The carbon dioxide solubility in alkali basalts: an experimental study

Experiments were conducted to determine CO₂ solubilities in alkali basalts from Vesuvius, Etna and Stromboli volcanoes. The basaltic melts were equilibrated with nearly pure CO₂ at 1,200°C under oxidizing conditions and at pressures ranging from 269 to 2,060 bars. CO₂ solubility was determined by FTIR measurements. The results show that alkalis have a strong effect on the CO₂ solubility and confirm and refine the relationship between the compositional parameter Π devised by Dixon (Am Mineral 82:368–378, 1997) and the CO₂ solubility. A general thermodynamic model for CO₂ solubility in basaltic melts is defined for pressures up to 2 kbars. Based on the assumption that O²⁻ and CO₃²⁻ mix ideally, we have:

Kinetics of heterogeneous bubble nucleation in rhyolitic melts: implications for the number density of bubbles in volcanic conduits and for pumice textures

We performed decompression experiments to simulate the ascent of a phenocryst-bearing rhyolitic magma in a volcanic conduit. The starting materials were bubble-free rhyolites water-saturated at 200 MPa–800°C under oxidizing conditions: they contained 6.0 wt% dissolved H₂O and a dense population of hematite crystals (8.7 ± 2 × 10⁵ mm⁻³). Pressure was decreased from the saturation value to a final value ranging from 99 to 20 MPa, at constant temperature (800°C); the rate of decompression was either 1,000 or 27.8 kPa/s. In all experiments, we observed a single event of heterogeneous bubble nucleation beginning at a pressure P _N equal to 63 ± 3 MPa in the 1,000 kPa/s series, and to 69 ± 1 MPa in the 27.8 kPa/s series. Below P _N, the degree of water supersaturation in the liquid rapidly decreased to a few 0.1 wt%, the nucleation rate dropped, and the bubble number density (BND) stabilized to a value strongly sensitive to decompression rate: 80 mm⁻³ at 27.8 kPa/s vs. 5,900 mm⁻³ at 1,000 kPa/s. This behaviour is like the behavior formerly described in the case of homogeneous bubble nucleation in the rhyolite-H₂O system and in numerical simulations of vesiculation in ascending magmas. Similar degrees of water supersaturation were measured at 27.8 and 1,000 kPa/s, implying that a faster decompression rate does not result in a larger departure from equilibrium. Our experimental results imply that BNDs in acid to intermediate magmas ascending in volcanic conduits will depend on both the decompression rate and the number density of phenocrysts, especially the number density of magnetite microphenocrysts (1–100 mm⁻³), which is the only mineral species able to reduce significantly the degree of water supersaturation required for bubble nucleation. Very low BNDs (≈1 mm⁻³) are predicted in the case of effusive eruptions ( ≈ 0.1 kPa/s). High BNDs (up to 10⁷ mm⁻³) and bimodal bubble size distributions are expected in the case of explosive eruptions: (1) a relatively small number density of bubbles (1–100 mm⁻³) will first nucleate in the lower part of the conduit ( ≈ 10 kPa/s), either at high pressure on magnetite or at lower pressure on quartz and feldspar (or by homogeneous nucleation in the liquid) and (2) then, extreme decompression rates near the fragmentation level ( ≈ 10³ kPa/s) will trigger a major nucleation event leading to the multitude of small bubbles, typically a few micrometers to a few tens of micrometers in diameter, which characterizes most silicic pumices.     

Chemistry of Neutral and Alkaline Waters with Low Al<Superscript>3+</Superscript> Activity Against Hydroxyaluminosilicate HAS<Subscript>B</Subscript> Solubility. The Evidence from Ground and Surface Waters of the Sudetes Mts. (SW Poland)

A wide set of aqueous chemistry data (574 water analyses) from natural environments has been used to testify and validate of the solubility of synthetic hydroxyaluminosilicate (HAS_B)_, Al₂Si₂O₅(OH)₄. The ground and surface waters represent regolith and/or fissure aquifers in various (magmatic, sedimentary and metamorphic) bedrocks in the Sudetes Mts. (SW Poland). The solubility of HAS_B in natural waters was calculated using the method proposed by Schneider et al. (Polyhedron 23:3185–3191, 2004). Results confirm usefulness and validity of this method. The HAS_B solubility obtained from the field data (logK_sp = −44.7 ± 0.58) is lower than it was estimated (logK_sp = −40.6 ± 0.15) experimentally (Schneider et al. Polyhedron 23:3185–3191, 2004). In the waters studied the equilibrium with HAS_B is maintained at pH above 6.7 and at [Al³⁺] ≤ 10⁻¹⁰. Silicon activity (log[H₄SiO₄]) ranges between −4.2 and −3.4. Due to the calculation method used, the K_sp mentioned above cannot be considered as a classical solubility constant. However, it can be used in the interpretation of aluminium solubility in natural waters. The HAS_B has solubility lower than amorphous Al(OH)₃, and higher than proto-imogolite. From water samples that are in equilibrium with respect to HAS_B, the solubility product described by the reaction, is calculated to be logK_sp = 14.0 (±0.7) at 7°C.     

Environmental geochemistry of toxic heavy metals in soils around Sarcheshmeh porphyry copper mine smelter plant,Rafsanjan, Kerman,Iran

The Sarcheshmeh copper mine smelter plant is one of the biggest copper producers in Iran. Long-time operation of about 25 years of the smelter plant causes release of potentially toxic heavy metals into the environment. In this paper, geochemical distribution of toxic heavy metals in 28 soil samples was evaluated around the Sarcheshmeh smelter plant. Soils developed over the nonmineralized and uncontaminated areas have an average background concentration of 41.25 mg kg⁻¹ Cu, 26.6 mg kg⁻¹ As, 12.7 mg kg⁻¹ Pb, 0.9 mg kg⁻¹ Sb, 1.9 mg kg⁻¹ Mo, 1.7 mg kg⁻¹ Sn, 0.2 mg kg⁻¹ Cd, 0.15 mg kg⁻¹ Bi, 235 mg kg⁻¹ S and 73.4 mg kg⁻¹ Zn, respectively. As a result of smelting process, the upper soil layers (0–5 cm) were polluted by Cu (>1,397 mg kg⁻¹), Cd (>3.42 mg kg⁻¹), S (>821 mg kg⁻¹), Mo (>10.3 mg kg⁻¹), Sb (>11.7 mg kg⁻¹), As (>120.6 mg kg⁻¹), Pb (>83.8 mg kg⁻¹), Zn (>214.9 mg kg⁻¹), and Sn (>3.7 mg kg⁻¹), respectively. These values are much higher than the normal concentration of the elements in the uncontaminated soil layers. The elemental values decrease with distance travelled away of the smelter plant, especially at minimum wind direction. Furthermore, high contaminated values of Cu (8,430 mg kg⁻¹), As (500 mg kg⁻¹), Pb (331 mg kg⁻¹), Mo (61 mg kg⁻¹), Sb (56.2 mg kg⁻¹), Zn (664 mg kg⁻¹), Cd (17.2 mg kg⁻¹), Bi (13.4 mg kg⁻¹), and S (3,780 mg kg⁻¹) were observed in the upper soil layers close to the smelting waste dumps. Sequential extraction analysis shows that about 270 mg kg⁻¹ Cu, 28 mg kg⁻¹ Pb, 50.33 mg kg⁻¹ Zn, and 47.84 mg kg⁻¹ As were adsorbed by Fe and Mn oxides. The carbonate phases include 151 mg kg⁻¹ Cu, 28 mg kg⁻¹ Pb, 25 mg kg⁻¹ Zn, and 32.99 mg kg⁻¹ As. Organic matter adsorbed 314.6 mg kg⁻¹ Cu and 29.18 mg kg⁻¹ Zn.     

Speciation and phytoavailability of heavy metals in sediments in Nanjing section of Changjiang River

Heavy metal pollution and their fractionations in the sediments of Changjiang River in Nanjing Reach was monitored for cadmium (Cd), lead (Pb), zinc (Zn), chromium (Cr), and copper (Cu). Moreover, the biological enrichment of metals by riverine plants was studied. The results demonstrated there were highly significant variations among different sampling stations for the concentrations of tested metals. The highest range was for Cu (38.8–120.4 mg kg⁻¹), followed by Cr (74.4–120.0 mg kg⁻¹), Zn (80.9–121.1 mg kg⁻¹), Ni (26.0–55.5 mg kg⁻¹), Pb (15.8–46.7 mg kg⁻¹) and Cd (0.28–0.48 mg kg⁻¹). Cd was the element with highest biological enrichment factor (BEF). The highest BEF of Cd in Erigeron bonariensis reached 3.0, indicating a significant Cd enrichment in this aquatic plant. In addition, 60% of Cd was found in reducible fraction and exchangeable and acid-soluble fraction, which was consistent with its high mobility. The consistency of Cd fraction in sediment and suspended particle indicated they came from the same source. Accumulated Cd concentration calculated according to the release curve showed significant relativity with the total Cd concentration in the sediment.     

Hyperaccumulation of lead,zinc, and cadmium in plants growing on a lead/zinc outcrop in Yunnan Province,China

A field survey was conducted to identify potential hyperaccumulators of Pb, Zn or Cd in the Beichang Pb/Zn mine outcrop in Yunnan Province, China. The average total concentrations of Pb, Zn, and Cd in the soils were up to 28,438, 5,109, and 52 mg kg⁻¹, respectively. A total of 68 plant species belonging to 60 genera of 37 families naturally colonizing the outcrop were recorded. According to metal accumulation in the plants and translocation factor (TF), Silene viscidula was identified as potential hyperaccumulator of Pb, Zn, and Cd with mean shoot concentrations of 3,938 mg kg⁻¹ of Pb (TF = 1.2), 11,155 mg kg⁻¹ of Zn (TF = 1.8) and 236 mg kg⁻¹ of Cd (TF = 1.1), respectively; S. gracilicanlis (Pb 3,617 mg kg⁻¹, TF = 1.2) and Onosma paniculatum (Pb 1,837 mg kg⁻¹, TF = 1.9) were potential Pb hyperaccumulators. Potentilla griffithii (Zn 8,748 mg kg⁻¹, TF = 1.5) and Gentiana sp. (Zn 19,710 mg kg⁻¹, TF = 2.7) were potential Zn hyperaccumulators. Lysimachia deltoides (Cd 212 mg kg⁻¹, TF = 3.2) was a potential Cd hyperaccumulator. These new plant resources could be used to explore the mechanisms of Pb, Zn and/or Cd hyperaccumulation, and the findings could be applied for the phytoremediation of Pb, Zn and/or Cd-contaminated soils.     

The impact of acid rain on phosphorus leaching from a sandy loam calcareous soil of western Iran

Simulated acidic precipitation (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 and 7.0 were conducted using column leaching to determine impacts of simulated acid rain on phosphorus (P) leaching from a calcareous sandy loam soil over a 40-day period. Soil columns were irrigated every day to make a total of 1,061 mm, equivalent to 3.5 years of rainfall (based on average annual rainfall). Leachates were collected and analyzed for anions and cations. There was significant nonlinear correlation between the amount of P leached and the simulated acid rain (R ² = 0.61). Losses of P from the pH 2.5 and 7.0 treatments were 1.23, and 1.32 mg kg⁻¹, respectively. The results showed that the amount of P leached from pH 4 (1.46 mg kg⁻¹) and 5 treatments (1.52 mg⁻¹ kg⁻¹) were significantly larger than other treatments. Linear equation adequately described leaching of P in different treatments. The slope (mg kg⁻¹ day⁻¹) in the linear equation was defined as the leaching rate and for the pH 2.5 was 0.0354, and 0.0382 and 0.0406 for pH 4.5 and 7.0, respectively. The geochemical code Visual MINTEQ was used to calculate saturation indices. Leaching of P in different treatments was controlled by rate-limited dissolution of hydroxyapatite, β-tricalcium phosphate and to some extent octacalcium phosphate. The results indicate that acid rain in calcareous sandy loam soils may pose a risk in terms of groundwater contamination with P.     

H2S fluxes from Mt. Etna, Stromboli, and Vulcano (Italy) and implications for the sulfur budget at volcanoes

We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO₂/H₂S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H₂S flux of 6 to 9 t · d⁻¹ for the summit crater. For Mt. Etna and Stromboli, we found SO₂/H₂S molar ratios of ≈20 and ≈15, respectively, which combined with SO₂ flux measurements, suggest H₂S emission rates of 50 to 113 t · d⁻¹ and 4 to 8 t · d⁻¹, respectively. We observe that “source” and plume SO₂/H₂S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H₂S emission.     

A 57Fe M?ssbauer spectroscopic study of sogdianite: an example of a symmetric electric field gradient around Fe3+

Sogdianite, a double-ring silicate of composition ( \textZr_{0. 7 6} \textTi_{0. 3 8}^{4 +} \textFe_{0. 7 3}^{3 +} \textAl_0.13 )_{\Upsigma = 2} ( \square _{1. 1 5} \textNa_{0. 8 5} )_{\Upsigma = 2} \textK[\textLi ₃ \textSi _{1 2} \textO ₃₀ ] ( {\text{Zr}}_{0. 7 6} {\text{Ti}}_{0. 3 8}^{4 + } {\text{Fe}}_{0. 7 3}^{3 + } {\text{Al}}_{0.13} )_{\Upsigma = 2} \left( {\square_{ 1. 1 5} {\text{Na}}_{0. 8 5} } \right)_{\Upsigma = 2} {\text{K}}[{\text{Li}}_{ 3} {\text{Si}}_{ 1 2} {\text{O}}_{ 30} ] from Dara-i-Pioz, Tadjikistan, was studied by the combined application of ⁵⁷Fe M?ssbauer spectroscopy and electronic structure calculations. The M?ssbauer spectrum confirms published microprobe and X-ray single-crystal diffraction results that indicate that Fe³⁺ is located at the octahedral A-site and that no Fe²⁺ is present. Both the measured and calculated quadrupole splitting, ΔE _Q, for Fe³⁺ are virtually 0 mm s⁻¹. Such a value is unusually small for a silicate and it is the same as the ΔE _Q value for Fe³⁺ in structurally related sugilite. This result is traced back to the nearly regular octahedral coordination geometry corresponding to a very symmetric electric field gradient around Fe³⁺. A crystal chemical interpretation for the regular octahedral geometry and the resulting low ΔE _Q value for Fe³⁺ in the M?ssbauer spectrum of sogdianite is that structural strain is largely “taken up” by weak Li–O bonds permitting highly distorted LiO₄ tetrahedra. Weak Li–O bonding allows the edge-shared more strongly bonded Fe³⁺O₆ octahedra to remain regular in geometry. This may be a typical property for all double-ring silicates with tetrahedrally coordinated Li.     

Geochemistry and health aspects of F-rich mountainous streams and groundwaters from sierras Pampeanas de Cordoba,Argentina

Symptoms of dental fluorosis have been observed in rural communities located in the Sierras Pampeanas de Córdoba, a mountainous area in Central Argentina. The clinical assessment was performed in the Charbonier Department, where the fluoride (F⁻) intake was determined to be 3.90 ± 0.20 mg day⁻¹ (n = 16). In this community, mild and severe fluorosis reach an incidence of 86.7% (total teeth surface = 636 teeth) among the children population. To determine the origin and distribution of fluorine in natural waters from the Charbonier Department and nearby regions, sampling was performed in the area covering the San Marcos River basin. The obtained results show that F⁻ concentrations vary between ~1 to ~2.5 mg l⁻¹, with an outlier value of 8 mg l⁻¹. The spatial distribution of F⁻ shows that the lowest concentrations are found at the basin’s catchments. Maximum values are located in two sectors of the basin: the Charbonier depression in the eastern part and at the San Marcos village, downstream the main collector, in the western part of the basin. In these two regions, the F⁻ contents in ground- and surface waters are >2.0 mg l⁻¹ and nearly constant. Dissolved F⁻ in natural waters from the study area has its origin in the weathering of F-bearing minerals present in the region’s dominant lithology. The extent of mineral weathering is mostly determined by the residence time of water within the aquatic reservoir. Longer residence times and a major solid–water interaction lead to enhanced release of F⁻. This explains the higher F⁻ concentrations found in basin areas with lower run off. The removal of F⁻ from water appears to occur by neither fluorite precipitation, nor by adsorption. Hence, variations in F⁻ concentrations seem to be more related to regional hydrological conditions.     

The Equation of State for Caspian Sea Waters

The density ρ of Caspian Sea waters was measured as a function of temperature (273.15–343.15) K at conductivity salinities of 7.8 and 11.3 using the Anton-Paar Densitometer. Measurements were also made on one of the samples (S = 11.38) diluted with water as a function of temperature (T = 273.15–338.15 K) and salinity (2.5–11.3). These latter results have been used to develop an equation of state for the Caspian Sea (σ = ±0.007 kg m⁻³)

Heavy metal concentrations and their possible sources in paddy soils of a modern agricultural zone,southeastern China

In a typical modern agricultural Zone of southeastern China, Haining City, 224 topsoil samples were collected from paddy fields to measure the total concentrations of copper (Cu), lead (Pb), zinc (Zn), cadmium (Cd), chromium (Cr), mercury (Hg), arsenic (As) and cobalt (Co). The total concentrations ranged from 15.30 to 78.40 mg kg⁻¹ for Cu, 20.10 to 41.40 mg kg⁻¹ for Pb, 54.98 to 224.4 mg kg⁻¹ for Zn, 0.04 to 0.24 mg kg⁻¹ for Cd, 54.90 to 197.1 mg kg⁻¹ for Cr, 0.03 to 0.61 mg kg⁻¹ for Hg, 3.44 to 15.28 mg kg⁻¹ for As, and 7.17 to 19.00 mg kg⁻¹ for Co. Chemometric techniques and geostatistics were utilized to quantify their spatial characteristics and define their possible sources. All eight metals had a moderate spatial dependency except that Pb had a strong spatial dependency. Both factor analysis and cluster analysis successfully classified the eight metals into three groups or subgroups, the first group included Cu, Zn and Cr, the second group included Cd, As and Co, and the last group included Pb and Hg. The Cu, Zn and Cr concentrations in majority samples were higher than their local background concentrations and they were highly correlated (r > 0.80), indicating that they had similar pollution source and anthropic factor controlled their spatial distribution; the Cd, As and Co concentrations in majority samples were lower than their local background concentrations, indicating that the source of these elements was mainly controlled by natural factors; the mean concentration of Pb exhibited generally low level, close to its local background concentration, the Hg concentration in about half of samples was higher than its local background concentration, and they were poor correlated with the other metals, indicating that the source of Pb and Hg was common controlled by natural factor and anthropic factor.     

Nitrate pollution of groundwater in Toyserkan,western Iran

A total of 95 groundwater samples were collected from Toyserkan, western Iran to assess the chemical composition and nitrate (NO₃ ⁻) status of groundwater. The most prevalent water type is Ca–HCO₃ followed by water types Ca–Mg–HCO₃. In comparison with the World Health Organization (WHO) drinking water guideline of 50 mg l⁻¹ for NO₃ ⁻, a total of nine wells (9.5%) showed higher concentrations. In 36% of samples (34) NO₃ ⁻ concentration was low (<20 mg l⁻¹), and in 53.7% of samples (51), in the range of 20–50 mg l⁻¹. The samples were classified into four groups based on NO₃ ⁻ and chloride (Cl⁻) concentrations. Of the samples, 40% were classified as group 4 and were relatively high in Cl⁻ and NO₃ ⁻ (Cl⁻ > 47 mg l⁻¹, NO₃ ⁻ > 27 mg l⁻¹). The high correlation between NO₃ ⁻ and Cl⁻ (r = 0.86, p < 0.01) is consistent with a manure source, resulting from the practice of adding salt to animal feed. Pollution of groundwaters appeared to be affected by the application of inorganic fertilizer at greater than agronomic rates, Cl-salt inputs, and irrigation practice.     

Influence of humic acids on the accumulation of copper and cadmium in <Emphasis Type="Italic">Vallisneria spiralis</Emphasis> L. from sediment

Physiological responses and metal accumulation in Vallisneria spiralis L. exposed to copper and cadmium contaminated sediment were examined at different metal concentrations and the influence of humic acids on copper and cadmium accumulation was also studied. The plants of V. spiralis accumulated high amount of copper and cadmium. The maximum accumulation of 396 and 114 mg kg⁻¹ DW copper were found in the roots and shoots, respectively, at 614 mg kg⁻¹ DW after 21 days’ copper exposure; they were 63.8 and 48.0 mg kg⁻¹ DW for cadmium at 88.69 mg kg⁻¹ DW. The plants showed decrease in chlorophyll content with the increasing concentration of copper/cadmium in sediment. With addition of humic acids from 3.09 to 7.89 g kg⁻¹ DW, both copper and cadmium accumulation in V. spiralis were significantly inhibited (p < 0.01). The cadmium concentrations of roots and shoots of plant decreased 26.4–50.3 and 14.3–33.0% under cadmium treatments, respectively; copper accumulation decreased much more with 44.0–77.0 and 35.0–62.7%, respectively. It was concluded that V. spiralis appeared to be an ideal candidate for the phytoremediation of copper and cadmium polluted sediments, and humic acids had an important role in regulating copper and cadmium bioavailability and toxicity in sediments.     

Thermodynamic Properties of Brucite Determined by Solubility Studies and Their Significance to Nuclear Waste Isolation

Solubility experiments were conducted for the dissolution reaction of brucite, Mg(OH)₂ (cr): Experiments were conducted from undersaturation in deionized (DI) water and 0.010–4.4 m NaCl solutions at 22.5°C. In addition, brucite solubility was measured from supersaturation in an experiment in which brucite was precipitated via dropwise addition of 0.10 m NaOH into a 0.10 m MgCl₂ solution also at 22.5°C. The attainment of the reversal in equilibrium was demonstrated in this study. The solubility constant at 22.5°C at infinite dilution calculated from the experimental results from the direction of supersaturation by using the specific interaction theory (SIT) is: with a corresponding value of 17.0 ± 0.2 (2σ) when extrapolated to 25°C. The dimensionless standard chemical potential (μ°/RT) of brucite derived from the solubility data in 0.010 m to 4.4 m NaCl solutions from undersaturation extrapolated to 25°C is −335.76 ± 0.45 (2σ), with the corresponding Gibbs free energy of formation of brucite, , being −832.3 ± 1.1 (2σ) kJ mol⁻¹. In combination with the auxiliary thermodynamic data, the is calculated to be 17.1 ± 0.2 (2σ), based on the above Gibbs free energy of formation for brucite. This study recommends an average value of 17.05 ± 0.2 in logarithmic unit as solubility constant of brucite at 25°C, according to the values from both supersaturation and undersaturation. Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.     

Mineralogy and geochemistry of the Texeo Cu–Co mine site (NW Spain): screening tools for environmental assessment

The Cu–Co–Ni Texeo mine has been the most important source of Cu in NW Spain since Roman times and now, approximately 40,000 m³ of wastes from mine and metallurgical operations, containing average concentrations of 9,263 mg kg⁻¹ Cu, 1,100 mg kg⁻¹ As, 549 mg kg⁻¹ Co, and 840 mg kg⁻¹ Ni, remain on-site. Since the cessation of the activity, the abandoned works, facilities and waste piles have been posing a threat to the environment, derived from the release of toxic elements. In order to assess the potential environmental pollution caused by the mining operations, a sequential sampling strategy was undertaken in wastes, soil, surface and groundwater, and sediments. First, screening field tools were used to identify hotspots, before defining formal sampling strategies; so, in the areas where anomalies were detected in a first sampling stage, a second detailed sampling campaign was undertaken. Metal concentrations in the soils are highly above the local background, reaching up to 9,921 mg kg⁻¹ Cu, 1,373 mg kg⁻¹ As, 685 mg kg⁻¹ Co, and 1,040 mg kg⁻¹ Ni, among others. Copper concentrations downstream of the mine works reach values up to 1,869 μg l⁻¹ and 240 mg kg⁻¹ in surface water and stream sediments, respectively. Computer-based risk assessment for the site gives a carcinogenic risk associated with the presence of As in surface waters and soils, and a health risk for long exposures; so, trigger levels of these elements are high enough to warrant further investigation.     

Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

Trace element partitioning between orthopyroxene and anhydrous silicate melt on the lherzolite solidus from 1.1 to 3.2 GPa and 1,230 to 1,535°C in the model system Na<Subscript>2</Subscript>O–CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>

We determined experimentally the Nernst distribution coefficient between orthopyroxene and anhydrous silicate melt for trace elements i in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂ (NCMAS) along the dry model lherzolite solidus from 1.1 GPa/1,230°C up to 3.2 GPa/1,535°C in a piston cylinder apparatus. Major and trace element composition of melt and orthopyroxene were determined with a combination of electron microprobe and ion probe analyses. We provide partitioning data for trace elements Li, Be, B, K, Sc, Ti, V, Cr, Co, Ni, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Sm, Nd, Yb, Lu, Hf, Ta, Pb, U, and Th. The melts were chosen to be boninitic at 1.1 and 2.0 GPa, picritic at 2.3 GPa and komatiitic at 2.7 and 3.2 GPa. Orthopyroxene is Tschermakitic with 8 mol% Mg-Tschermaks MgAl[AlSiO₆] at 1.1 GPa while at higher pressure it has 18–20 mol%. The rare earth elements show a continuous, significant increase in compatibility with decreasing ionic radius from D _La^opx−melt ∼ 0.0008 to D _Lu^opx−melt ∼ 0.15. For the high-field-strength elements compatibility increases from D _Th^opx−melt ∼ 0.001 through D _Nb^opx−melt ∼ 0.0015, D _U^opx−melt ∼ 0.002, D _Ta^opx−melt ∼ 0.005, D _Zr^opx−melt ∼ 0.02 and D _Hf^opx−melt ∼ 0.04 to D _Ti^opx−melt ∼ 0.14. From mathematical and graphical fits we determined best-fit values for D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1, and E ₀^M2 for the two different M sites in orthopyroxene according to the lattice strain model and calculated the intracrystalline distribution between M1 and M2. Our data indicate extreme intracrystalline fractionation for most elements in orthopyroxene; for the divalent cations D _i ^M2−M1 varies by three orders of magnitude between D _Co^M2−M1 = 0.00098–0.00919 and D _Ba^M2−M1 = 2.3–28. Trivalent cations Al and Cr almost exclusively substitute on M1 while the other trivalent cations substitute on M2; D _La^M2−M1 reaches extreme values between 6.5 × 10⁷ and 1.4 × 10¹⁶. Tetravalent cations Ti, Hf, and Zr almost exclusively substitute on M1 while U and Th exclusively substitute on M2. Our new comprehensive data set can be used for polybaric-polythermal melting models along the Earth’s mantle solidus. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Thermal behaviour and kinetics of dehydration of gypsum in air from in situ real-time laboratory parallel-beam X-ray powder diffraction

Thermal behaviour and kinetics of dehydration of gypsum in air have been investigated using in situ real-time laboratory parallel-beam X-ray powder diffraction data evaluated by the Rietveld method. Thermal expansion has been analysed from 298 to 373 K. The high-temperature limits for the cell edges and for the cell volume, calculated using the Einstein equation, are 4.29 × 10⁻⁶, 4.94 × 10⁻⁵, 2.97 × 10⁻⁵, and 8.21 × 10⁻⁵. Thermal expansion of gypsum is strongly anisotropic being larger along the b axis mainly due to the weakening of hydrogen bond. Dehydration of gypsum has been investigated in isothermal conditions within the 348–403 K range with a temperature increase of 5 K. Dehydration proceeds through the CaSO₄·2H₂O → CaSO₄·0.5H₂O → γ-CaSO₄ steps. Experimental data have been fitted with the Avrami equation to calculate the empirical activation energy of the process. No change in transformation mechanism has been observed within the analysed temperature range and the corresponding E _a is 109(12) kJ/mol.     

Concentration and spatial variability of mercury and other heavy metals in surface soil samples of periurban waste mine tailing along a transect in the Almadén mining district (Spain)

Mercury (Hg) is one of the elements with increasing environmental significance. A total of 22 samples (soils, rocks and gels) were collected along a 6 km transect around the Valdeazogues River valley in the southwest of the Iberian Peninsula (Almadén, Spain). Samples were characterized by different soil types of depositional sequences associated with mining tailings, type and system tracts: 15 surface soil samples included in the transect; 3 of a Haploxerept soil profile developed on slates; 2 of quartzite and slates rocks (reference rocks in the area). Moreover, two of a gel substance (in the lower tract of the river). Soil samples were analyzed for Hg, Cu, Ni, Cr, V, Pb, Cd and As, as well as for organic matter, pH abrasion and calcium carbonate content. All samples were collected from the Almadén mining district. The level of occurrence of the elements (especially Hg) and the effect of some properties on its concentration distributions were investigated. The total mercury contents varied in the range 7,315–3.44 mg kg⁻¹. The mean concentration of total mercury in soils and rocks was 477.03 mg kg⁻¹dry mass. This value is very high compared to the regional background value of other areas. Only rarely is it higher than 1%: in one sample (7,315 mg kg⁻¹) it was almost eight times in comparison with the affected zones, with a high value of 1,000 mg kg⁻¹. Significant differences between samples were found in the total content of mercury. A large percentage of the samples registered detectable levels of V, Cr, Ni, Pb, As and Cu. Cd readings were below the detectable range for all samples tested. Cr mean concentration was 216.95 mg kg⁻¹ (minimun concentration 86, maximun 358); V mean concentration was 119.09 mg kg⁻¹ (minimun concentration 69, maximun 1,209); As mean concentration was 51.24 mg kg⁻¹ (minimun 13.3 and maximun 319.4); Ni mean concentration was 45.64 mg kg⁻¹ (minimun concentration 21.2 and maximun 125.6); Cu mean concentration was 33.25 mg kg⁻¹ (minimun concentration 19.3 and maximun 135); Pb mean concentration was 15.19 mg kg⁻¹ (minimun 1.12 and maximun 1013). Metal distribution generally showed spatial variability ascribed to significant anthropogenic perturbation by mining tailing type. Hg showed vertical profile characterized by surface enrichment, with concentrations in the upper layer (93.7–82.2 mg kg⁻¹ in front of 3.4 of the rock value) exceeding, in several occasions, the background value. The results obtained denote a potential toxicity of some heavy metals in some of the studied samples. Water-soluble mercury could enter the aquatic system and accumulate in sediments. Mercury and other heavy metals contamination depended on the duration and intensity of mining activities.