Aqueous heavy metals removal by adsorption on β-diketone-functionalized styrene–divinylbenzene copolymeric resin

An investigation was undertaken regarding the adsorption of different heavy metal ions from aqueous solutions using ??-diketone-functionalized styrene divinylbenzene resin under different experimental conditions such as initial concentration of metal ions, contact time, pH, and chelating capacity. The functionalization of resin was carried out by the condensation reaction of sodium salt of ??-diketones (pentane-1,3-dione) and chloromethylated styrene?Cdivinylbenzene resin in dichloromethane. Functionalized resin beads were characterized by Fourier transform infrared spectroscopy. The batch method was employed using different metal ions solution from 5 to 15?mg/L at different contact times. The adsorption kinetics was tested for the pseudo-first order, pseudo-second order reaction at different experimental conditions. The rate constant of adsorption kinetic models were also calculated and good correlation coefficient (R ²?>?0.9941) was obtained for pseudo-second order kinetic model. The maximum adsorption value obtain for lead (0.725728?mg/g), chromium (0.9199?mg/g), nickel (0.4974?mg/g), cobalt (0.6196?mg/g) and cadmium (0.6519?mg/g) at equilibrium condition, which shows that ??-diketone-functionalized styrene divinylbenzene resin is an effective adsorbent for toxic metal ions.     

Fate of aluminium released by sacrificial anodes – Contamination of marine sediments by environmentally available compounds

To protect their steel structures from corrosion by cathodic protection, many harbours use aluminium sacrificial anodes, which induces aluminium release and potential contamination of the surrounding waters and sediments. To study the impact on Al mobility, a natural marine sediment was artificially contaminated with aluminium from different sources: sulphate or chloride salts, or sacrificial anodes. To estimate Al mobility in sediments, single (HCl) and sequential (F6) extractions were performed; they highlighted that aluminium is poorly mobile in natural sediment (HCl-leachable: 2% and F6-leachable: 9%). Contamination by aluminium salts inhibits HCl-leachability (≤ 2%), whereas the Al F6-leachability is intensified up to 18%, suggesting that the additional aluminium is scavenged in a mobile fraction that HCl is not able to solubilise. In case of aluminium anode contamination, sediments present surging Al HCl-leachable (15%) and F6-leachable (32%) fractions, which are related to aluminium mineralogical speciation. Indeed, contrary to the Al naturally present or introduced by salts, Al released by anodes is partly bound to the acid-soluble fraction, probably because of the integration of the released Al into the calcareous deposit produced at the anodes surfaces that finally comes away and gets mixed up with the sediment. The presence of aluminium in the acid-soluble fraction of sediments could have an important environmental impact as this fraction is easily available. Indeed, Al scavenged in the acid-soluble fraction of sediments participates in enhancing Al lability near the sacrificial anodes and may affect the surrounding ecosystems.     

Is most hummocky cross‐stratification formed by large‐scale ripples?

Although normal isotropic hummocky cross‐stratification is commonly interpreted to be the deposit of large‐scale ripples, there are many reasons why this may not usually be the case. These reasons include: (i) that the stratification produced by large‐scale ripples does not particularly look like isotropic hummocky cross‐stratification; (ii) that it is difficult reconciling the abundance of HCS with the restricted hydraulic stability of large‐scale ripples in silt to fine sand (i.e. the grain sizes in which hummocky cross‐stratification is usually found); (iii) that the distribution of hummocky cross‐stratification within ancient storm beds is not the distribution that would be expected from large‐scale ripples; (iv) that the flows calculated to have formed ancient examples of hummocky cross‐stratification would be expected to generate an upper stage plane bed rather than ripples; and (v) that it is difficult to explain why large‐scale ripples would predominate in the proximal parts of storm beds when modern storm flows commonly exceed the threshold for entrainment. In contrast to the various hypotheses which propose that isotropic hummocky cross‐stratification is generated by ripples, an alternative hypothesis which suggests that it is generated by instabilities, does seem to adequately explain the origin of hummocky cross‐stratification. However, it is difficult to accept this hypothesis given that the origin of the proposed instabilities is unproven. These conclusions highlight the continued uncertainty regarding the process, which generates hummocky cross‐stratification.     

Toward the understanding of the treatment of textile industries’ effluents by clay: adsorption of anionic dye on kaolinite

Clays, particularly kaolinite, are promising adsorbents for the treatment of textile effluents, but there is a need of better understanding the mechanisms of adsorption, especially in the case of anionic dyes. Thus, the removal of RR120 anionic dye was investigated using Tunisian raw clay (TBK) composed of kaolinite and illite, and a standard kaolinite (KGa-2), and conducting batch experiments by varying different parameters (contact time, ionic strength, concentration, temperature). We investigated the clays’ surface charges by electrophoretic mobility measures and the dye-clay interactions during adsorption, by the streaming-induced potentials (SIP). The results showed that KGa-2 has higher adsorption capacity for RR120 dye than TBK clay, moreover enhanced by increasing the ionic strength and/or lowering the pH of the aqueous. The SIP results showed an increase of negative charges for both clays, reflecting the adsorption of the anionic dye on the positive charges of the amphoteric surfaces of the clays. The SIP magnitudes indicated a higher adsorption rate for KGa-2 in accordance with the kinetic study. The Sips model that described the best adsorption isotherms indicates lateral interactions of the dye molecules, stronger in the case of KGa-2 than TBK. Also, the dye molecules form a thinner layer on KGa-2 surfaces. In addition, the dye molecule’s structure was not altered, as verified by mass spectrometry. The adsorption process was feasible and spontaneous and favored at ambient temperature. Thus, kaolinite-rich clays are effective in the removal of anionic dyes in aqueous solution and potential good adsorbents in wastewater treatment.     

Structural characterization of high-pressure C–Na<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>5</Subscript> by single-crystal diffraction and <Superscript>29</Superscript>Si MAS NMR

Single crystals of C–Na₂Si₂O₅ have been synthesized from the hydrothermal recrystallization of a glass. The title compound is monoclinic, space group P2₁/c with Z= 8 and unit-cell parameters a= 4.8521 (4)Å, b=23.9793(16)Å, c=8.1410(6)Å, β=90.15(1)° and V=947.2(2)ų. The structure has been determined by direct methods and belongs to the group of phyllosilicates. It is based on layers of tetrahedra with elliptically six-membered rings in chair conformation. The sequence of directedness within a single ring is UDUDUD. The sheets are parallel to (010) with linking sodium cations in five- and sixfold coordination. Concerning the shape and the conformation of the rings, C–Na₂Si₂O₅ is closely related to β-Na₂Si₂O₅. However, both structures differ in the stacking sequences of the layers. A possible explanation for the frequently observed polysynthetic twinning of phase C is presented. In the ²⁹Si MAS-NMR spectrum of C–Na₂Si₂O₅ four well-resolved lines of equal intensity are observed at ?86.0, ?86.3, ?87.4, and ?88.2?ppm. The narrow range of isotropic chemical shifts reflects the great similarity of the environments of the different Si sites. This lack of pronounced differences in geometry renders a reliable assignment of the resonance lines to the individual sites on the basis of known empiric correlations and geometrical features impossible.     

Efficient removal of Evans blue dye by Zn–Al–NO<Subscript>3</Subscript> layered double hydroxide

Evans blue (EB) dye has been successfully removed from aqueous solution through chemisorption process with synthetic layered double hydroxides (LDH) [Zn_1?x Al _x (OH)₂NO₃·nH₂O, x = 0.2–0.33]. Detailed evaluation of dye adsorption characteristics in aqueous medium has been studied for different layer charged hydroxides. The objective of the study was efficient removal of a dye by LDH and understanding the structure–property relationship of the LDH on its adsorption behaviour. Highest Langmuir monolayer adsorption capacity (Qt) of 113.64 mg g^?1 was observed for highest layer charge x = 0.33, and it is higher than previously reported values for the LDH-EB dye system. Under optimized condition, 99% of EB dye is removed from aqueous solution within 60 min at 313 K. The monotonous increase in Qt value with increasing layer charge is correlated with layer charge density (LCD) and lower particle size of the synthetic LDH. The variation in Qt among different layer charged materials is marginal (3.46–4.17%) with respect to the respective anion exchange capacity (AEC) of LDH NO₃. The limited contribution of AEC surmises the occurrence of surface-only adsorption and absence of intercalation as validated by the XRD analysis. The spontaneity of the EB dye removal increases with increasing temperature and LCD. The chemisorption nature of the adsorption reaction is well supported by the thermodynamics values.     

Bearing capacity factor, <Emphasis Type="Italic">N</Emphasis><Subscript><Emphasis Type="Italic">γ</Emphasis></Subscript>, for unsaturated soils by ZEL method

Bearing capacity of foundations is often determined for saturated state of the soil, regarding its simple and conservative results. This assumption, however, results in very uneconomic and overconservative design for a wide range of climates in the world. In this paper, plasticity equations were employed and extended for unsaturated soils to establish a theoretical approach to investigate the bearing capacity of unsaturated soils. It is achieved by combining the concept of effective stress and plasticity equations in terms of effective stress in unsaturated soils. The advantage of Bishop’s (4) effective stress concept was employed to simplify the equations. The equations were then transformed onto the zero extension lines directions to generalize this method for both associative and non-associative problems by which both stress and velocity field can be determined for unsaturated soils. A computer code was also developed to solve the relatively complex plasticity equations for a wide range of soil friction angles and matric suctions to compute the corresponding bearing capacity factor, N _γ , for strip foundations with smooth and rough base. This factor seems to be one of the major contributors in the bearing capacity of shallow foundations. The results have been presented in design charts and theoretical equations.     

Fractal-like adsorption kinetics of Pb^2＋ in rocks

The adsorption kinetics of Pb^2＋ in rocks has been studied using ion selective electrodes and atomic absorption spectrophotometer. The results showed that the adsorption process is a fractal-like reaction. The adsorption rate was relatively high before 30 minutes, and then dropped. The saturated adsorption capacity （a） of Pb^2＋ and kinetic parameters （b, a, D and k） increased with increasing initial concentrations of Pb^2＋. These parameters （except a） decreased while Na^＋ was present in the solution. Furthermore, the smaller the rocks were in grain size, the bigger these kinetic parameters would be, though the parameter a was almost constant.     

The Laalam (Algeria) damaging landslide triggered by a moderate earthquake (M<Subscript>w</Subscript> = 5.2)

On March 20th, 2006, a moderate earthquake (M_w = 5.2) struck the Laalam (NE-Algeria). The damage was centred in the Laalam village where four deaths, 68 injured and more than 40 housing units destroyed making dozens of peoples homeless. Damage and casualties are directly related to an earthquake-induced landslide occurred at 10 km far from the epicenter (ISC relocation). The landslide rupture, mapped by using a ground based survey, is striking NE-SW along a 1-km length rupture with a 45 cm of lateral displacement. The rupture plan is dipping 40° at the surface and showing horizontal striations. A 75 cm of pre-2006 lateral displacement is also observed indicating a repetitive behaviour of the landslide. The last time where the landslide was activated extends back to 1974 following another moderate earthquake. This landslide reminds us the high level hazard of induced ground failures due slope instabilities in mountainous zones of seismically active areas.     

The crystal structure and thermal expansion tensor of MgSO<Subscript>4</Subscript>–11D<Subscript>2</Subscript>O(meridianiite) determined by neutron powder diffraction

We have collected high-resolution neutron powder diffraction patterns from MgSO₄·11D₂O over the temperature range 4.2–250 K. The crystal is triclinic, space-group \( \text{P} \bar{1} \) (Z = 2) with a = 6.72746(6) Å, b = 6.78141(6) Å, c = 17.31803(13) Å, α = 88.2062(6)°, β = 89.4473(8)°, γ = 62.6075(5)°, and V = 701.140(6) ų at 4.2 K, and a = 6.75081(3) Å, b = 6.81463(3) Å, c = 17.29241(6) Å, α = 88.1183(3)°, β = 89.4808(3)°, γ = 62.6891(3)°, and V = 706.450(3) ų at 250 K. Structures were refined to wRp = 3.99 and 2.84% at 4.2 and 250 K, respectively. The temperature dependence of the lattice parameters over the intervening range have been fitted with a modified Einstein oscillator model which was used to obtain the coefficients of the thermal expansion tensor. The volume thermal expansion, α_V, is considerably smaller than ice Ih at all temperatures, and smaller even than MgSO₄·7D₂O (although ?α_V/?T is very similar for both sulfates); MgSO₄·11D₂O exhibits negative α_V below 55 K (compared to 70 K in D₂O ice Ih and 20 K in MgSO₄·7D₂O) The relationship between the magnitude and orientation of the principal axes of the expansion tensor and the main structural elements are discussed.     

Assessment of groundwater contamination by NO<Subscript>3</Subscript><Superscript>−</Superscript> using geographical information system in the Zhangye Basin,Northwest China

Geographical information system (GIS) technology was used to investigate NO₃ ⁻ concentration of groundwater in the Zhangye Basin, Northwest China. Thematic information and NO₃ ⁻ data of groundwater from the Zhangye Basin were analyzed in a GIS environment to study the extent and variation of NO₃ ⁻ concentration and to establish spatial relationships with corresponding land use types. About 38.8% of groundwater samples showed NO₃ ⁻ concentration above the human affected value (13 mg/l NO₃ ⁻), while more than 10.2% exceeded the maximum acceptable level (50 mg/l NO₃ ⁻) according to WHO regulations. The spatial distribution of NO₃ ⁻ of groundwater in the Zhangye Basin showed an obvious character of zonation; the high NO₃ ⁻ concentration was mainly located in the city seat areas, and Zhangye City was the high-value center. The probability of over 90% for NO₃ ⁻ concentration exceeding 13 mg/l was found in urban seat areas. The spatial analyses indicated that groundwater contamination by NO₃ ⁻ was closely related to one specific land use class, the urban. The NO₃ ⁻ concentration of groundwater under urban was significantly higher than that under irrigation land or sand dune. Most of the unacceptable NO₃ ⁻ levels were found in groundwater samples assigned to urban area, but a few were also found allotted to irrigation land class. Therefore, urban source was considered the principal source of NO₃ ⁻ contamination of groundwater in the Zhangye Basin, while irrigation land source was still a possible source of NO₃ ⁻ contamination.     

Does air ionization by radon cause low-frequency atmospheric electromagnetic earthquake precursors?

Natural Hazards - The aim of this work is to study the relationship between the pre-earthquake emissions of radon and ULF/ELF (1–30&nbsp;Hz) atmospheric electromagnetic radiation. The...     

Treatment of Loose to Medium Dense Sands by Granular Piles: Improved SPT ‘N<Subscript>1</Subscript>’ Values

The effect of granular pile installation on the modifications induced in loose to medium dense granular deposits is studied. SPT is the most often used to evaluate the in situ soil properties. Expressions for modified SPT N₁ values for different soils, i.e., for different initial SPT N₁ values, were determined as functions of replacement ratio from the available field data. Improvements in the ground are presented in the form of modified or improved SPT N₁ values versus replacement ratio charts, which can then be used to design the required degree of treatment for the expected improvement or to estimate the improved values of treated ground for different initial states of sands.     

Characterization of synthetic hedenbergite (CaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)–petedunnite (CaZnSi<Subscript>2</Subscript>O<Subscript>6</Subscript>) solid solution series by X-ray powder diffraction and <Superscript>57</Superscript>Fe Mössbauer spectroscopy

Clinopyroxenes along the solid solution series hedenbergite (CaFeSi₂O₆)–petedunnite (CaZnSi₂O₆) were synthesized under hydrothermal conditions and different oxygen fugacities at temperatures of 700 to 1200 °C and pressures of 0.2 to 2.5 GPa. Properties were determined by means of X-ray diffraction, electron microprobe analysis and ⁵⁷Fe Mössbauer spectroscopy at 298 K. Unit-cell parameters display a linear dependency with changing composition. Parameters a₀ and b₀ exhibit a linear decrease with increasing Zn content while the monoclinic angle increases linearly. Parameter c₀ is not affected by composition and remains constant at a value of 5.248 Å. The molar volume can be described according to the equation V_mol (ccm mol^–1)=33.963(16)–0.544(31)*Zn pfu. The isomer shifts of ferrous iron on the octahedral M1 site in hedenbergite are not affected by composition along the hedenbergite–petedunnite solid solution series and remain constant at an average value of 1.18 mm s^–1. Quadrupole splittings of Fe²⁺ on the M1 are, however, strongly affected by composition, and they decrease linearly with increasing petedunnite component in hedenbergite, ranging from 2.25 mm s^–1 for pure hedenbergite end member to 1.99 mm s^–1 for a solid solution containing 84 mole% petedunnite. The half-widths of intermediate solid solutions vary between 0.26 and 0.33 mm s^–1, indicating, in accordance with the microprobe analyses and X-ray diffraction, that samples are homogeneous and well-crystallized. The data from this study demonstrate that the crystallinity of hedenbergitic clinopyroxenes can be improved by using oxide mixtures as starting materials. Crystal sizes for intermediate compositions range up to 70 m, suitable for standard single-crystal X-ray analysis.This paper is dedicated to Prof. Dr. Georg Amthauer, Salzburg, on occasion of his 60th birthday     

The preference of nitrate uptake in Chinese prickly ash estimated by δ<Superscript>15</Superscript>N values and cation concentrations

The nitrogen isotopic compositions of plant tissue could reflect its uptake of and preference for ammonium or nitrate. However, various factors may influence the field-collected δ¹⁵N values under field condition, which causes the interpretation problematic. The spatial variation of nitrogen (N) concentrations and the isotopic compositions were investigated in the soils and tissues of Chinese prickly ash from the southwest China to the east China. The objectives were to investigate the variation in soil and tissue δ¹⁵N values and N forms taken up by the plant. The leaf and root δ¹⁵N values varied significantly in response to the pattern of soil δ¹⁵N values. The difference in δ¹⁵N values between the leaves and roots was 2.57‰ and may be caused by an increase in the transport of unassimilated \( {\text{NO}}_{3}^{ - } \) and \( {\text{NH}}_{4}^{ + } \) to the leaves. Leaf nitrogen was significantly and positively correlated with leaf potassium and negatively related to leaf calcium. Because potassium is the favoured counter-cation for nitrate transport in the xylem, the enrichment of ¹⁵N in leaf relative to root induced by preferenced uptake of nitrate should be accompanied by significant and positive relationship of leaf nitrogen with leaf potassium concentrations. These results suggest that Chinese prickly ash prefers \( {\text{NO}}_{3}^{ - } \) over \( {\text{NH}}_{4}^{ + } \).     

Archaean fluid-assisted crustal cannibalism recorded by low δ<Superscript>18</Superscript>O and negative ε<Subscript>Hf(T)</Subscript> isotopic signatures of West Greenland granite zircon

The role of fluids during Archaean intra-crustal magmatism has been investigated via integrated SHRIMP U–Pb, δ¹⁸O and LA-MC-ICPMS ¹⁷⁶Hf isotopic zircon analysis. Six rock samples studied are all from the Nuuk region (southern West Greenland) including two ~3.69 Ga granitic and trondhjemitic gneisses, a 3.64 Ga granitic augen gneiss, a 2.82 Ga granodioritic Ikkattoq gneiss, a migmatite with late Neoarchaean neosome and a homogeneous granite of the 2.56 Ga Qôrqut Granite Complex (QGC). All zircon grains were thoroughly imaged to facilitate analysis of magmatic growth domains. Within the zircon analysed, there is no evidence for metamictization. Initial ε_Hf zircon values (n = 63) are largely sub-chondritic, indicating the granitic host magmas were generated by the remelting of older, un-radiogenic crustal components. Zircon from some granite samples displays more than one ²⁰⁷Pb/²⁰⁶Pb age, and correlated with ¹⁷⁶Hf/¹⁷⁷Hf compositions can trace multiple phases of remelting or recrystallization during the Archaean. Model ages calculated using Lu/Hf arrays for each sample indicate that the crustal parental rocks to the granites, granodiorites and trondhjemites segregated from a chondrite-like reservoir at an earlier time during the Archaean, corresponding to known formation periods of more primitive tonalite–trondhjemite–granodiorite (TTG) gneisses. Zircon from the ~3.69 Ga granite, the migmatite and QGC granite contains Eoarchaean cores with chondritic ¹⁷⁶Hf/¹⁷⁷Hf and mantle-like δ¹⁸O compositions. The age and geochemical signatures from these inherited components are identical to those of surrounding tonalitic gneisses, further suggesting genesis of these granites by remelting of broadly tonalitic protoliths. Zircon oxygen isotopic compositions (n = 62) over nine age populations (six igneous and three inherited) have weighted mean or mean δ¹⁸O values ranging from 5.8 ± 0.6 to 3.7 ± 0.5‰. The 3.64 Ga granitic augen gneiss sample displays the highest δ¹⁸O with a mildly supra-mantle composition of 5.8 ± 0.6‰. Inherited Eoarchaean TTG-derived zircon shows mantle-like values. Igneous zircon from all other samples, spanning more than a billion years of Archaean time, record low δ¹⁸O sub-mantle compositions. These are the first low δ¹⁸O signatures reported from Archaean zircon and represent low δ¹⁸O magmas formed by the remelting and metamorphism of older crustal rocks following high-temperature hydrothermal alteration by meteoric water. Meteoric fluid ingress coupled with crustal extension, associated high heat flow and intra-crustal melting are a viable mechanism for the production of the low δ¹⁸O granites, granodiorites and trondhjemites reported here. Both high and low δ¹⁸O magmas may have been generated in extensional environments and are distinct in composition from Phanerozoic I-type granitic plutonic systems, which are typified by increasing δ¹⁸O during intra-crustal reworking. This suggests that Archaean magmatic processes studied here were subtly different from those operating on the modern Earth and involved extensional tectonic regimes and the predominance of remelting of hydrothermally altered crystalline basement.     

In situ U–Pb rutile dating by LA-ICP-MS: <Superscript>208</Superscript>Pb correction and prospects for geological applications

Rutile is a common accessory mineral that occurs in a wide spectrum of metamorphic rocks, such as in blueschists, eclogites, and granulites and as one of the most stable detrital heavy minerals in sedimentary rocks. The advent of rutile trace element thermometry has generated increased interest in a better understanding of rutile formation. This study documents important analytical advances in in situ LA-ICP-MS U/Pb geochronology of rutile: (1) Matrix matching, necessary for robust in situ dating is fulfilled by calibrating and testing several rutile standards (R10, R19, WH-1), including the presentation of new TIMS ages for the rutile standard R19 (489.5 ± 0.9 Ma; errors always stated as 2 s). (2) Initial common lead correction is routinely applied via ²⁰⁸Pb, which is possible due to extremely low Th/U ratios (usually <0.003) in most rutiles. Employing a 213 nm Nd:YAG laser coupled to a quadrupole ICP-MS and using R10 as a primary standard, rutile U/Pb concordia ages for the two other rutile standards (493 ± 10 Ma for R19; 2640 ± 50 Ma for WH-1) and four rutile-bearing metamorphic rocks (181 ± 4 Ma for Ivrea metapelitic granulite; 339 ± 7 Ma for Saidenbach coesite eclogite; 386 ± 8 Ma for Fjortoft UHP metapelite; 606 ± 12 Ma for Andrelandia metepelitic granulite) always agree within 2% with the reported TIMS ages and other dating studies from the same localities. The power of in situ U/Pb rutile dating is illustrated by comparing ages of detrital rutile and zircon from a recent sediment from the Christie Domain of the Gawler Craton, Australia. While the U/Pb age spectrum from zircons show several pronounced peaks that are correlated with magmatic episodes, rutile U/Pb ages are marked by only one pronounced peak (at ca 1,675 Ma) interpreted to represent cooling ages of this part of the craton. Rutile thermometry of the same detrital grains indicates former granulite-facies conditions. The methods outlined in this paper should find wide application in studies that require age information of single spots, e.g., provenance studies, single-crystal zoning and texturally controlled dating.     

The thermal expansion and crystal structure of mirabilite (Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·10D<Subscript>2</Subscript>O) from 4.2 to 300 K,determined by time-of-flight neutron powder diffraction

We have collected high resolution neutron powder diffraction patterns from Na₂SO₄·10D₂O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P2₁/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å³ at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å³ at 300 K. Structures were refined to R _P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10^?7 T ³ + 0.00047(2) T² ? 0.027(2) T + 1437.0(1) Å³ (R ² = 99.98%). The coefficient of volume thermal expansion, α _V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α _V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.     

Kinetic and equilibrium studies on the removal of <Superscript>14</Superscript>C-ethion residues from wastewater by copper-based metal–organic framework

There are compelling economic and environmental reasons to remove pesticides from wastewater because they are toxic and carcinogenic. The effectiveness of copper-based metal–organic framework (Cu-BTC) for adsorbing the insecticide ¹⁴C-ethion from wastewater has been studied as function of contact time, adsorbent dosage, temperature and pH. ¹⁴C-ethion/Cu-BTC isotherms exhibit two plateaus (BET type IV) and are reliably represented by Brunauer–Deming–Deming–Teller and Zhu–Gu models, with deviations of only 1.99 and 3.95%, respectively. The removal curve measured under batch operation is well represented by a pseudo-first-order equation, yielding results equivalent to the theoretical linear driving force model of Glueckauf. At pH 7, 75 mg L^?1 ethion concentration, 150 min, 25 °C and 0.425 g L^?1 Cu-BTC dose, the sorbent capacity is ca. 122 mg g^?1. Moreover, Cu-BTC has a good stability after six adsorptions cycles. Finally, our results disclose the fundamental understanding of the adsorption mechanism: the ethion molecule coordinates to two copper(II) atoms across the metal–organic framework channel via the phosphoryl (P–O) group.