Minerals, Volume 10, Issue 10 (October 2020) – 95 articles

Archaeometric investigation of ancient pottery with regard to their material composites allows insights into the material structures, production techniques and manufacturing processes. The applied methods depend on the classification of the pottery: some finds should remain unchanged for conservation reasons, other finds are less valuable or more common. While the first group cannot be destroyed for material analyses and the choice of analytical methods is limited, the latter can be investigated using destructive methods and thus can widen the spectrum of possible devices. Multi-element analyses of portable energy-dispersive X-ray fluorescence spectrometry (portable XRF) have become important for archaeological research, as portable XRF provides a quick overview about the chemical composition of potteries and can be used in non-destructive as well as destructive ways in addition to conventional microscopic examination and petrographic thin sections. While most portable XRF analyses of solely fracture surfaces do not provide satisfying results, portable XRF analyses on pulverized samples are a cost-efficient and fast alternative to wavelength-dispersive XRF (WD-XRF). In comparison to WD-XRF, portable XRF on pulverized samples provides reliable concentration data (K, Fe, Rb, Ti, V, Y, Zn, Zr), but other elements need to be corrected. X-ray microtomography (µCT) has proven to be a non-destructive technique to derive not only the porosity of ancient pottery but also to characterize temper components and non-plastic inclusions. Hence, the µCT technique has the potential to extract valuable information needed by archaeologists, for example, to deduce details about manufacturing. Full article

Elastic properties of mixtures of illitic clay, thermal power plant fly ash (fluidized fly ash—FFA and pulverized fly ash—PFA), and grog were investigated during the heating and cooling stages of the firing. The grog part in the mixtures was replaced with 10, 20, 30, and 40 mass% of the fly ash, respectively. The temperature dependence of Young’s modulus was derived using the dynamical thermomechanical analysis, in which dimensions and mass determined from thermogravimeric and thermodilatometric results were used. Flexural strength was measured at the room temperature using the three-point bending test. The following results were obtained: (1) Bulk density showed a decreasing trend up to 900 °C and a steep increase above 900 °C. During cooling, the bulk density slightly increased down to the room temperature. (2) Young’s modulus increased significantly during heating up to ~300 °C. Dehydroxylation was almost not reflected in Young’s modulus. At temperatures higher than 800 °C, Young’s modulus began to increase due to sintering. (3) During cooling, down to the glass transformation, Young’s modulus slightly increased and then began to slightly decrease due to microcracking between phases with different thermal expansion coefficients. (4) Around the β→α quartz transition, radial stresses on the quartz grain altered from compressive to tensile, creating microcracks. Below 560 °C, the radial stress remained tensile, and consequently, the microcracking around the quartz grains and a decreasing Young’s modulus continued. (5) With a lower amount of PFA and FFA, a higher Young’s modulus was reached after sintering. The final values of Young’s modulus, measured after firing, show a decreasing trend and depend linearly on the part of fly ash. (6) The flexural strength measured after firing decreased linearly with the amount of the fly ash for both mixtures. Full article

The Silante Formation is a thick series of continental deposits, exposed along a trench-parallel distance of approximately 300 km within the Western Cordillera of Ecuador. The origin, tectonic setting, age and stratigraphic relationships are poorly known, although these are key to understand the Cenozoic evolution of the Ecuadorian Andes. We present new sedimentological, stratigraphic, petrographic, radiometric and provenance data from the Silante Formation and underlying rocks. The detailed stratigraphic analysis shows that the Silante Formation unconformably overlies Paleocene submarine fan deposits of the Pilalo Formation, which was coeval with submarine tholeiitic volcanism. The lithofacies of the Silante Formation suggest that the sediments were deposited in a debris flow dominated alluvial fan. Provenance analysis including heavy mineral assemblages and detrital zircon U-Pb ages indicate that sediments of the Silante Formation were derived from the erosion of a continental, calc-alkaline volcanic arc, pointing to the Oligocene to Miocene San Juan de Lachas volcanic arc. Thermochronological data and regional correlations suggest that deposition of the Silante Formation was coeval with regional rock and surface uplift of the Andean margin that deposited alluvial fans in intermontane and back-arc domains. Full article

Changes in stable chromium isotopes (denoted as δ⁵³Cr) in ancient carbonate sediments are increasingly used to reconstruct the oxygenation history in Earth’s atmosphere and oceans through time. As a significant proportion of marine carbonate older than the Cambrian is microbially-mediated, the utility of δ⁵³Cr values in ancient carbonates hinges on whether these sediments accurately capture the isotope composition of their environment. We report Cr concentrations (Cr) and δ⁵³Cr values of modern marginal marine and non-marine microbial carbonates. These data are supported by stable C and O isotope compositions, as well as rare earth elements and yttrium (REY) concentrations. In addition, we present data on ancient analogs from Precambrian strata. Microbial carbonates from Marion Lake (Australia, δ⁵³Cr ≈ 0.99‰) and Mono Lake (USA, ≈0.78‰) display significantly higher δ⁵³Cr values compared with ancient microbialites from the Andrée Land Group in Greenland (720 Ma, ≈0.36‰) and the Bitter Springs Formation in Australia (800 Ma, ≈−0.12‰). The δ⁵³Cr values are homogenous within microbialite specimens and within individual study sites. This indicates that biological parameters, such as vital effects, causing highly variable δ⁵³Cr values in skeletal carbonates, do not induce variability in δ⁵³Cr values in microbialites. Together with stable C and O isotope compositions and REY patterns, δ⁵³Cr values in microbialites seem to be driven by environmental parameters such as background lithology and salinity. In support, our Cr and δ⁵³Cr results of ancient microbial carbonates agree well with data of abiotically precipitated carbonates of the Proterozoic. If detrital contamination is carefully assessed, microbialites have the potential to record the δ⁵³Cr values of the waters from which they precipitated. However, it remains unclear if these δ⁵³Cr values record (paleo-) redox conditions or rather result from other physico-chemical parameters. Full article

An integrated zircon geochronological, elemental geochemical, and Sr–Nd–Hf isotopic investigation was carried out on a suite of dioritic–granitic rocks at Zalute in the southern Great Xing’an Range (SGXR), NE China, in order to probe the source and petrogenesis of these granitoid rocks and further constrain the geodynamical setting of early Early Cretaceous magmatism. The results of Sensitive High-Resolution Ion Micro Probe (SHRIMP) zircon U–Pb dating reveal that the Zalute dioritic–granitic rocks have a consistent crystallization age of ca. 137–136 Ma, consisting of quartz diorite (136 ± 1.4 Ma), monzogranite (136 ± 0.8 Ma), and granite porphyry (137 ± 1.3 Ma), which record an early Early Cretaceous magmatic intrusion. Geochemically, the quartz diorites, monzogranites, and granite porphyries are mostly high-K calc-alkaline and show features of typical I-type affinity. They possess uniform and depleted Sr–Nd–Hf isotopic compositions (e.g., initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7035 to 0.7049, ε_Nd(t) of −0.02 to +2.61, and ε_Hf(t) of +6.8 to +9.6), reflecting a common source, whose parental magma is best explained as resulting from the partial melting of juvenile source rocks in the lower crust produced by underplating of mantle-derived mafic magma, with minor involvement of ancient crustal components. Evidence from their close spatio–temporal relationship, common source, and the compositional trend is consistent with a magmatic differentiation model of the intermediate-felsic intrusive suite, with continued fractional crystallization from quartz diorites, towards monzogranites, then to granite porphyries. Combined with previously published data in the SGXR, our new results indicate that the Zalute intermediate-felsic intrusive suite was formed during the post-collisional extension related to the closure of the Mongol–Okhotsk Ocean and subsequent slab break-off. Full article

Within due diligence concepts for raw material supply chains, the traceability of a shipment is a major aspect that has to be taken into account. Cassiterite and coltan are two so-called conflict minerals for which traceability systems have been established. To provide additional credibility to document-based traceability systems the German Federal Institute for Geosciences and Natural Resources (BGR) has developed the analytical fingerprint (AFP) for the minerals coltan, cassiterite, and wolframite. AFP is based on the analysis of a sample from a shipment with a declared origin and evaluates whether the declared origin is plausible or not. This is done by comparison to reference samples previously taken at the declared mine site. In addition to the generation of the analytical data, the data evaluation step, with the aim to state whether the declared origin is plausible or not, is of special importance. Two data evaluation approaches named “Kolmogorov–Smirnov distance (KS-D) approach” and “areas ratio approach” are applied to coltan and cassiterite and result in very low rates of false negative results, which is desired for AFP. The areas ratio approach based on hypothesis testing and a more sophisticated evaluation of the multivariate data structure has some advantages in terms of producing lower rates of false positive results compared to the KS-D approach. Full article

This paper presents a review of measurement while drilling (MWD) technology as applied to the mining industry, describes its development path, provides a global review of literature on this topic, and outlines further trends of development for research on MWD application in drilling and blasting (D&B) operations at mining enterprises. The current review serves as a starting point for anyone interested in the research or application of MWD technology in Mining and Construction. In the paper, the authors examine major works of researchers in this area, describe current state of the art, and propose a way to improve MWD for drilling equipments. The paper contains examples of technology application in various processes, associated with drilling and mining operations, describes approaches and problems of MWD system utilization, revealed in the course of data collection and analysis of drilling processes. The study also presents a summary of existing approaches in the area of data validation and verification, applied up to the present day to cope with the problems of global MWD use in Mining and Construction. The authors outline future areas of study which are of interest and deserve the attention of the scientific community and researchers working on the development of MWD technology. Full article

The structural chemistry of carbonates under mantle conditions facilitates our understanding of carbon recycling pathways in the earth’s interior. It also has impacts on the dynamics of mantle–slab interactions. Aragonite is a common calcium carbonate mineral in pelagic marine sediments. The structural chemistry of single-crystal aragonite during successive compression and the behavior of a structural H⁺ have been investigated by micro-vibrational spectroscopy and synchrotron X-ray diffraction techniques in diamond anvil cells. We describe a reduction of the b-axial compressibility beginning at ~15 GPa, and the related discontinuities in the first-order derivatives of the vibrational modes. The structural modifications of aragonite are manifested by mutations occurring in the pressure relations of the wavenumbers of the O-C-O bending modes, and of the bandwidth and band intensities of the measured internal and external modes. These anomalies are indicative of changes occurring in the force constant of the C-O bonds, and possibly a second-order phase transition. Besides, the [CaO₉] polyhedra begin to deform, possibly with some Ca-O bonds becoming elongated and the others shortening. An increase in the co-ordination number for the Ca²⁺ sites could be expected under higher pressures. Additionally, the weakening of the OH modes may imply H⁺-loss from the aragonite lattice above 11.5 GPa. Full article

This experimental laboratory study examines the potential use of tire-derived aggregate (TDA) products as an additive to alleviate the inferior geotechnical properties of a subgrade deposit of clay soil with high expansivity. A total of ten mix designs—the unamended soil and nine soil–TDA blends prepared at 5%, 10% and 20% TDA contents (by dry mass) using three different TDA gradations/sizes—were examined. The experiments included standard Proctor compaction, oedometer swell and unconfined compression tests. The TDA materials’ lower specific gravity, hydrophobic character and higher energy absorption capacity compared with the soil solids led to notable reductions in the soil compaction characteristics. The amendment of the soil with TDA resulted in notable decreases in the rate and magnitude of swelling—the observed reductions were in favor of higher TDA contents, with larger TDA particle size being a secondary factor. Further, for any given TDA size, the variations of strength and toughness with respect to TDA content exhibited rise–fall relationships, peaking at 5% TDA and then decreasing for higher TDA contents. The stiffness and ductility parameters, however, were found to monotonically decrease and increase with the TDA content, respectively. Finally, TDA contents of up to 10%, with gradations equivalent to those of medium and coarse sands, were found to reduce the soil’s swelling potential from high to moderate expansivity, while simultaneously improving its strength-related features, and thus can be deemed as optimum mix design choices from a geotechnical perspective. Full article

Understanding the flow process of cemented tailings backfill (CTB) is important for successful pumping into underground stopes. This study examines the effects of solid content (SC), cement/tailings (c/t) ratio, and curing time (CT) on rheological and mechanical properties of CTB mixes. The slurry concentration of the mixes was 65, 67, and 69 wt. %, with c/t ratios ranging from 1:4 to 1:20. Unconfined compressive strength (UCS) tests were performed on hardened CTB mixes after curing 3, 7, and 28 days. The rheological properties of CTB slurries are mainly related to SC. The yield stress and viscosity of fresh mixes increase with increasing SC, but the pipeline resistance loss (PRL) also increases with increasing SC. According to the analysis of variance, the SC and flow rate are the most significant parameters which greatly affect the PRL performance. The c/t and CT parameters are the most significant parameters for affecting the shrinkage rate. The findings offer a reference for theoretical optimization for mine filling systems of similar type. Full article

Tooeleite [Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O] was synthesized and characterized to investigate its possible immobilization for arsenic in acidic and alkali environments by a long-term dissolution of 330 d. The synthetic tooeleite was platy crystallites of ~1μm across, giving the lattice parameters of a = 6.4758 Å, b = 19.3737 Å and c = 8.9170 Å. For the tooeleite dissolution, the dissolved arsenic concentration showed the lowest value of 427.3~435.8 mg/L As at initial pH 12 (final pH 5.54). The constituents were dissolved preferentially in the sequence of SO₄²⁻ > AsO₃³⁻ > Fe³⁺ in the aqueous medium at initial pH 2–12. The dissolved iron, arsenite and sulfate existed mainly as FeSO₄⁺/Fe³⁺, H₃AsO₃⁰ and SO₄²⁻ at initial pH 2, and in the form of Fe(OH)₃⁰/Fe(OH)₂⁺, H₃AsO₃⁰ and SO₄²⁻ at initial pH 12, respectively. The tooeleite dissolution was characterized by the preferential releases of SO₄²⁻ anions from solid surface into aqueous medium, which was fundamentally controlled by the Fe-O/OH bond breakages and the outer OH⁻ group layers. From the data of the dissolution at 25 °C and initial pH 2 for 270–330 d, the ion-activity product [logˍIAP], which equaled the solubility product [K_sp] at the dissolution equilibrium, and the Gibbs free energy of formation [ΔG_f^o] were estimated as −200.28 ± 0.01 and −5180.54 ± 0.07 kJ/mol for the synthetic tooeleite, respectively. Full article

The effects of curing temperature, blast furnace slag content, and Ms on the initial and final setting times, and compressive strengths of geopolymer paste and mortars are examined. The present work demonstrates that ambient-cured geopolymer pastes and mortars can be fabricated without requiring high alkalinity activators or thermal curing, provided that the ratios of Class F fly ash (40–90 wt%), blast furnace slag (10–60 wt%), and low alkalinity sodium silicate (Ms = 1.5, 1.7, 2.0) are appropriately balanced. Eighteen mix designs were assessed against the criteria for setting time and compressive strength according to ASTM C150 and AS 3972. Using these data, flexible and reproducible mix designs in terms of the fly ash/slag ratio and Ms were mapped and categorised. The optimal mix designs are 30–40 wt% slag with silicate modulus (Ms) = 1.5–1.7. These data were used to generate predictive models for initial and final setting times and for ultimate curing times and ultimate compressive strengths. These projected data indicate that compressive strengths >100 MPa can be achieved after ambient curing for >56 days of mixes of ≥40 wt% slag. Full article

The study of active and fossil hydrothermal systems shows clay minerals to be a fundamental tool for the identification and characterization of hydrothermal alteration facies. The occurrence and composition of hydrothermal alteration facies could provide useful information on the physicochemical conditions of the hydrothermal activity affecting a rock volume. In particular, clay minerals (i.e., smectite group, chlorite, illite, kaoline group, pyrophyllite, biotite) are pivotal for extrapolating important parameters that strongly affect the development of water/rock interaction processes such as the temperature and pH of the hydrothermal environment. This work aims to give a general reference scheme concerning the occurrence of clay minerals in hydrothermal alteration paragenesis, their significance, and the information that can be deduced by their presence and chemical composition, with some examples from active and fossil hydrothermal systems around the world. The main mineralogical geothermometers based on chlorite and illite composition are presented, together with the use of hydrogen and oxygen isotope investigation of clay minerals in hydrothermal systems. These techniques provide a useful tool for the reconstruction of the origin and evolution of fluids involved in hydrothermal alteration. Finally, a list of oxygen and hydrogen fractionation factor equations between the main clay minerals and water is also provided. Full article

Geochemical and mineralogical characterization studies play an important role in the definition of mineral deposits. Each mineral system has a unique set of minerals with different chemical makeup and physical properties. Platinum-group elements (PGEs), for example, are scarce resources with many applications. The optimization of extraction process efficiency is therefore crucial to prevent resource shortage and increased bulk prices. To improve the mineral liberation process, high throughput sensors must be added alongside the production line as part of fast process analysis implementation. Current analytical methods are either ineffective to assess PGE content, or unusable in the conditions of the processing facilities. This article shows how Laser-induced breakdown spectroscopy (LIBS) technology, developed by ELEMISSION Inc, can circumvent these drawbacks by enabling automated, ultra-fast, and precise quantitative mineral analyses in any working environment. The drill core samples that were used in this study were collected at the Stillwater platinum group element mine in the United States. The data used for the mineralogical database was validated using the TESCAN Integrated Mineral Analyzer (TIMA) instrument. Full article

The mature transgressive Albian quartz sands in the Miechów Synclinorium contain a poor (<1%) heavy mineral suite consisting of tourmaline, rutile, garnet, staurolite, ilmenite, zircon, monazite, kyanite, and gahnite. The other minerals, especially those containing Fe and Ti (e.g., biotite), are subordinate. Over 512 tourmaline grains from seven outcrops in the Miechów Segment were analysed using electron probe microanalysis (EPMA). The majority of grains belong to the alkali tourmaline group in which the X-site is dominated by Na (0.4 to 0.9 apfu). Detrital tourmalines are mainly dravite with a prevalent schorl end-member with average X_Mg values over 0.6. Apart from Mg and Fe, the other Y-site cations rarely exceed 0.1 apfu. Fluorine content is usually below the detection limit. Their chemical composition suggests that most tourmaline grains were sourced from Al-rich and Al-poor metapelites/metapsammites. The main source rocks for the Albian sands were rocks from low- to medium-grade metamorphism, probably from Al-rich quartz-muscovite schist and/or muscovite rich gneisses. Additional minor source rocks were granites and pegmatites coexisting with them. A comparison of the examined tourmaline to tourmaline from possible source areas indicates that these areas were located in the eastern part of the Bohemian Massif and/or eastern Sudetes. Full article

The country or mine of origin is an important economic and societal issue inherent in the diamond industry. Consumers increasingly want to know the provenance of their diamonds to ensure their purchase does not support inhumane working conditions. Governments around the world reduce the flow of conflict diamonds via paper certificates through the Kimberley Process, a United Nations mandate. However, certificates can be subject to fraud and do not provide a failsafe solution to stopping the flow of illicit diamonds. A solution tied to the diamonds themselves that can withstand the cutting and manufacturing process is required. Here, we show that multivariate analysis of LIBS (laser-induced breakdown spectroscopy) diamond spectra predicts the mine of origin at greater than 95% accuracy, distinguishes between natural and synthetic stones, and distinguishes between synthetic stones manufactured in different laboratories by different methods. Two types of spectral features, elemental emission peaks and emission clusters from C-N and C-C molecules, are significant in the analysis, indicating that the provenance signal is contained in the carbon structure itself rather than in inclusions. Full article

Turbidite-associated black shale of the Semanggol Formation is extensively distributed in the northwestern part of the Western Belt, Peninsular Malaysia. The black shale occurs as a dark grey to black and thick to medium-bedded deposit. It represents the distal part of submarine fan system (outer-fan) overlying interbedded sandstone to shale facies of the mid-fan and conglomeratic pebbly sandstone facies of the inner-fan. Field observations and its widespread occurrence have resulted in the black shale being considered as a potential analog for a source rock in offshore Peninsular Malaysia. The present study includes detailed mineralogical (XRD, SEM, and EDX analysis), inorganic geochemical (major oxides, trace elements TEs, and rare earth elements REEs), and Rock-Eval pyrolysis analyses of the black shale samples, collected from the Gunung Semanggol, Bukit Merah, and Nami areas in northwestern Peninsular Malaysia. The primary focus of this study is to investigate the provenance, paleoredox conditions, paleoclimate, sedimentary rate, paleoproductivity, and upwelling system that would be helpful to understanding the role of these parameters in the enrichment of organic matter (OM) in the black shale. The Rock-Eval analysis shows that the black shale of the Semanggol Formation comprises type-III kerogens, which suggests organic input from a terrestrial source. The black shale also contains mature to postmature organic matter. Based on the mineralogical analysis, the mineral composition of the black shale comprises illite and kaolinite, with abundant traces of quartz and feldspar as well as few traces of titanium and zircon. Inorganic geochemical data designate black shale deposition in a passive margin setting that has experienced moderate to strong weathering, semi-arid to hot arid climate, and moderate sedimentation rate. Ratios of Ni/Co, U/Th, and V/(V+Ni) along with slightly negative to positive Ce* anomalies and U_EF-Mo_EF cross-plot unanimously indicate anoxic/dysoxic water conditions that are suitable for organic matter preservation. Geochemical proxies related to modern upwelling settings (i.e., Cd/Mo, Co vs. Mn) show that the deep marine black shale was strongly influenced by persistent upwelling, a first-order controlling factor for organic matter enrichment in the distal part (outer fan of the submarine fan system) of the Semanggol Basin. However, productivity-controlled upwelling and a high sedimentary rate, as well as high-productivity in oxygen-depleted settings without strong anoxic conditions, has played an essential role in the accumulation of organic matter. Full article

While the first part of this study took a detailed look at the properties, defects and classification of brown diamonds with deformation-related (DR) brown color and compared them to pink to purple to red diamonds, this second part covers diamonds with non-deformation-related (referred to as NDR in this study) brown color, including diamonds with treatment-induced brown color and synthetic brown diamonds. It was found that the natural NDR brown diamonds include CO₂ and Pseudo CO₂ diamonds as well as certain hydrogen-rich diamonds. Based on these, the new classification of NDR brown diamonds has been elaborated, resulting in 5 different classes. The detailed defect study performed has shown and confirmed the complexity of the CO₂ and Pseudo CO₂ diamonds; the probable link between structurally bound oxygen and some of the spectroscopic features such as the 480 nm absorption band is apparent in these diamonds. One of the most interesting findings was made through the low temperature NIR spectroscopy of some usually hydrogen-rich diamonds, which has defined a defect of great interest, the 1330 nm center; we suggest that this defect, together with the many lines in the 970 to 1000 nm range—referred to as the 990 nm series in this study—are responsible for the complex UV-Vis-NIR spectra seen of these diamonds. The results indicate that both features are nickel-nitrogen-related defects, the 1330 nm defect without involvement of hydrogen and the 990 nm series likely with hydrogen involved. Another surprising result was that during various treatment experiments performed we created dark orangish brown color in originally pale yellow “cape” diamonds by HPHT treatment at 2500 °C. It is suggested that the creation of this brown hue is related to the destruction or transformation of the N3 center at such extreme conditions. Full article

Four kinetic models are studied as first-order reactions with flotation rate distribution f(k): (i) deterministic nth-order reaction, (ii) second-order with Rectangular f(k), (iii) Rosin–Rammler, and (iv) Fractional kinetics. These models are studied because they are considered as alternatives to the first-order reactions. The first-order representation leads to the same recovery R(t) as in the original domain. The first-order R_∞-f(k) are obtained by inspection of the R(t) formulae or by inverse Laplace Transforms. The reaction orders of model (i) are related to the shape parameters of first-order Gamma f(k)s. Higher reaction orders imply rate concentrations at k ≈ 0 in the first-order domain. Model (ii) shows reverse J-shaped first-order f(k)s. Model (iii) under stretched exponentials presents mounded first-order f(k)s, whereas model (iv) with derivative orders lower than 1 shows from reverse J-shaped to mounded first-order f(k)s. Kinetic descriptions that lead to the same R(t) cannot be differentiated between each other. However, the first-order f(k)s can be studied in a comparable domain. Full article

Naturally occurring biogenic pyrite has been found in Holocene fluvial aquifers in the Uphapee watershed, Macon County, Alabama. The electron microprobe (EMP) analysis showed that the pyrite grains contain 0.20–0.92 weight% of arsenic (As). The scanning electron microscope and energy dispersive spectroscopy (SEM-EDS) analysis confirmed a similar concentration of As in the pyrite that was consistent with the EMP analysis. The SEM analysis also confirmed the presence of additional trace elements such as cobalt (0.19 wt.%), and nickel (0.15 wt.%), indicative of pyrite’s capacity to sequester As and other trace elements. Pyrite grains were naturally formed and developed as large (20–200 μm) euhedral (i.e., cube, octahedron) crystals and non-framboid aggregates. However, the inductively coupled plasma mass spectrometry (ICP-MS) analysis showed that the As concentration in the groundwater was not high, and it was within the EPA drinking water standard for As (10 µg/L). These results indicate that dissolved As is sequestered in naturally formed pyrite found in the fluvial sediments. The groundwater was moderately reducing to slightly oxidizing (Eh = 46 to173 mV), and nearly neutral to slightly acidic (pH = 5.53 to 6.51). Groundwater geochemistry data indicated a redox sequence of oxidation, denitrification, Mn(IV) reduction, Fe(III) reduction, and sulfate reduction along the flow path in the fluvial aquifer. The downgradient increases in dissolved Mn and then Fe concentrations reflect increased Mn(II) and Fe(II) production via microbial competition as the aquifer becomes progressively more reduced. Bacterial sulfate reduction seems to dominate near the end of the groundwater flow path, as the availability of Mn- and Fe-oxyhydroxides becomes limited in sediments rich in lignitic wood where increasing sulfate reduction leads to the formation of biogenic pyrite. The groundwater is a Ca-SO₄ type and is not SO₄ limited; thus, sulfate may serve as an electron acceptor for the bacterial sulfate-reducing reactions that sequester As into pyrite, which in turn results in very low groundwater As concentration (<2 µg/L). Full article

In order to study the liberation characteristics of different macerals in coal, one must improve the liberation degree of macerals in coal and promote the utilization of macerals based on their properties. Based on the idea of quick cooling to change the brittleness and toughness of different macerals, the characteristics of macerals in coal are studied here by liquid nitrogen quenching pretreatment. In particular, coarse-grained samples (with a particle size of 1–3 mm) were. For this study, coal samples were sourced from the Yan’an Formation (J₂y), a middle Jurassic coal formation in the Huangling no. 1 coal mine, located in northern Shaanxi Province, China. Firstly, we analyzed the coal properties and coal petrographic characteristics by the Chinese national standard method. Secondly, the distribution characteristics of macerals in different particle sizes (>0.9, 0.5–0.9, 0.1–0.5, and <0.1) were studied. Then, the samples with different particle sizes were quenched with or without liquid nitrogen to obtain the experimental group and blank group products. Finally, the differences in the liberation characteristics between the experimental group and the blank group products were studied via analyzing the micromorphology, specific surface area, pore volume, pore size and liberation degree. Our results for the particles size and liberation degree analysis indicate that inertinite and vitrinite were enriched in the coarse particles (>0.5 mm) and fine particles (<0.1 mm) here, respectively. Moreover, quenching pretreatment could contribute to the liberation of different macerals from coal, mainly because of the different effects of stress on the different components when they suddenly encounter cold, and this kind of liberation is mainly arc-shaped liberation between different macerals. In addition, along with the above results, this paper presents an optimized model for the liberation of macerals based on a combination of screening, liquid nitrogen quenching pretreatment and re-crushing. Full article

This study investigated the influence of different cooling regimes on the microstructure and consequent reactivity of belite-sulfoaluminate clinkers. The cement clinkers were synthesized by incorporating secondary raw materials, such as titanogypsum and bottom ash, to the natural raw materials. Clinker phases were determined by Rietveld quantitative phase analysis, while the distribution morphology and the incorporation of substitute ions in the phases were characterized by scanning electron microscopy using energy-dispersive X-ray spectroscopy (SEM/EDS). Clinker reactivity was studied using isothermal calorimetry and was additionally investigated through compressive strength, which was determined for the cement prepared from the synthesized clinkers. X-ray diffraction analysis showed that, as well as the three main phases (belite, calcium sulfoaluminate, and ferrite), the clinkers contained additional minor phases (mayenite, gehlenite, arkanite, periclase, and perovskite), the ratios of which varied according to the cooling regime utilized. Microscopic observations indicated that the cooling regime also influenced the crystal size and morphology of the main phases, which consequently affected clinker reactivity. Furthermore, a smaller amount of substitute elements was incorporated in the main phases when cooling was slowed. Results showed that, in comparison to clinkers cooled at slower rates, air quenched clinkers reacted faster and exhibited a higher compressive strength at 7 days. Full article

Acid mine drainage (AMD) is globally recognized as one of the environmental pollutants of the priority concern due to high concentrations of toxic metals and sulfates. More rigorous environmental legislation requires exploitation of effective technologies to remove toxic metals from contaminated streams. In view of high selectivity, effectiveness, durability, and low energy demands, the separation of toxic metal ions using immobilized membranes with admixed extractants could ameliorate water quality. Cellulose triacetate based polymer inclusion membranes (PIMs), with extractant and plasticizer, were studied for their ability to transport of As(V) ions from synthetic aqueous leachates. The effects of the type and concentration of extractant, plasticizer content, and sulfuric acid concentration in source phase on the arsenic removal efficiency have been assessed. Under the best of applied conditions, PIM with Cyanex 921 as extractant and o-nitrophenyl octyl ether (o-NPOE) as plasticizer showed high repeatability and excellent transport activity for selective removal of As(V) from AMD. Full article

The Ross(–Delamerian) Orogeny significantly impacted the formation of the tectonic structure of the Pacific Gondwana margin during the early Paleozoic era. Northern Victoria Land (NVL) in Antarctica preserves the aspect of the Ross Orogeny that led to the union of the Wilson (WT)–Bowers (BT)–Robertson Bay Terrane. The aspect of the Ross Orogeny in the NVL is characterized by subduction of oceanic domains toward the continental margin (continental arc) and the accretion of the associated marine–continental substances from 530–480 Ma. In the Mountaineer Range in NVL, the Ross Orogeny strain zone is identified at the WT/BT boundary regions. In these areas, fold and thrust shear zones are observed and aspects of them can be seen at Mt. Murchison, the Descent Unit and the Black Spider Greenschist zone. The Dessent Unit corresponds to a tectonic slice sheared between the WT and BT. The metamorphic evolution phase of the Dessent Unit is summarized in the peak pressure (M₁), peak temperature (M₂) and retrograde (M₃). The sensitive high-resolution ion microprobe (SHRIMP) zircon U–Pb ages of 514.6 ± 2.0 Ma and 499.2 ± 3.4 Ma obtained from the Dessent Unit amphibolite are comparable to the M₁ and M₂ stages, respectively. The Dessent Unit underwent intermediate pressure (P)/temperature (T)-type metamorphism characterized by 10.0–10.5 kbar/~600 °C (M₁) and ~7 kbar/~700 °C (M₂) followed by 4.0–4.5 kbar/~450 °C (M₃). Mafic to intermediate magmatism (497–501 Ma) within the WT/BT boundary region may have given rise to the M₂ stage of the Dessent Unit, and this magmatism is synchronous with the migmatization period of Mt. Murchison (498.3 ± 3.4 Ma). This indicates that a continuous process of fold-shearing–magmatic intrusion–partial melting, which is typically associated with a continental arc orogeny, occurred before and after c. 500 Ma in the Mountaineer Range. During the Ross Orogeny, the Dessent unit was initially subducted underneath the WT at depth (10.0–10.5 kbar, ~35 km) and then thrust into the shallow (~7 kbar, ~23 km), hot (≥700 °C) magmatic arc docking with the Mt. Murchison terrain, where migmatization prevailed. Full article

Fire hazard assessment in coal mines is performed on the basis of concentrations of particular gases emitted from the heating coal deposit, but more precise criteria and indicators are needed to assess fire hazard properly—both during the temperature rise phase and in the coal bed cooling phase. In the paper the impact of coal grinding on hazard assessment of spontaneous fire development in the coal deposit during heating and cooling the fire source was analyzed. The intensity of desorption of ethane, ethylene, propane, propylene, acetylene, carbon monoxide and hydrogen is the resultant of temperature and grinding of coal samples. The results proved that the ratio of concentrations emitted by standard versus coarsely crushed coal for each of the gases, changed both in the growth phase as well as in the temperature drop phase. It was found that as the temperature rose, the effect of coal grinding on the release of ethane, ethylene, propane, propylene and carbon monoxide decreased. The greatest effect of coal grinding was observed in the case of ethane and propane, while the lowest in the case of hydrogen and carbon monoxide. Full article

Slags coming from stainless steel (SS) and ferrochromium (FeCr) production generally contain between 1 and 10% Cr, mostly present in entrapped metallic particles (Fe–Cr alloys) and in spinel structures. To recover Cr from these slags, magnetic and gravity separation techniques were tested for up-concentrating Cr in a fraction for further processing. In case of SS slag and low carbon (LC) FeCr slag a wet high intensity magnetic separation can up-concentrate Cr in the SS slag (fraction <150 µm) from 2.3 wt.% to almost 9 wt.% with a yield of 7 wt.%, and in the LC FeCr slag from 3.1 wt.% to 11 wt.% with a yield of 3 wt.%. Different behavior of Cr-containing spinel’s in the two slag types observed during magnetic separation can be explained by the presence or absence of Fe in the lattice of the Cr-containing spinel’s, which affects their magnetic susceptibility. The Cr content of the concentrates is low compared to chromium ores, indicating that additional processing steps are necessary for a recovery process. In the case of high carbon (HC) FeCr slag, a Cr up-concentration by a factor of more than three (from 9 wt.% to 28 wt.%) can be achieved on the as received slag, after a single dry low intensity magnetic separation step, due to the well-liberated Cr-rich compounds present in this slag. After gravity separation of the HC FeCr slag, a fraction with a Cr content close to high grade Cr ores (≥50% Cr₂O₃) can be obtained. This fraction represents 12 wt.% of the HC FeCr slag, and can probably be used directly in traditional smelting processes. Full article

Mineral surface wettability and its regulation by the adsorption of collectors have an important influence on the flotation performance. The adsorption behavior of C₁₈ fatty acid with different unsaturation and its effect on rhodochrosite wettability was investigated with surface tension, contact angle, and atomic force microscopy (AFM) measurements. The results indicated that rhodochrosite hydrophobicity increased with the increasing concentration of fatty acid, along with the maximum contact angle (θ_max) between hemimicelle concentration (HMC) and critical micelle concentration (CMC). Oleic acid (OA), linoleic acid (LA), and α-linolenic acid (ALA) had a higher θ_max than stearic acid (SA), but the value decreased with the increase of C=C bond number. Besides, preferential adsorption of unsaturated fatty acids on the liquid-air interface can be attributed to the molecule’s steric hindrance resulting from C=C double bond, and the θ kept almost invariant with a higher value of Γ_LG than Γ_SL until HMC. The oriented monolayer and bilayer structure of fatty acids formed gradually on rhodochrosite surface with increasing concentration. However, the θ_max may not necessarily correspond to the beginning of bilayer formation. Cylindrical monolayer and bilayer micelles of SA molecules were observed on rhodochrosite surface at HMC and CMC, respectively. While bilayer structures of unsaturated fatty acids formed before complete coverage of monolayer on rhodochrosite surface because of surface heterogeneity. This work provided a good understanding on the adsorption mechanism of fatty acid on rhodochrosite for flotation. Full article

The Doig Phosphate Zone (DPZ) is a phosphate-bearing marine unit located at the base of the Doig Formation, in the Triassic section of the Western Canada Sedimentary Basin. The DPZ has a maximum thickness of 90 m and extends across northeastern British Columbia and west-central Alberta. In this study, we characterize the significance and interpret the origin of apatite in the DPZ through mineralogical and geochemical analyses, thin section study, and field emission scanning electron microscopy. The occurrence of apatite in the DPZ is not evenly distributed but restricted to discrete 10 to 20 cm thick beds, located near the base of the DPZ. Phosphorites are of two types: grainstones composed primarily of unconformity-bounded coated grains, and intraclastic phosphorites composed of detrital silt-sized grains and apatite coated grains in a cryptocrystalline phosphatic matrix. The phosphorite beds are records of stratigraphic condensation due to low detrital input during transgression. The erosionally truncated phosphatic coated grains and intraclasts are interpreted to be a result of various phases of phosphatization, exhumation, erosion, reworking, winnowing, and redeposition in alternating quiescence and storms or bottom currents. The abundance of pyrite and chalcophile trace elements, as well as the low concentration of proxy elements for organic matter productivity and preservation, are further evidence of stratigraphic condensation, with sulfidic pore water development and extensive organic recycling promoted by biological activity during the long exposure times. The phosphorites were formed under oxygenated water conditions, as suggested by the depletion in Ce and the presence of a diverse benthic fauna. Full article

For this study, the properties of a large sample of various types of brown diamonds with a deformation-related (referred to as “DR” in this work) color were studied to properly characterize and classify such diamonds, and to compare them to pink to purple to red diamonds. The acquisition of low temperature NIR spectra for a large range of brown diamonds and photoexcitation studies combined with various treatment experiments have opened new windows into certain defect characteristics of brown diamonds, such as the amber centers and naturally occurring H1b and H1c centers. It was determined that the amber centers (referred to as “AC” in this work) exhibit rather variable behaviors to annealing and photoexcitation; the annealing temperature of these defects were determined to range from 1150 to >1850 °C and it was found that the 4063 cm⁻¹ AC was the precursor defect of many other ACs. It is suggested that the amber centers in diamonds that contain at least some C centers are essentially identical to the ones seen in diamonds without C centers, but that they likely have a negative charge. The study of the naturally occurring H1b and H1c link them to the amber centers, specifically to the one at 4063 cm⁻¹. Annealing experiments have shown that the H1b and H1c defects and the 4063 cm⁻¹ AC were in line with each other. The obvious links between these defects points towards our suggestion that the H1b and H1c defects are standalone defects that consist of multiple vacancies and nitrogen and that they are—in the case of brown diamonds—a side product of the AC formation. A new classification of DR brown diamonds was elaborated that separates the diamonds in six different classes, depending on type and AC. This classification had been completed recently with the classification of brown diamonds with a non-deformation-related color (referred to as “NDR”), giving a total of 11 classes of brown diamonds. Full article

Recent discoveries have demonstrated that the surfaces of Mars, Ceres and other celestial bodies, as well as asteroids and comets, are characterized by the presence of ammonium-bearing minerals. A careful study of remote data compared with the analyses of more accurate laboratory data might allow a better remote characterization of planetary bodies. In this paper, the reflectance spectra of some ammoniated hydrous and anhydrous salts, namely sal-ammoniac NH₄Cl, larderellite (NH₄)B₅O₇(OH)₂·H₂O, mascagnite (NH₄)SO₄, struvite (NH₄)MgPO₄·6H₂O and tschermigite (NH₄)Al(SO₄)₂·12H₂O, were collected at 293 and at 193 K. The aim is to detect how the NH₄ vibrational features are affected by the chemical and structural environment. All samples were recovered after cooling cycles and were characterized by X-ray powder diffraction. Reflectance spectra of the studied minerals show absorption features around 1.3, 1.6, 2.06, 2.14, 3.23, 5.8 and 7.27 μm, related to the ammonium group. Between them, the 2ν₃ at ~1.56 μm and the ν₃ + ν₄ at ~2.13 μm are the most affected modes by crystal structure type, with their position being strictly related to both anionic group and the strength of the hydrogen bonds. The reflectance spectra of water-rich samples [struvite (NH₄)MgPO₄·6(H₂O) and tschermigite (NH₄)Al(SO₄)₂·12(H₂O)] show only H₂O fundamental absorption features in the area from 2 to 2.8 μm and a band from hygroscopic water at 3 μm. Thermal analyses (TA), thermal gravimetry (TG) and differential scanning calorimetry (DSC) allowed to evaluate the dehydration temperatures and the occurring phase transitions and decompositions in the analyzed samples. In almost all samples, endothermic peaks at distinct temperatures were registered associated to loss of water molecules, differently linked to the structures. Moreover, an endothermic peak at 465 K in sal-ammoniac was associated to the phase transition from CsCl to NaCl structure type. Full article