Crocoite: an unusual mode of occurrence for lead in coal

What is believed to be a very unusual mode of occurrence for lead in coal has been identified as crocoite (PbCrO₄). As part of a larger study on trace elements and mineralogy in the Cretaceous Main Seam in New Zealand, crocoite was found in raw coal samples within the lower part of the coal seam. X-ray diffraction (XRD) and bulk chemical data from a SEM equipped with an energy dispersive X-ray analyser (EDXA) have confirmed the identity of this mineral. This is apparently the first time that crocoite has been reported in coal. Crocoite usually occurs only in the oxidised zone of lead mineral deposits. The occurrence of this mineral in the Main Seam coal implies that the deposit was exposed to an oxidising environment at some stage, most likely after coalification.     

Calcite and barite precipitation in CaCO<Subscript>3</Subscript>-BaSO<Subscript>4</Subscript>-NaCl and BaSO<Subscript>4</Subscript>-NaCl-CaCl<Subscript>2</Subscript> aqueous systems: kinetic and microstructural study

During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca²⁺ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO₄° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO₃)₂-BaSO₄-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.     

Fluoride hydrogeochemistry and bioavailability in groundwater and soil of an endemic fluorosis belt,central Iran

Presence of fluoride in groundwater is a public health problem in the so-called endemic fluorosis belt of the central Iran, where the groundwater is the major source of drinking water in most urban and rural areas. Therefore, an attempt has been made to determine the hydrogeochemical factors controlling fluoride enrichment in the groundwater resources at this belt. Fluoride concentrations ranged from 0.20 to 1.99 mg/L (1.02 ± 0.47) in groundwater samples. The presence of different F-bearing minerals and also clay minerals in the soils and aquifer materials was confirmed using XRD analysis. To identify probable sources of dissolved F^? and investigate groundwater quality, multivariate statistical analyses were carried out. Geochemical modeling indicated that all samples were undersaturated with respect to fluorite, halite, gypsum and anhydrite and mostly oversaturated with respect to calcite and dolomite. Contrary to most high-fluoride regions in the World, the high F^? content was dominated by Na–Cl- and Ca–SO₄-type groundwater in the study area. Besides, fluoride showed negative relationship with pH and HCO₃ ^? in groundwater. In order to assess the bioavailability of fluoride in soils, a two-step chemical fractionation method was applied. The results showed that fluoride in soils mostly accompanied with the residual and water-soluble fractions and was poorly associated with soil’s bonding sites. Calculated aqueous migration coefficient demonstrated that fluoride in the studied soils was mobile to easily leachable to the groundwater. Finally, the results demonstrated that combination of water–rock interaction and influence of clay minerals is geochemical mechanism responsible for controlling fluoride enrichment in groundwater.     

Calcite twinning strain variations across the Proterozoic Grenville orogen and Keweenaw-Kapuskasing inverted foreland,USA and Canada

We report the calcite twinning strain results of a traverse across the Grenville orogen from Parry Sound, Ontario (NW) to Ft. Ann, New York (SE), including the younger, adjacent Ordovician Taconic allochthon. Fifty four carbonates (marbles, calcite veins, Ordovician limestone) were collected resulting in 68 strain analyses on mechanically twinned calcite (n = 2337 grains) across the Central Gneiss Belt (CGB; 3 samples), the Central Metasedimentary Belt (CMB; 27 samples), the Central Granulite Terrane (CGT; Adirondack's; 13 samples) and the Ottawan Orogenic Lid (OOL; 11 samples). Twinning strains in the greenschist-grade OOL marbles preserve N–S shortening and U-Pb titanite ages (～1150 Ma; n = 4) document these marbles formed during the Shawinigan (1190–1140 Ma) part of the Grenville orogen. From northwest to southeast, the Ottawan (1095–1020 Ma) twinning strain is dominantly a layer-parallel shortening fabric oriented N–S (Parry Sound), then becomes parallel to the Grenville thrust direction (NW–SE) across the CMB to the Adirondack Highlands where the sub-horizontal shortening strain becomes margin-parallel (SW–NE). Within the regional sample suite there are two areas studied in detail, the Bancroft shear zone (n = 11) and a roadcut on the southeast side of the Adirondack Mountains (Ft. Ann, NY; n = 8). Marbles from the Bancroft shear zone contain calcite grains with 2 sets of twin lamellae (e₁ and e₂). The better-developed e₁ sets (n = 406) record a horizontal fabric oriented NW–SE whereas the younger e₂ lamellae (n = 146) preserve a margin-parallel (SW–NE) horizontal fabric. Both the e₁ and e₂ strains record an overprint vertical shortening strain (NEV), perhaps related to extensional orogenic collapse. We also report an Ottawan orogen-aged granoblastic mylonite (1093 Ma, U-Pb zircon; 1102 Ma Ar-Ar biotite) in the Keweenaw thrust hanging wall 500 km inboard of the Grenville front and interpret the relations of Grenville-Keweenaw far-field dynamics.     

Chemical Dynamics and Evaluation of Biogeochemical Processes in Alpine River Kamniška Bistrica, North Slovenia

Biogeochemical processes were investigated in alpine river—Kamni?ka Bistrica River (North Slovenia), which represents an ideal natural laboratory for studying anthropogenic impacts in catchments with high weathering capacity. The Kamni?ka Bistrica River water chemistry is dominated by HCO₃ ^?, Ca²⁺ and Mg²⁺, and Ca²⁺/Mg²⁺ molar ratios indicate that calcite weathering is the major source of solutes to the river system. The Kamni?ka Bistrica River and its tributaries are oversaturated with respect to calcite and dolomite. pCO₂ concentrations were on average up to 25 times over atmospheric values. δ¹³C_DIC values ranged from ?12.7 to ?2.7 ‰, controlled by biogeochemical processes in the catchment and within the stream; carbonate dissolution is the most important biogeochemical process affecting carbon isotopes in the upstream portions of the catchment, while carbonate dissolution and organic matter degradation control carbon isotope signatures downstream. Contributions of DIC from various biogeochemical processes were determined using steady state equations for different sampling seasons at the mouth of the Kamni?ka Bistrica River; results indicate that: (1) 1.9–2.2 % of DIC came from exchange with atmospheric CO₂, (2) 0–27.5 % of DIC came from degradation of organic matter, (3) 25.4–41.5 % of DIC came from dissolution of carbonates and (4) 33–85 % of DIC came from tributaries. δ¹⁵N values of nitrate ranged from ?5.2 ‰ at the headwater spring to 9.8 ‰ in the lower reaches. Higher δ¹⁵N values in the lower reaches of the river suggest anthropogenic pollution from agricultural activity. Based on seasonal and longitudinal changes of chemical and isotopic indicators of carbon and nitrogen in Kamni?ka Bistrica River, it can be concluded that seasonal changes are observed (higher concentrations are detected at low discharge conditions) and it turns from pristine alpine river to anthropogenic influenced river in central flow.     

Structural change in lead fluorapatite at high pressure

The structure of lead fluorapatite [PbFAP; Pb₁₀(PO₄)₆F₂], crystallized from the melt in a platinum capsule at 1,000°C and 1 atm, has been investigated by single-crystal X-ray diffraction. Crystal data are a = 9.7638 (6), c = 7.2866 (4) Å, space group P6₃/m, R = 0.043, R _w = 0.034. We have also studied the compressional behaviour of the c-axis channel of PbFAP up to 9 GPa at 25°C, using a diamond-anvil cell, synchrotron X-radiation, and Rietveld powder structure refinement. Pressure–volume data for the channel polyhedron of PbFAP fitted to the third-order Birch–Murnaghan equation resulted in K _T  = 33.2 ± 1.2 GPa when K _T ′ is fixed at 4. The c-axis channel of PbFAP is about twice as compressible as the unit-cell volume of PbFAP and the channel of calcium apatites. This is attributed to the anomalous narrowing of the channel of PbFAP with increase in confining pressure. Flexibility of the apatite channel is a key factor in the scavenging of toxic heavy metals by calcium apatites.     

Assessment of sandstone deterioration at Ta Keo temple (Angkor): first results and future prospects

A first application of geomorphological methods to the assessment of sandstone deterioration at Angkor is presented. Damage diagnosis was carried out on the first eastern tier of the central pyramid of the 1,000 year-old Ta Keo temple. Methods combine field observations and measurements at 230 sampling points, high-resolution lasergrammetry and stereophotogrammetry on a 2-m² test zone, and SEM observations. The first results indicate that decay operates through a synergistic combination of weathering phenomena dominated by scaling and solution, and exhibits a high spatial variability. Percentages of deteriorated surfaces vary from 17.6 to 93.8%, and average stone recession values from 0.00 to 2.71 cm (minimum) and 0.34 to 5.49 cm (maximum). On the test-zone, stereophotogrammetry and 3D-mapping of the present and reconstructed initial states using lasergrammetry indicate that erosion scars up to 6 cm deep have formed since 1963. On the whole, the amount of deteriorated surfaces more than tripled between 1963 and 2008. The degree of implication of salts in stone decay remains unclear for most efflorescences are composed of calcite (CaCO3), with secondary importance of barite (BaSO4) and gypsum (CaSO₄·2H₂O). Future prospects aim to evaluate the impact on stone decay of the clearing out of the temple from the forest in the 1920s.     

Heavy metal pollution in urban topsoils: mineralogical analyses and magnetic characterization

Urban soil samples collected from the city of Xuzhou were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for Pb and Zn. The samples were also investigated for mineralogy using X-ray diffraction, thermal analyses and scanning electron microscopy (SEM). The identified minerals are mainly composed of quartz and calcite as major minerals. Soil samples contained elevated Zn (2,049 ± 5,439 mg/kg) and Pb (115 ± 58 mg/kg). According to the index of geoaccumulation, the soils of the study area are considered to be moderately to strongly contaminated with respect to Zn, moderately contaminated with respect to Pb. The magnetic measurements indicate that the dominant magnetic components are multidomain grains of ferrimagnetic minerals and that superparamagnetic and stable single-domain ferrimagnetic grains and non-ferrimagnetic minerals are present in small magnetic concentrations in this area. The measured metals correlated positively with the determined magnetic parameters (χ, χ _ARM, SIRM and SOFT). This result suggests that simple, rapid, and non-destructive magnetic measurements could provide useful information about Pb and Zn pollution in Xuzhou urban surface soils.     

Genesis of wollastonite- and grandite-rich skarns in a suite of marble-calc-silicate rocks from Sittampundi, Tamil Nadu: constraints on the P–T–fluid regime in parts of the Pan-African mobile belt of South India

The Pan-African tectonothermal activities in areas near Sittampundi, south India, are characterized by metamorphic changes in an interlayered sequence of migmatitic metapelites, marble and calc-silicate rocks. This rock sequence underwent multiple episodes of folding, and was intruded by granite batholiths during and subsequent to these folding events. The marble and the calc-silicate rocks develop a variety of skarns, which on the basis of mineralogy; can be divided into the following types: Type I: wollastonite?+?clinopyroxene (mg#?=?71–73)?+?grandite (16–21 mol% Adr)?+?quartz?±?calcite, Type II: grandite (25–29 mol% Adr )?+?clinopyroxene (mg#?=?70)?+?calcite?+?quartz, and Type III: grandite (36–38 mol% Adr)?+?clinopyroxene (mg#?=?55–65)?+?epidote?+?scapolite?+?calcite?+?quartz. Type I skarn is 2–10 cm thick, and is dominated by wollastonite (>70 vol%) and commonly occurs as boudinaged layers parallel to the regional foliation Sn₁ related to the Fn₁ folds. Locally, thin discontinuous lenses and stringers of this skarn develop along the axial planes of Fn₂ folds. The Type II skarn, on the other hand, is devoid of wollastonite, rich in grandite garnet (40–70 vol%) and developed preferentially at the interface of clinopyroxene-rich calc-silicates layers and host marble during the later folding event. Reaction textures and the phase compositional data suggest the following reactions in the skarns: 1. calcite?+?SiO₂?→?wollastonite?+?V, 2. calcite?+?clinopyroxene?+?O₂?→?grandite?+?SiO₂?+?V, 3. scapolite?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V and 4. epidote?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V Textural relations and composition of phases demonstrate that (a) silica metasomatism of the host marble by infiltration of aqueous fluids (X_CO2?<?0.15) led to production of large volumes of wollastonite in the wollastonite-rich skarn whereas mobility of FeO, SiO₂ and CaO across the interface of marble and calc-silicate and infiltration of aqueous fluids (X_CO2?<?0.35) were instrumental for the formation of grandite skarns. Composition of minerals in type II skarn indicates that Al₂O₃ was introduced in the host marble by the infiltrating fluid. Interpretation of mineral assemblages observed in the interlayered metapelites and the calcareous rocks in pseudosections, isothermal P-X_CO2 and isobaric T-X_CO2 diagrams tightly bracket the “peak” metamorphic conditions at c.9?±?1 kbar and 750°?±?30°C. Subsequent to ‘peak’ metamorphic conditions, the rocks were exhumed on a steeply decompressive P–T path. The estimated ‘peak’ P–T estimates are inconsistent with the “extreme” metamorphic conditions (>11 kbar and >950°C) inferred for the Pan-African tectonothermal events from the neighboring areas. Field and petrological attributes of these skarn rocks are consistent with the infiltration of aqueous fluid predominantly during the Fn₁ folding event at or close to the ‘peak’ metamorphic conditions. Petrological features indicate that the buffering capacity of the rocks was lost during the formation of type I and II skarns. However, the host rock could buffer the composition of the permeated fluids during the formation of type III skarn. Aqueous fluids derived from prograde metamorphism of the metapelites seem to be the likely source for the metasomatic fluids that led to the formation of the skarn rocks.     

Investigation of the hydrogeochemical processes in an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa

An investigation was conducted to assess the hydrogeochemical processes of an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa. The investigation was aimed at identifying and describing the groundwater chemistry evolution and its contribution to the overall groundwater quality. X-ray fluorescent spectrometry (XRF) and X-ray diffractometry (XRD) analyses were performed on geological samples to identify and quantify the major element oxides and minerals. The study utilises the conventional Piper diagram, bivariate plots and PHREEQC hydrogeochemical model to analyse groundwater chemistry data obtained during the wet (February and May) and dry seasons (August and December) of 2011. The XRF and XRD results show that the channel deposits are dominated by SiO₂ element oxides and quartz minerals, thus elevated concentrations of silicon (Si⁴⁺) were found in the groundwater. Dolomite and calcite minerals were also detected in the unconsolidated aquifer sediments. The detailed study of the alluvial aquifer system has shown that dissolution of dolomite and calcite minerals and ion exchange are the dominant hydrogeochemical processes influencing the groundwater quality. The groundwater evolves from Ca²⁺–Mg²⁺–HCO₃ ^? recharge water that goes through ion exchange with Na⁺ in the clay-silt sediment to give a Na⁺–HCO₃ ^? water type. The groundwater is supersaturated with respect to quartz, dolomite and calcite minerals. The study shows the potential usefulness of simple bivariate plots as a complimentary tool to the conventional methods for analyzing groundwater hydrogeochemical processes.     

Geochemical and mineralogical composition of black weathering crusts on limestones from seven different European countries

Twenty-seven samples of black weathering crust and host carbonates were studied from seven European countries (Germany, Hungary, Belgium, Czech Republic, France, Italy and Poland) representing 11 different sites. The samples were collected for sites for which long-term air pollution records are available. The mineralogical analyses (XRD, polarizing microscopy, SEM) have shown that despite decreasing SO₂ emissions crust samples are still very rich in gypsum. Further, in all host rock samples gypsum was also detected. Good correlations (R² > 0.9) were also found between water-soluble calcium and gypsum content and between sulphate and gypsum content both for black crusts and host rocks. The black gypsum crusts are four or five times richer in sulphate than the host rock. The conductivity of dissolved crust and host rock samples also shows a positive correlation with gypsum content of the samples. LA-ICP-MS analyses allowed the detection of high Pb-levels in black crusts and a negative shift in lead concentration at the crust/host rock transition. The lead content of the host rock is 2–5 mg/kg, while that of the crust is 3–25 mg/kg in the sample collected from Germany, while in the Belgian sample these values are 2–14 mg/kg and 80–870 mg/kg for the host rock and crust, respectively. The GC–MS technique allowed to detect the PAH content of black crusts and host rocks. The former one contains 0.6–15.6 (102.5) mg/kg, while in the host rock values between 0.2 and 2.4 mg/kg were found. The present study suggests that still large amounts of air pollution-related minerals and organic pollutants are found in the black weathering crusts of European carbonate buildings despite decreasing trends in air pollution.     

Transition metals (Mn,Ni, Co) doping in TiO<Subscript>2</Subscript> nanoparticles and their effect on degradation of diethyl phthalate

Transition metal-doped TiO₂ nanoparticles are synthesized by sol–gel method. The as-prepared samples are characterized by various techniques to correlate structural and optical properties with chemical nature of dopants and their effect on photocatalytic degradation of diethyl phthalate esters. X-ray diffraction (XRD) reveals that all the samples are crystalline and exhibit anatase as a major phase. Chemical nature of dopants could not affect the formation of anatase and its volume fraction. The crystallite size of undoped and doped TiO₂ nanoparticles varies between 10 and 12 nm as confirmed by XRD and transmission electron microscope. The lowest optical band gap observed is 2.47 eV in Mn-doped TiO₂. Among all the samples, Ni-doped TiO₂ sample shows better photocatalytic activity and degradation of diethyl phthalate due to its lower crystallite size and higher surface area than those of Mn- and Co-doped TiO₂ samples.     

Geochemical and isotope hydrological characterisation of geothermal resources at Godavari valley,India

Thermal waters at the Godavari valley geothermal field are located in the Khammam district of the Telangana state, India. The study area consists of several thermal water manifestations having temperature in the range 36–76 °C scattered over an area of ~35 km². The thermal waters are Na–HCO₃ type with moderate silica and TDS concentrations. In the present study, detailed geochemical (major and trace elements) and isotope hydrological investigations are carried out to understand the hydrogeochemical evolution of these thermal waters. Correlation analysis and principal component analysis (PCA) are performed to classify the thermal waters and to identify the different geochemical processes controlling the thermal water geochemistry. From correlation matrix, it is seen that TDS and EC of the thermal springs are mainly controlled by HCO₃ and Na ions. In PCA, thermal waters are grouped into two distinct clusters. One cluster represents thermal waters from deeper aquifer and other one from shallow aquifer. Lithium and boron concentrations are found to be similar followed by rubidium and caesium concentrations. Different ternary plots reveal rock–water interaction to be the dominant mechanism for controlling trace element concentrations. Stable isotopes (δ¹⁸O, δ²H) data indicate the meteoric origin of the thermal waters with no appreciable oxygen-18 shift. The low tritium values of the samples originating from deeper aquifer reveal the long residence time (>50 years) of the recharging waters. XRD results of the drill core samples show that quartz constitutes the major mineral phase, whereas kaolinite, dolomite, microcline, calcite, mica, etc. are present as minor constituents. Quartz geothermometer suggests a reservoir temperature of 100 ± 20 °C which is in good agreement with the values obtained from K–Mg and Mg-corrected K–Mg–Ca geothermometers.     

Palygorskite from cave sediments: case study from Wadi Haqil,United Arab Emirates

The x-ray powder diffraction identification of clay minerals both in bulk samples and in separated clay fraction confirmed the presence of palygorskite in samples of cave sediments from Wadi Haqil (the western slopes of Musandam Mountains; Ras Al-Khaimah Emirate, UAE). Samples contain quartz, gypsum, smectite, kaolinite, calcite, and palygorskite, some of them chlorite, illite, feldspars, and goethite. Calcite dominates in most samples; smectite prevails in clay fraction. After heating, the 001 reflection of chlorite shifts to higher diffraction angles and its intensity decreases; these features indicate that the chlorite represent a Fe-dominant species. Unit-cell dimensions of major phases as refined by the Rietveld method are in agreement with literature data. Chemical composition of palygorskite was derived from unit-cell dimensions as follows: MgO content is 11–14 wt% and Al₂O₃ 10–13 wt%. Clay mineralogy is only hard to ascertain from the scanning electron microscope (SEM) images even after being combined with the energy-dispersive spectrometer data. The SEM was also used to characterize gypsum grains; they often display flow deformation features. Studied cave sediments represent palygorskite-bearing weathering products and desert soils re-deposited from the cave surroundings by slope processes and wind and/or surface runoff. The mixture with other clay minerals, quartz, feldspars, etc. supports this interpretation. Fine-grained quartz fraction is probably wind-blown. Gypsum and calcite are the precipitates (crusts and/or cements), although gypsum can also be re-deposited from omnipresent gypsum-cemented surface sediments.     

Sulphur- and lead-isotope geochemistry of the Arapuçandere lead–zinc–copper deposit,Biga Peninsula,northwest Turkey

The Arapuçandere Pb–Zn–Cu ore body is a typical vein-type lead–zinc deposit of the Biga Peninsula, and is currently being mined for lead and zinc. In the study area, Permian–Triassic metamorphic rocks, Triassic metaclastic and metabasic rocks, Oligocene–Miocene granitoids, Miocene volcanic rocks, and Quaternary terrigenous sediments crop out. The ore deposits developed as Pb–Zn–Cu-bearing veins along faults in Triassic metasandstone and metadiabase. Microscopic studies reveal that the veins contain galena, sphalerite, chalcopyrite, pyrite, marcasite, covellite, and specular hematite as ore minerals, and quartz, calcite, and barite as gangue minerals. Analysed sulphur-isotope compositions (δ³⁴S_VCDT) of galena, sphalerite, and chalcopyrite range from ? 5.9 to ? 1.9‰ (average ? 3.4‰), from ? 5.5 to ? 1.7‰ (average ? 4.2 ‰), and from ? 3.5 to ? 0.9‰ (average ? 2.6‰), respectively; that of H₂S in the hydrothermal fluid was in the calculated range of ? 5.8 to +0.1‰ (average ? 2.5‰). These isotopic values suggest that magmatic sulphur dominates in sulphides, mixed with minor, isotopically light sulphur. Because no contemporaneous magmatic activity is associated with mineralization, it may be assumed that sulphur was leached from the surrounding Triassic units, mainly from metabasic, partly from metaclastic rocks. Lead-isotope studies indicate a model age of 114–63 Ma for the lead reservoir, in accord with possible sulphur-bearing local source rocks. Thus, the sulphur and lead deposited in the studied ore veins were probably leached from Triassic metabasic and metaclastic rocks some time during the Early Cretaceous to the Palaeocene.     

Assessment of chemical properties and hydro-geochemical coefficients at the Qareh Sou Basin,Golestan Province,Iran

This paper focuses on the Qareh Sou Basin in Golestan Province, Iran. Golestan Province is the third largest cereal producer in Iran and water scarcity and salinity are major problems in this area. This study attempts to facilitate the comprehension of system behavior with respect to water quality issues and hydro-geochemical coefficients within the Qareh Sou Basin. This study was carried out during the year 2010. Various parameters, such as pH, EC, chloride, sulfate, bicarbonate, sodium, potassium, calcium and magnesium have been determined for evaluation purposes. Then, Ca/Mg, Na/Cl, Mg/(Ca + Mg), Ca/HCO₃, (Ca + Mg)–(HCO₃ + SO₄), (Na + K)–Cl, (Ca + Mg + Na + K)–Cl, HCO₃ + SO₄, Ca + Mg and chloro-alkaline indices (CAI) were calculated. Results show that cation exchange probably is an important factor in the hydrochemistry and silicate mineral weathering. Also, CAI-1 plot against CAI-2 demonstrates that most of samples have positive values which suggest normal ion exchange in the system. The carbonic acid is the main agent of calcite, limestone and dolomite weathering which occurs in some stations. According to Chadha’s diagram, the type of water is determined as Ca–Mg–HCO₃.     

Weathering Processes in the Min Jiang: Major Elements, {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} }

We investigated the dissolved major elements, $ {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ composition of the Min Jiang, a headwater tributary of the Chang Jiang (Yangtze River). A forward calculation method was applied to quantify the relative contribution to the dissolved load from rain, evaporite, carbonate, and silicate reservoirs. Input from carbonate weathering dominated the major element composition (58–93%) and that from silicate weathering ranged from 2 to 18% in unperturbed Min Jiang watersheds. Most samples were supersaturated with respect to calcite, and the CO₂ partial pressures were similar to or up to ～5 times higher than atmospheric levels. The Sr concentrations in our samples were low (1.3–2.5 μM) with isotopic composition ranging from 0.7108 to 0.7127, suggesting some contribution from felsic silicates. The Si/(Na^* + K) ratios ranged from 0.5 to 2.5, which indicate low to moderate silicate weathering intensity. The $ \delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } \;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ for five select samples showed that the source of dissolved sulfate was combustion of locally consumed coal. The silicate weathering rates were 23–181 × 10³ mol/km²/year, and the CO₂ consumption rates were 31–246 × 10³ mol/km²/year, which are moderate on a global basis. Upon testing various climatic and geomorphic factors for correlation with the CO₂ consumption rate, the best correlation coefficients found were with water temperature (r ² = 0.284, p = 0.009), water discharge (r ² = 0.253, p = 0.014), and relief (r ² = 0.230, p = 0.019).     

Pink manganian phengite in a high P/T meta-conglomerate from northern Syros (Cyclades, Greece)

A new occurrence of Mn-rich rocks was discovered within the high-pressure/low-temperature metamorphic rocks on the Palos peninsula of Syros (Greece). Near the summit of Mount Príonas, a meta-conglomerate consists of calcite (~63 wt%), pink manganian phengite, blue–purple manganian aegirine–jadeite, microcline, albite and quartz. In addition, it contains abundant braunite-rich aggregates (up to ~1.5 cm in diameter) that include hollandite [(Ba_0.98–1.02K_<0.01Na_<0.02Ca_<0.03) (Mn _1.02–1.52 ³⁺ Fe _0.38–0.88 ³⁺ Ti_0.29–0.92Mn _5.11–5.76 ⁴⁺ )O₁₆], barite and manganian hematite. Due to metamorphic recrystallization and deformation, the contacts between clasts and matrix are blurred and most clasts have lost their identity. In back-scattered electron images, many aegirine–jadeite grains appear patchy and show variable jadeite contents (Jd_10–67). These pyroxenes occur in contact with either quartz or albite. Manganian phengite (3.41–3.49 Si per 11 oxygen anions) is of the 3T type and contains 1.4–2.2 wt% of Mn₂O₃. At the known P–T conditions of high-pressure metamorphism on Syros (~1.4 GPa/ 470 °C), the mineral sub-assemblage braunite + quartz + calcite (former aragonite) suggests high oxygen fugacities relative to the HM buffer (+7 ≤ ?f_O2 ≤ + 17) and relatively high CO₂ fugacities. The exact origin of the conglomerate is not known, but it is assumed that the Fe–Mn-rich and the calcite-rich particles originated from different sources. Braunite has rather low contents of Cu (~0.19 wt%) and the concentrations of Co, Ni and Zn are less than 0.09 wt%. Hollandite shows even lower concentrations of these elements. Furthermore, the bulk-rock compositions of two samples are characterized by low contents of Cu, Co and Ni, suggesting a hydrothermal origin of the manganese ore. Most likely, these Fe–Mn–Si oxyhydroxide deposits consisted of ferrihydrite, todorokite, birnessite, amorphous silica (opal-A) and nontronite. Al/(Al + Fe + Mn) ratios of 0.355 and 0.600 suggest the presence of an aluminosilicate detrital component.     

The electrical conductivity of calcite between 300 and 1200° C at a CO2 pressure of 40 bars

The electrical conductivity of calcite cleavage fragments was measured using direct current. Five temperature intervals, characterized by different activation energies of conduction, were established — T ₁: (300°)–500° C, T ₂: 500–725° C, T ₃: 725°–800° C, T ₄: 800°–985° C and T ₅: 985°–(1,200)° C. The data above 600° C indicate various intrinsic conduction mechanisms which are likely to be related to disorder in the CO₃-sublattice of calcite. The transitions between the temperature intervals T ₂-T ₃-T ₄ and T ₄-T ₅ are probably correlated with high-temperature transitions of calcite at 800° and 985° C. Measurement of the thermoelectric voltage indicates a conductivity dominated by negatively charged carriers.     

Assessment of hydrogeochemistry and contamination of Varamin deep aquifer,Tehran Province,Iran

The present study investigates the hydrogeochemistry and contamination of Varamin deep aquifer located in the southeast of Tehran province, Iran. The study also evaluates groundwater suitability for irrigation uses. The hydrogeochemical study was conducted by collecting and analyzing 154 groundwater samples seasonally during 2014. Based on evolutionary sequence of Chebotarev, the aquifer is in the stage of SO₄ + HCO₃ in the north half of the plain and it has evolved into SO₄ + Cl in the south half. The unusual increase in TDS and Cl^? toward the western boundaries of the aquifer indicates some anomalies. These anomalies have originated from discharge of untreated wastewater of Tehran city in these areas. The studied aquifer contains four dominant groundwater types including Na–Ca–SO₄ (55%), Na–Ca–HCO₃ (22%), Na–Cl (13%) and Ca–Cl (10%). The spatial distributions of Na–Cl and Ca–Cl water types coincide with observed anomalies. Ionic relationships of SO₄ ^2? versus Cl^? and Na⁺ versus Cl^? confirm that water–rock interaction and anthropogenic contribution are main sources of these ions in the groundwater. The main processes governing the chemistry of the groundwater are the dissolution of calcite, dolomite and gypsum along the flow path, and direct ion exchange. Reverse ion exchange controls the groundwater chemistry in the areas contaminated with untreated wastewater. Based on Na% and SAR, 10.3 and 27% of water samples are unsuitable for irrigation purposes, respectively. Regarding residual sodium carbonate, there is no treat for crop yields. Only 6% of water samples represent magnesium adsorption ratios more than 50% which are harmful and unsuitable for irrigation.