Geochemical and thermodynamic aspects of sorption of strontium on kaolinite dominated clay samples at Kalpakkam

The mobility of strontium in subsurface is largely influenced by sorption on to clay minerals. In the present study, kaolinite clay samples collected from the Kalpakkam nuclear plant site were employed to understand the sorption characteristics of strontium by batch method. The effect of several parameters such as time, strontium ion concentration, pH, temperature and ionic strength was investigated. The kinetic studies suggested pseudo-second-order mechanism. The experimental sorption data was fitted to Langmuir adsorption model for obtaining the sorption capacity of the sorbent. The maximum sorption capacity was 5.77 mg/g at 298 K and was found to increase with an increase in temperature. It was observed that the distribution coefficient (K _d) of strontium on clay increased as the pH of the solution increased. The distribution coefficient was found to decrease with an increase in concentration of Na⁺ and Ca²⁺ ions. This variation of K _d suggests that cation exchange is the predominant sorption process. It was also observed that sorption process is endothermic. The thermodynamic parameters such as ∆G ⁰, ∆H ⁰ and ∆S ⁰ were calculated. The negative values obtained for ∆G ⁰ indicated that the sorption of strontium on clay was spontaneous at all studied concentrations. ∆G ⁰ becomes more negative with an increase in temperature, suggests that the sorption process is more favorable at higher temperatures.     

Arsenic removal from aqueous solutions by mixed magnetite–maghemite nanoparticles

In this study, magnetite–maghemite nanoparticles were used to treat arsenic-contaminated water. X-ray photoelectron spectroscopy (XPS) studies showed the presence of arsenic on the surface of magnetite–maghemite nanoparticles. Theoretical multiplet analysis of the magnetite–maghemite mixture (Fe₃O₄-γFe₂O₃) reported 30.8% of maghemite and 69.2% of magnetite. The results show that redox reaction occurred on magnetite–maghemite mixture surface when arsenic was introduced. The study showed that, apart from pH, the removal of arsenic from contaminated water also depends on contact time and initial concentration of arsenic. Equilibrium was achieved in 3 h in the case of 2 mg/L of As(V) and As(III) concentrations at pH 6.5. The results further suggest that arsenic adsorption involved the formation of weak arsenic-iron oxide complexes at the magnetite–maghemite surface. In groundwater, arsenic adsorption capacity of magnetite–maghemite nanoparticles at room temperature, calculated from the Langmuir isotherm, was 80 μmol/g and Gibbs free energy (∆G⁰, kJ/mol) for arsenic removal was −35 kJ/mol, indicating the spontaneous nature of adsorption on magnetite–maghemite nanoparticles.     

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.     

Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks

The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2 ± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation of state: V _P,T  = V ₂₉₈° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K ₂₉₈ × (1 – 1.5 × 10⁻⁴ [T − 298]) + 4P)]^1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V ₂₉₈° = 5.568 J/bar, a° = 3.1 × 10⁻⁵ K⁻¹, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°_f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases. The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites and 10 kbar for ultra-high pressure titanite-bearing assemblages.     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Effects of pH on isotherm modeling and cation competition for Cd(II) and Cu(II) biosorption on Myriophyllum spicatum from aqueous solutions

The biosorption characteristics of Cd(II) and Cu(II) ions from aqueous solutions obtained using submerged aquatic plant (Myriophyllum spicatum) biomass were investigated in terms of equilibrium, kinetics, thermodynamics, and cation competition. Langmuir and Freundlich models were applied to describe the biosorption isotherm of metal ions by M. spicatum biomass and isotherm constants considering the most important parameter, pH. The variation of sorption isotherm constants showed pH dependence. The Langmuir and Freundlich models fitted the equilibrium data well. The maximum biosorption capacity (q _m) of M. spicatum biomass was determined to be 29.07 mg/g for the Cd(II) ion at pH 5.0 and 12.12 mg/g for the Cu(II) ion at pH 6.0. Chi square analysis showed that the Freundlich model fitted the equilibrium data better than the Langmuir isotherm. Competition of Cd(II) and Cu(II) in a binary solution showed that the Langmuir monolayer capacity of Cd(II) decreased from 29.07 mg/g with only Cd(II) in solution to 12.02 mg/g in the presence of Cu(II). Kinetics results showed that the biosorption processes of both metal ions followed the pseudo-second-order kinetics well. The calculated thermodynamic parameters (?G ⁰, ?H ⁰, and ?S ⁰) showed that biosorption of Cd(II) and Cu(II) ions onto M. spicatum biomass was feasible, spontaneous, and endothermic in nature. Fourier transform infrared spectroscopy spectrum analysis revealed that Cd(II) and Cu(II) sorption was mainly ascribed to carboxyl, hydroxyl, amine, and C–N groups in M. spicatum.     

Mobility and ecological risk assessment of heavy metals in surface sediments of Xiamen Bay and its adjacent areas,China

Xiamen Bay (XMB) has received substantial loadings of pollutants from industrial and municipal wastewater discharged since the 1980s. To assess ecological risks and the current spatial changes of metal contaminants in bottom surface sediments, 12 samples were collected. Samples were subjected to a total digestion technique and analyzed by ICP–OES for Cu, Pb, Zn, Cr, and Cd, and by AFS for Hg and As. Among these metals, Zn had the highest values (68–268 mg kg⁻¹), followed by Pb (27–71 mg kg⁻¹), and lower concentrations were found for Cd (42–1,913 μg kg⁻¹) and Hg (0–442 μg kg⁻¹). In comparison with the average crustal abundance values, the results indicated that nearly half of the sediment samples of XMB and its adjacent areas were contaminated by Cd, Pb, Zn, and As. Furthermore, based on the modified BCR sequential extraction procedure, the chemical speciation of heavy metals (Cd, Cr, Cu, Pb, Zn, Hg, and As) in selected sediment samples were evaluated in this study. Data from BCR sequential extractions indicated that Cd posed a medium ecological risk, whereas, Cr posed low risk since its exchangeable and carbonate fractions were below 4%, and the mobility of heavy metals in XMB decreased in the order Cd > Pb > Cu > Zn > Hg > As > Cr. By applying mean effects range median quotients (mERMQ), the results showed that Yuandang Lagoon with mERMQ value >0.5 would be expected to have the greatest potential toxic risk in amphipod within XMB and its adjacent areas.     

Effects of Environmental Variation and Non-point Source (NPS) Nutrient Pollution on Aquatic Plant Communities in Weeks Bay National Estuarine Research Reserve (WBNERR), AL

This study was designed to investigate non-point source nutrient pollution and its influences on submerged aquatic plant community structure and biological invasion in the Weeks Bay National Estuarine Research Reserve (WBNERR). A monthly vegetation survey was conducted to document plant abundance and changes in community structure; physicochemical data and water samples were collected on a bi-monthly basis to monitor environmental conditions (i.e., pH, salinity, dissolved oxygen, light intensity, and attenuation) and water column nutrient (NO₂⁻/NO₃⁻ and NH₄⁺) and chlorophyll a concentrations. A total of seven submerged aquatic species were identified at the WBNERR with the occurrence of only one non-native species (Hydrilla verticillata). Statistical analyses suggest that water column nitrogen concentrations along with variations in dissolved oxygen (0.6–11.5 mg L⁻¹), light attenuation, pH (5.6–8.6), and temperature (11–33°C) play key roles in determining the aquatic plant abundance and distribution in the WBNERR.     

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.     

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.     

Competitive adsorption of trace elements in calcareous soils as affected by sewage sludge,poultry manure,and municipal waste compost

The competitive adsorption of trace elements is a key issue in assessing the mobility of trace elements in calcareous soils and can be affected by disposal of sewage sludge, municipal waste, and poultry manure. The effect of municipal sewage sludge, poultry manure, and municipal waste compost on the sorption of cadmium (Cd), copper (Cu), zinc (Zn), and nickel (Ni) in surface samples of three calcareous soils was studied. As the applied concentrations increased, Cu and Cd adsorption increased, while Zn and Ni adsorption decreased in all treatments. Based on the distribution coefficient (K _d) values and proportion of increase or decrease in metal adsorption, the selectivity sequence in control and amended soils found was Cu ≫ Cd ≫ Ni > Zn and Cu ≫ Cd ≫ Zn > Ni, respectively. In general, among control and amended soils, control soils showed the highest K _d for Cd, Cu, and Ni, while sludge, poultry manure, and composted waste-amended soils had lowest K _d for Cd, Cu, and Ni, respectively. In the case of Zn, composted waste-amended and control soils had highest and lowest K _d, respectively. The present experimental results indicated that the addition of organic amendments to these calcareous soils reduced the sorption of Cd, Cu, and Ni. Thus, the effects of preferential adsorption and organic matter should be considered in assessing the risk associated with applying sewage sludge, poultry manure, and composted material to calcareous soils.     

Influences of Salinity and Light Availability on Abundance and Distribution of Tidal Freshwater and Oligohaline Submersed Aquatic Vegetation

Submersed aquatic vegetation (SAV) communities have undergone declines worldwide, exposing them to invasions from non-native species. Over the past decade, the invasive species Hydrilla verticillata has been documented in several tributaries of the lower Chesapeake Bay, Virginia. We used annual aerial mapping surveys from 1998 to 2007, integrated with spatial analyses of water quality data, to analyze the patterns and rates of change of a H. verticillata-dominated SAV community and relate them to varying salinity and light conditions. Periods of declining SAV coverage corresponded to periods where salinities exceeded 7 and early growing season (April to May) Secchi depths were <0.4 m. Increases were driven by the expansion of H. verticillata along with several other species into the upper estuary, where some areas experienced an 80% increase in cover. Field investigations revealed H. verticillata dominance to be limited to the upper estuary where total suspended solid concentrations during the early growing season were <15 mg l⁻¹ and salinity remained <3. The effect of poor early growing season water clarity on annual SAV growth highlights the importance of water quality during this critical life stage. Periods of low clarity combined with periodic salinity intrusions may limit the dominance of H. verticillata in these types of estuarine systems. This study shows the importance of the use of these types of biologically relevant episodic events to supplement seasonal habitat requirements and also provides evidence for the potential important role of invasive species in SAV community recovery.     

Impact of internal waves on the acoustic field at a coastal station off Paradeep,east coast of India

Internal Wave (IW) characteristics and the impact of IW on acoustic field have been studied utilizing the hourly time series of temperature and salinity data collected at a coastal site off Paradeep (north Bay of Bengal) during 24–25 October 2008. The IW characteristics, viz. period (t _per ), velocity (C _vel ), wavelength (L), and wave numbers (k), are found to be 2.133–34.72 h, 0.135 km h⁻¹, 0.37–6.2 km and 2.70–0.16 cycles km⁻¹, respectively. The semi-diurnal tidal forces are predominant than diurnal as well as at other frequencies and its contribution is about 64% towards the total potential energy (E ₀ = 3.34 J m⁻²). Sound velocity perturbations with space and time in the presence of IW field are examined from Garrettt-Munk (GM) model. Transmission loss anomaly for optimized source-receiver configuration at the depth of 53 m and range of 9 km has been computed from acoustic modelling. The loss in the acoustic transmission is found to be 38.4 dB in the presence of low-frequency IW field.     

A comparison of organic wastes as bioadsorbents of heavy metal cations in aqueous solution and their capacity for desorption and regeneration

The adsorption capacity of seven organic wastes/by-products (slash pine, red gum and western cypress bark, composted green waste, prawn exoskeletons, spent brewery yeast and mill mud from a sugar mill) for transition metals were determined at two metal concentrations (10 and 100 mg L⁻¹) and three equilibrium pH values (4.0, 6.0 and 8.0) in batch adsorption experiments. All tested materials indicate a positive affinity to adsorb metal cations from aqueous solution and spent yeast was the least effective. Adsorption generally increased with increasing pH and the order of selectivity of metals was: Cr³⁺ > Cu²⁺ > Pb²⁺ > Zn²⁺ ≥ Cd²⁺. For pine bark, compost, spent yeast and prawn shell, quantities of previously adsorbed Pb and Cd desorbed in 0.01 M NaNO₃ electrolyte were negligible. However, 0.01 M HNO₃, and more particularly 0.10 and 0.50 M HNO₃ were effective at removing both adsorbed Pb and Cd. Using 0.10 M HNO₃ as the regenerating agent, pine bark and compost maintained their Pb and Cd adsorption capacity over eight successive adsorption/regeneration cycles. For mill mud and prawn shell, there was a pronounced decrease in adsorption capacity after only one regeneration cycle. A subsidiary experiment confirmed that acid pre-treatment of the latter two materials appreciably reduced their Pb and Cd adsorption capacity. This was ascribed to the metal adsorption capacity of prawn shell and mill mud being partially attributable to their significant CaCO₃ content and acid treatment induces dissolution of the CaCO₃. It was shown that in relation to both adsorption capacity and desorption/regeneration capability, composted green waste showed the greatest potential.     

High‐Precision Cd Isotope Measurements of Soil and Rock Reference Materials by MC‐ICP‐MS with Double Spike Correction

This study presents a high‐precision Cd isotope measurement method for soil and rock reference materials using MC‐ICP‐MS with double spike correction. The effects of molecular interferences (e.g., ¹⁰⁹Ag¹H⁺, ⁹⁴Zr¹⁶O⁺, ⁹⁴Mo¹⁶O⁺ and ⁷⁰Zn⁴⁰Ar⁺) and isobaric interferences (e.g., Pd, In and Sn) to Cd isotope measurements were quantitatively evaluated. When the measured solution has Ag/Cd ≤ 5, Zn/Cd ≤ 0.02, Mo/Cd ≤ 0.4, Zr/Cd ≤ 0.001, Pd/Cd ≤ 5 × 10^?5 and In/Cd ≤ 10^?3, the measured Cd isotope data were not significantly affected. The intermediate measurement precision of pure Cd solutions (BAM I012 Cd, Münster Cd and AAS Cd) was better than ± 0.05‰ (2s) for δ^114/110Cd. The δ^114/110Cd values of soil reference materials (NIST SRM 2709, 2709a, 2710, 2710a, 2711, 2711a and GSS‐1) relative to NIST SRM 3108 were in the range of ?0.251 to 0.632‰, the δ^114/110Cd values of rock reference materials (BCR‐2, BIR‐1, BHVO‐2, W‐2, AGV‐2, GSP‐2 and COQ‐1) varied from ?0.196‰ to 0.098‰, and that of the manganese nodule (NOD‐P‐1) was 0.163 ± 0.040‰ (2s, n = 8). The large variation in Cd isotopes in soils and igneous rocks indicates that they can be more widely used to study magmatic and supergene processes.     

Elasticity and equation of state of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>

A single crystal X-ray diffraction study on lithium tetraborate Li₂B₄O₇ (diomignite, space group I4₁ cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I4₁ cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V ₀  = 923.21(6) ų, K ₀  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a ₀  = 9.4747(3) Å, K _0a  = 73.3(9) GPa, K′ _a  = 5.1(3) and c ₀  = 10.2838(4) Å, K _0c  = 24.6(3) GPa, K′ _c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li₂B₄O₇ is very large with the zero-pressure compressibility ratio β _0c /β _0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B₄O₇]²⁻ forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B₄O₇]²⁻ units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).     

Effects of pH and Ca competition on complexation of cadmium by fulvic acids and by natural organic ligands from a river and a lake

The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca²⁺ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd²⁺] ranged from 10⁻¹³ to 10⁻¹² mol/l, and the conditional stability constant with natural ligands was log K _CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10⁻⁶ mol/g C. In the softwater River Wyre, dissolved [Cd²⁺] ranged from 4 × 10⁻¹² to 1 × 10⁻¹¹ mol/l, and the ligands were weaker (log K _CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10⁻⁶ mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.     

Enthalpies and entropies of proton and cadmium adsorption onto Bacillus subtilis bacterial cells from calorimetric measurements

We used titration calorimetry to measure the bulk heats of proton and Cd adsorption onto a common Gram positive soil bacterium Bacillus subtilis at 25.0 °C. Using the 4-site non-electrostatic model of Fein et al. [Fein, J.B., Boily, J.-F., Yee, N., Gorman-Lewis, D., Turner, B.F., 2005. Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches. Geochim. Cosmochim. Acta69 (5), 1123-1132.] to describe the bacterial surface reactivity to protons, our bulk enthalpy measurements can be used to determine the following site-specific enthalpies of proton adsorption for Sites 1-4, respectively: −3.5 ± 0.2, −4.2 ± 0.2, −15.4 ± 0.9, and −35 ± 2 kJ/mol, and these values yield the following third law entropies of proton adsorption onto Sites 1-4, respectively: +51 ± 4, +78 ± 4, +79 ± 5, and +60 ± 20 J/mol K. An alternative data analysis using a 2-site Langmuir-Freundlich model to describe proton binding to the bacterial surface (Fein et al., 2005) resulted in the following site-specific enthalpies of proton adsorption for Sites 1 and 2, respectively: −3.6 ± 0.2 and −35.1 ± 0.3 kJ/mol. The thermodynamic values for Sites 1-3 for the non-electrostatic model and Site 1 of the Langmuir-Freundlich model of proton adsorption onto the bacterial surface are similar to those associated with multifunctional organic acid anions, such as citrate, suggesting that the protonation state of a bacterial surface site can influence the energetics of protonation of neighboring sites. Our bulk Cd enthalpy data, interpreted using the 2-site non-electrostatic Cd adsorption model of Borrok et al. [Borrok, D., Fein, J.B., Tischler, M., O’Loughlin, E., Meyer, H., Liss, M., Kemner, K.M., 2004b. The effect of acidic solutions and growth conditions on the adsorptive properties of bacterial surfaces. Chem. Geol.209 (1-2), 107-119.] to account for Cd adsorption onto B. subtilis, yield the following site-specific enthalpies of Cd adsorption onto bacterial surface Sites 2 and 3, respectively: −0.2 ± 0.4 and +14.4 ± 0.9 kJ/mol, and the following third law entropies of Cd adsorption onto Sites 2 and 3, respectively: +57 ± 4 and +128 ± 5 J/mol K. The calculated enthalpies of Cd adsorption are typical of those associated with Cd complexation with anionic oxygen ligands, and the entropies are indicative of inner sphere complexation by multiple ligands. The experimental approach described in this study not only yields constraints on the molecular-scale mechanisms involved in proton and Cd adsorption reactions, but also provides new thermodynamic data that enable quantitative estimates of the temperature dependence of proton and Cd adsorption reactions.     

Pottery glaze—An excellent adsorbent for the removal of Cu(II) from aqueous solution

In the present study,pottery glaze was investigated as an excellent adsorbent for the removal of Cu(Ⅱ) ions from aqueous solution.Effect of concentration,contact time,pH,and effect of electrolyte concentration,adsorbent doses and temperature were studied by using batch process to optimize conditions for maximum adsorption. Equilibrium isotherm data were analyzed using Langmuir,Freundlich and Temkin isotherms at 30,40 and 50℃. Thermodynamic parameters such as standard enthalpy change(ΔH0),free energy change(ΔG 0)and entropy change (ΔS0)were also evaluated.These parameters indicated that adsorption process is endothermic and spontaneous in nature.The mean energy calculated from Dubinin-Radushkeuich(D-R)isotherms showed chemical nature of adsorption.The kinetic data were evaluated using the pseudo-first-order and pseudo-second order kinetic equations and it was found that data best fitted pseudo-second-order model over a wide range of initial Cu(Ⅱ)concentrations supporting that chemisorption process was involved.The adsorption and desorption studies carried out by batch process suggested 100% desorption of Cu(Ⅱ)ions with 0.1 N HCl solution.