared to determine their initial and final setting times, consistency and density. Continuing, the density, weight and compressive strength of the specimens were determined at 2, 7, 28, 90 and 365 days. Finally, the specimens were studied using SEM, XRD and XRF. The results of the study of the mordenite sample showed a complex constitution where the major mineral component is mordenite, and to a lesser degree smectite (montmorillonite), halloysite, illite, mica, quartz, plagioclase and feldspar, in addition to altered volcanic glass. Tests with fresh cement/mordenite mortar (CMM) showed an initial setting time of 320 min and a final setting time of 420 min, much longer than the 212–310 min of portland cement mortar (PCM). It was established that the consistency of the cement/mordenite mortar (CMM) was greater than that of the PCM. The results of the density study showed that the CMM has a lower density than the PCM. On the other hand, the density of cement/mordenite specimens (CMS) was lower than that of portland cement specimens (PCS). The CMS compressive strength studies showed a significant increase from 18.2 MPa, at 2 days, to 72 MPa, at 365 days, with better strength than PCS at 28 and 365 days, respectively. XRD, XRF and SEM studies conducted on CMS showed a good development of primary and secondary tobermorite, the latter formed at the expense of portlandite; also, ettringite developed normally. This work proves that the partial replacement of PC by mordenite does not have a negative effect on the increase in the mechanical strength of CMS. It indicates that the presence of mordenite inhibits the spontaneous hydration of C3A and controls the anomalous formation of ettringite (Ett). All this, together with the mechanical strength reported, indicates that mordenite has a deep and positive influence on the evolution of the mortar setting and is an efficient pozzolan, meaning it can be used in the manufacture of mortars and highly resistant pozzolanic cement, with low hydration heat, low density, stability in extremely aggressive places and a low impact on the environment.

Volcaniclastic deposits and sedimentation processes around volcanic ocean islands: the central Azores

Geological histories of volcanic ocean islands can be revealed by the sediments shed by them. Hence there is an interest in studying cores of volcaniclastic sediments that are particularly preserved in the many flat-floored basins lying close to the Azores islands. We analyse four gravity cores collected around the central group of the islands. Three sedimentary facies (F1-F2a, F2b) are recognized based on visual core logging, particle morphometric and geochemical analyses. F1 is clay-rich hemipelagite comprising homogeneous mud with mottled structures from bioturbation. F2a and F2b are both clay-poor volcaniclastic deposits, which are carbonate-rich and carbonate-poor, respectively. More biogenic carbonate in F2a reflects the incorporation of unconsolidated calcareous material from island shelves or bioturbation. Within F2a and F2b we identify deposits emplaced by pyroclastic fallout, primary or secondary turbidity currents by combining multiple information from lithological composition, sedimentary structures, chemical composition of volcanic glass shards and morphometric characteristics of volcanic particles. Primary volcaniclastic sediments were found in all four cores, echoing activity known to have occurred up to historical times on the adjacent islands. These preliminary results suggest that greater details of geological events could be inferred for other volcanic islands by adopting a similar approach to core analysis.Supplementary material at https://doi.org/10.6084/m9.figshare.c.5602176