Evaluation of the use of legumes for biodegradation of petroleum hydrocarbons in soil

The aim of this research was to evaluate the potential of six legumes: Medicago sativa L., Glycine max, Arachis hypogea, Lablab purpureus, Pheseolus vulgaris and Cajanus cajan to restore within a short period of time soil contaminated with 3% crude oil. The legumes in five replications were grown in crude oil-contaminated and crude oil-uncontaminated soil in a completely randomized design. Plants were assessed for seedling emergence, plant height and leaf number. GC–MS was used to analyze the residual crude oil from the rhizosphere of the legumes. Plant growth parameters were reduced significantly (P < 0.05) for legumes in contaminated soil compared to their controls. In the 4th week after planting (WAP), shoot height increased across the species up to the 8th WAP. However, in the 12 WAP no significant increase in the shoot of all species was observed. Two WAP legumes planted in contaminated soil had significantly (P < 0.05) higher leaf number than these planted in uncontaminated soil with the exception of M. sativa. In the 4th WAP, only A. hypogea and P. vulgaris had increased leaf number, while in the 6th WAP, only L. purpureus had increased leaf number and survived up to the 12th WAP while most of the legumes species died. Chromatographic profiles indicated 100% degradation of the oil fractions in C. cajan and L. purpureus after 90 days. For other legumes however, greater losses of crude oil fractions C₁–C₁₀ and C₁₀–C₂₀ were indicated in rhizosphere soil of P. vulgaris and G. max, respectively. The most effective removal (93.66%) of C₂₁–C₃₀ components was observed in G. max-planted soil even though vegetation was not established. The legumes especially C. cajan, L. purpureus and A. hypogea are promising candidates for phytoremediation of petroleum hydrocarbon-impacted soil.     

Electron paramagnetic resonance and ENDOR studies of Cr3+ - Al3+ pairs in forsterite

The electron paramagnetic resonance (EPR) spectrum of Cr³⁺ in synthetic crystals of forsterite consists primarily of lines of Cr³⁺ “isolated” at the M1 and M2 positions in a “perfect” crystal environment without local charge compensation. In addition it shows two nonequivalent superhyperfine-split sextets with different intensities which are due to strong interaction of the Cr³⁺ electron spin S (S=3/2) with an adjacent nuclear spin I(I=5/2). Electron nuclear double resonance (ENDOR) experiments revealed that the sextets result from Cr³⁺ (M1) - Al³⁺ and Cr³⁺ (M2) - Al³⁺ pairs, Al being located at adjacent tetrahedral Si sites. The g, D, A, and A′ tensor components of the Cr³⁺ - Al³⁺ pairs have been determined at room temperature. The values of the pairs are distinct although they are not very different from the corresponding data of “isolated” Cr³⁺. From the intensities of the EPR spectra the relative concentration of the Cr³⁺ - Al³⁺ pairs with respect to “isolated” Cr³⁺ has been estimated.     

Mechanisms of expansion for an introduced species of cordgrass, Spartina densiflora, in Humboldt Bay, California

The dominant plant in Humboldt Bay salt marshes in Spartina densiflora, a species of cordgrass apparently introduced from South America. At several salt marshes and restoration sites around Humboldt Bay, distribution of this plant has increased significantly. We investigated the relative contributions of vegetative tiller production and seed germination to the establishment and expansion of S. densiflora. Lateral spread of plants surrounded by competitors were compared to areas without competing plant species. Plants growing in areas without competitors had significantly higher rates of vegetative expansion (p<0.0001). Viable seed production, germination rates, seedling survivorship, and growth of adult plants were measured in six salinity treatments. Approximately 1,977±80 viable seeds are produced per plant (0.25–0.5 m²). The number of germinating seeds was inversely related to increases in salinity. Salinity treatments between 19‰ and 35‰ produced significantly lower germination rates than salinities of 0–18‰ (p<0.0001). Seedling survivorship was 50% at ≤4‰ and 8–14% at ≥11‰. Lateral expansion of adult, greenhouse-grown plants occurred in all salinity treatments, with modest decreases in the highest salinity treatments (p<0.05). Our findings indicate that S. densiflora expands primarily by vegetative expansion, and lateral tillers are produced by throughout the year. Spartina densiflora produces prolific amounts of seed, but recruitment in mature salt marshes may be limited by competitors and higher salinities. At restoration sites, planting of native species such as Salicornia virginica, Distichlis spicata, or Jaumea carnosa may prevent monospecific stands of S. densiflora from developing.     

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study

Four samples of synthetic chromium-bearing spinels of (Mg, Fe²⁺)(Cr, Fe³⁺)₂O₄ composition and four samples of natural spinels of predominantly (Mg, Fe²⁺)(Al, Cr)₂O₄ composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr₂O₄ spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr³⁺ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed ⁴ A _2g  → ⁴ T _2g and ⁴ A _2g  → ⁴ T _1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions ⁴ A _2g  → ² E _g and ⁴ A _2g  → ² T _1g of Cr³⁺, intensified by exchange-coupled interaction between Cr³⁺ and Fe³⁺ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm^?1. A vague broad band in the range from ca. 15,000 to 12,000 cm^?1 in synthetic spinels is tentatively attributed to ^IVCr²⁺ + ^VICr³⁺ → ^IVCr³⁺ + ^VICr²⁺ intervalence charge-transfer transition. Iron, mainly as octahedral Fe³⁺, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O^2? → Fe³⁺, Fe²⁺ transitions). As tetrahedral Fe²⁺, it appears as a strong infrared absorption band at around 4,850 cm^?1 caused by electronic spin-allowed ⁵ E → ⁵ T ₂ transitions of ^IVFe²⁺. From the composition shift of the U-band in natural and synthetic MgCr₂O₄ spinels, the coefficient of local structural relaxation around Cr³⁺ in spinel MgAl₂O₄–MgCr₂O₄ system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O₆ polyhedra known so far. The octahedral modulus of Cr³⁺ in MgCr₂O₄, derived from pressure-induced shift of the U-band of Cr³⁺, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr³⁺ in natural and synthetic MgCr₂O₄ spinels indicates that Cr–O-bonding in octahedral sites of MgCr₂O₄ has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl₂O₄ spinel, B does not much depend on pressure.     

Structure analysis on synthetic emerald crystals

Single crystals of emerald synthesized by means of the flux method were adopted for crystallographic analyses. Emerald crystals with a wide range of Cr³⁺-doping content up to 3.16 wt% Cr₂O₃ were examined by X-ray single crystal diffraction refinement method. The crystal structures of the emerald crystals were refined to R ₁ (all data) of 0.019–0.024 and wR ₂ (all data) of 0.061–0.073. When Cr³⁺ substitutes for Al³⁺, the main adjustment takes place in the Al-octahedron and Be-tetrahedron. The effect of substitution of Cr³⁺ for Al³⁺ in the beryl structure results in progressively lengthening of the Al–O distance, while the length of the other bonds remains nearly unchanged. The substitution of Cr³⁺ for Al³⁺ may have caused the expansion of a axis, while keeping the c axis unchanged in the emerald lattice. As a consequence, the Al–O–Si and Al–O–Be bonding angles are found to decrease, while the angle of Si–O–Be increases as the Al–O distance increases during the Cr replacement.     

Electron spin resonance of trivalent chromium in forsterite,Mg2SiO4

The electron spin resonance (ESR) spectrum of Cr³⁺ in a synthetic single crystal of forsterite doped with Cr₂O₃ was studied at room temperature in the X-band frequency range. The dependence of the observed spectra on the crystal orientation with respect to the applied magnetic field was investigated. The ESR spectra are described by the spin Hamiltonian \(H = \beta HgS + D(S_Z^{\text{2}} - {\text{1/3}}S{\text{(}}S{\text{ + 1)) + }}E{\text{(}}S_x^{\text{2}} - S_y^{\text{2}} {\text{)}}\) with S=3/2. The spin resonance reveals that the chromium ions are located at both the M1 and M2 positions. Other possible substitutional or interstitial Cr³⁺ positions may be possible, but were not observed. The site occupancy numbers of Cr³⁺ at M1 and M2 are roughly 1.2×10^?4 and 0.8×10^?4, respectively, assuming that chromium is oxidized completely. The preference of the chromium ions for M1 was interpreted qualitatively in terms of crystal field criteria. The rhombic and axial spin Hamiltonian parameters, D and E, and the directions of the magnetic axes obtained for M1 and M2 are consistent with the respective oxygen coordination polyhedra.     

Polarized electronic absorption spectra of Cr2SiO4 single crystals

Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm^–1 were obtained for the orthorhombic thenardite-type phase Cr₂SiO₄, unique in its Cr²⁺-allocation suggesting some metal-metal bonding in Cr²⁺Cr²⁺ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr₂SiO₄, synthesized at 35?kbar, above 1440?°C from high purity Cr₂O₃, Cr (10% excess) and SiO₂ in chromium capsules. The Cr₂SiO₄-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm^–1, in the absorption spectra of Cr₂SiO₄ single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr²⁺ in a distorted square planar coordination of point symmetry C₂. The crystal field parameter of Cr²⁺ is estimated to be 10?Dq?10700?cm^–1. A relatively intense, sharp band at 18400?cm^–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr²⁺. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm^–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr₂ ⁴⁺, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr²⁺ as well as δ-δ* transitions of Cr₂ ⁴⁺ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Cr_loc ²⁺?Cr_{2, cpl} ⁴⁺ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.     

Hyperfine interactions and spin transfer between Cr3+ and Al3+ in a synthetic single crystal of Mg2SiO4. A theoretical approach to the interpretation of EPR data

The occurrence of Cr-Al pairs in Mg₂SiO₄ has been detected by EPR spectroscopy. In the case where Cr³⁺ replaces Mg at the M2 position three different neighboring Si sites may be substituted by Al³⁺, which should yield different superhyperfine interactions. A new spectrum is presented which shows the presence of two of these possible pair configurations. An assignment of the spectral features to a specific Cr-Al pair with Cr at M2 from the experimental data alone was not possible, therefore, MSX _α cluster calculations have been performed from which the differences in the superhyperfine interaction for the various pair configurations could be obtained. Best agreement with the data of the Cr³⁺(M2)-Al pair exhibiting the most intense group of lines in the EPR spectrum was obtained for the situation where Al³⁺ is at the Si position with the shortest distance to M2. The second observed Cr³⁺(M2)-Al pair, which is significantly weaker in intensity, could not yet be assigned.     

Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil – pH as the master variable

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of Cr^III potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic Cr^III into hazardous Cr^VI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of Cr^VI from the easily soluble Cr^III and 2) the potential bioavailability of Cr^III and that of Cr^VI species produced in the oxidation of Cr^III in agricultural soil (fine sand, organic carbon 3.2%). The amount of Cr^VI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of Cr^III into Cr^VI by manganese oxide (Mn^IVO₂) and 2) the subsequent reduction of Cr^VI by organic matter back to Cr^III. The effect of pH on this net-oxidation of Cr^III and on the chemical availability of both Cr^III and Cr^VI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO₂, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO₂, the net-oxidation of Cr^III into Cr^VI (1 mM CrCl₃ in soil suspensions, 1:10 w/V) was negligible. As for the MnO₂-treated soils, at maximum only 4.7% of added Cr^III was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of Cr^VI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of Cr^VI back to Cr^III. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of Cr^III, which lowered the overall amount of Cr^III susceptible for oxidation. Moreover, the oxidation reactions by MnO₂ were inhibited by formation of Cr(OH)₃ coverage on its surface. The pH-dependent chemical bioavailability of added Cr^III differed from that of the Cr^VI formed. At elevated pHs the chemical availability of Cr^III decreased, whereas that of Cr^VI produced increased. However, the risk of Cr^VI formation through oxidation of the easily soluble inorganic Cr^III was considered to be low in agricultural soils high in organic matter and low in innate MnO₂.     

Optical absorption spectroscopy of synthetic tourmalines

Tourmaline solid solutions containing Fe, Fe+ Ti, Cr, Ni, Cu, Co, Mn chromophoric centers have been grown hydrothermally at 650° C and 1,5 kbar on natural seeding plates close to the elbaite composition. The newly grown tourmalines were characterized by chemical analyses and optical absorption spectroscopy in the range 26316-5000 cm^-1 at 297 K and in the range 26316-9090 cm^-1 at 77 K. Most characteristic of Fe²⁺, Fe³⁺-bearing specimens is the presence of intensive σpolarized absorption bands caused by exchange-coupled Fe²⁺-Fe³⁺ pairs in Y- and Z-sites of the tourmaline structure. An additional intensive absorption band 12500 cm^-1 (σ-polarisation) appears in some specimens but is not yet found in spectra of natural tourmalines. The colour and spectroscopic properties of the Fe³⁺, Mn³⁺ and Cu²⁺ containing tourmalines are significantly affected by the presence of even the smallest Li-contents. The results suggest that Fe²⁺, Cu²⁺, Co²⁺, Ni²⁺-ions occupy, predominantly, Y-sites of the tourmaline structure, whereas the Cr³⁺-ions seem to enter the smaller Z-octachedra.     

EPR study of chromium-doped forsterite crystals: Cr3+(M1) with associated trivalent ions Al3+ and Sc3+

Electron paramagnetic resonance (EPR) study of single crystals of forsterite co-doped with chromium and scandium has revealed, apart from the known paramagnetic centers Cr³⁺(M1) and Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) (Ryabov in Phys Chem Miner 38:177–184, 2011), a new center Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ formed by a Cr³⁺ ion substituting for Mg²⁺ at the M1 structural position with a nearest-neighbor Mg²⁺ vacancy at the M2 position and a Sc³⁺ ion presumably at the nearest-neighbor M1 position. For this center, the conventional zero-field splitting parameters D and E and the principal g values have been determined as follows: D?=?33,172(29) MHz, E?=?8,482(13) MHz, g?=?[1.9808(2), 1.9778(2), 1.9739(2)]. The center has been compared with the known ion pair Cr³⁺(M1)–Al³⁺ (Bershov et al. in Phys Chem Miner 9:95–101, 1983), for which the refined EPR data have been obtained. Based on these data, the known sharp M1″ line at 13,967?cm^?1 (with the splitting of 1.8?cm^?1), observed in low-temperature luminescence spectra of chromium-doped forsterite crystals (Glynn et al. in J Lumin 48, 49:541–544, 1991), has been ascribed to the Cr³⁺(M1)–Al³⁺ center. It has been found that the concentration of the new center increases from 0 up to 4.4?×?10¹⁵?mg^?1, whereas that of the Cr³⁺(M1) and Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) centers quickly decreases from 7.4?×?10¹⁵?mg^?1 down to 3?×?10¹⁵?mg^?1 and from 2.7?×?10¹⁵?mg^?1 down to 0.5?×?10¹⁵?mg^?1, i.e., by a factor of 2.5 and 5.4, respectively, with an increase of the Sc content from 0 up to 0.22 wt?% (at the same Cr content 0.25 wt?%) in the melt. When the Sc content exceeds that of Cr, the concentration of the new center decreases most likely due to the formation of the Sc³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ complex instead of the Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ center. The formation of such ordered neutral complex is in agreement with the experimental results, concerning the incorporation of Sc into olivine, recently obtained by Grant and Wood (Geochim Cosmochim Acta 74:2412–2428, 2010).     

Chromium solubility in anhydrous Phase B

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.     

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.     

Evaluation,characterization and analytical application of a new composite material for removing metal ions from wastewater

A new organic/inorganic composite based on polyacrylonitrile and stannic molybdophosphate (PAN–SMP) as an adsorbent was synthesized under various conditions. The physicochemical properties of this material were specified by elemental analysis, scanning electron microscopy, infrared spectroscopy and thermogravimetry studies. The synthesized material was found to be stable in demineralized water, in dilute acids, under gamma radiation up to the total radiated of 100 kGy doses and in high temperature up to 500 °C. Ion exchange capacity of the synthesized composite and its distribution coefficient (K _d) for several metal ions were determined. The results showed that PAN–SMP has a great affinity toward some metal ions such as T^l+, Sr²⁺, Ba²⁺, UO₂ ²⁺ and La⁴⁺. Based on the determined K _d values, two binary quantitative separations of metal ions (Cr⁶⁺ from Cu²⁺ and Pb²⁺ from Cu²⁺) have been achieved on columns of this ion exchanger. The ability of PAN–SMP to decontaminate low-level liquid waste was also investigated.     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

The Cr<Superscript>6+</Superscript> impurity in supergene oxosalts in chromate mineralization occurrences of the Urals

Based on the results of more than 600 electron microprobe analyses of 25 minerals the distribution pattern of the Cr⁶⁺ impurity in vanadates, phosphates, and arsenates collected in oxidation zones of six ore deposits of the Urals was studied. Among them are Pb minerals of the brackebuschite, apatite, adelite, and tsumcorite groups and alunite supergroup, as well as carminite, cornwallite, and bayidonite. Vanadates and arsenates with brackebuschite-type structures show a high affinity to Cr⁶⁺. The maximum content of the Cr⁶⁺ impurity is characteristic of minerals with specified Fe³⁺ trivalent cations (ferribushmakinite, arsenbrackebuschite, and gartrellite) or Al³⁺ (plumbogummite and bushmakinite). The prevailing scheme of isomorphous substitution, according to which chromium enters into the compositions of these minerals, is heterovalent: Cr⁶⁺ + M ²⁺ → Т ⁵⁺ + M ³⁺ (where Т = V, As, P; M ³⁺ = Fe, Al; M ²⁺ = Сu, Zn), whereas the role of isovalent substitutions Cr⁶⁺ → S⁶⁺ and Cr⁶⁺ → Mo⁶⁺ in oxosalts that formed in mineral occurrences of the Urals is insignificant.     

The geochemistry of pyroxenes from the lower layered series of the Jimberlana intrusion,Western Australia

Most of the Al³⁺ entering the pyroxenes does so by substituting for tetrahedral Si⁴⁺. This creates a charge imbalance that requires the simultaneous entry of Cr³⁺, Ti⁴⁺, Fe³⁺ or Al³⁺ into octahedral sites. Cr³⁺, because of its high crystal field stabilisation energy (CFSE), is the most important of these elements to enter the early-formed pyrosenes but it is replaced by Ti⁴⁺ later in fractionation when the Cr³⁺ content of the melt becomes depleted. The dependence of Cr³⁺ and Ti⁴⁺ on charge balance controls their partition between coexisting pyroxenes and olivines. Ca-rich pyroxene which contains more Al³⁺ than Ca-poor pyroxene also has more Ti⁴⁺ and Cr³⁺ whereas olivine, which contains negligible Al³⁺, has low Cr³⁺ and Ti⁴⁺. The Al³⁺ content of pyroxenes is influenced by changes in P, T, \(a_{{\text{SiO}}_{\text{2}} }\) and \(a_{{\text{Al}}_{\text{2}} {\text{O}}_{\text{3}} }\) of the magma and by the nature of the ion providing charge balance in the octahedral site. Of these \(a_{{\text{SiO}}_{\text{2}} }\) is dominant and variations in the Al³⁺ content of the Jimberlana pyroxenes correspond closely with the expected changes in the \(a_{{\text{SiO}}_{\text{2}} }\) of the melt. The substitution of divalent ions, such as Mn²⁺ and Ni²⁺, in the pyroxene lattice is by replacement of Fe²⁺ or Mg²⁺ in the octahedral M ₃ and M ₂ sites and is therefore independent of charge balance. If there are no size restrictions, the principal factor to be considered is the CFSE the ion receives in octahedral co-ordination. Ni²⁺, which receives a high CFSE, partitions strongly between the early-formed pyroxenes and olivines and therefore becomes depleted in the magma with fractionation. Conversely Mn²⁺, which receives zero CFSE, concentrates in the magma with fractionation and becomes a more important substitute in the later-formed pyroxenes. Its geochemical behaviour is controlled by its size. The narrow miscibility gap of the Jimberlana pyroxenes and the high En content of the Ca-poor pyroxenes at the bronzite pigeonite changeover suggest that these pyroxenes crystallised at a higher temperature than pyroxenes of comparable composition from other intrusions.     

In situ formation of AgNPs on <Emphasis Type="Italic">S. cerevisiae</Emphasis> surface as bionanocomposites for bacteria killing and heavy metal removal

Novel bionanocomposites, S. cerevisiae–AgNPs, were synthesized by in situ formation of AgNPs on S. cerevisiae surface using fulvic acids as reductants under simulated sunlight. S. cerevisiae–AgNPs were characterized using UV–Vis spectroscopy, scanning electron microscope, transmission electron microscope and Fourier transform infrared spectroscopy. These analyses showed that AgNPs were distributed on the surface of S. cerevisiae. The application of S. cerevisiae–AgNPs in bacteria killing and heavy metal removal was studied. S. cerevisiae–AgNPs effectively inhibited the growth of E. coli with increasing concentrations of S. cerevisiae–AgNPs. E. coli was killed completely at high concentration S. cerevisiae–AgNPs (e.g., 100 or 200 µg mL^?1). S. cerevisiae–AgNPs as excellent heavy metal absorbents also have been studied. Using Cd²⁺ as model heavy metal, batch experiments confirmed that the adsorption behavior fitted the Langmuir adsorption isotherms and the Cd²⁺ adsorption capacity of S. cerevisiae–AgNPs was 15.01 mg g^?1. According to adsorption data, the kinetics of Cd²⁺ uptake by S. cerevisiae–AgNPs followed pseudo second-order kinetic model. Moreover, S. cerevisiae–AgNPs possessed ability of different heavy metals’ removal (e.g., Cr⁵⁺, As⁵⁺, Pb²⁺, Cu²⁺, Mn²⁺, Zn²⁺, Hg²⁺, Ni²⁺). The simulated contaminated water containing E. coli, Cd²⁺ and Pb²⁺ was treated using S. cerevisiae–AgNPs. The results indicated that the bionanocomposites can be used to develop antibacterial agents and bioremediation agents for water treatment.     

Effect of aluminum and chromium on the germination and growth of two Vigna species

The study deals with the effect of metal toxicity (aluminum, chromium and combination of both the metals) on seed germination, root length, shoot length, seedling length and dry biomass of Vigna radiata and V. sinensis. Chromium adversely affected the seedling by significantly reducing the growth whereas aluminum did not show such effect in both the species. Percentage of germination was good in both the species at different concentration of treatment (aluminum, chromium and combined treatment). Shoot length was also not much affected in V. sinensis as it was greatly inhibited in V. radiata. Both the species showed the purpling of stem. Dry biomass of V. radiata showed positive effect than V. sinensis. However, dry biomass decreased to a lesser extent when treated with aluminum, chromium and combined treatment as compared to control.     

Germination ecology of a Maryland population of saltmarsh bulrush (Scirpus robustus)

Germination and growth responses ofScirpus robustus Pursh were determined for a variety of environmental conditions. A period of after-repening was required for seed germination; the most effective pretreatment was chilling at 2 C. Alternate freezing and thawing, freezing, and warm dry storage resulted in lower germination. Scarification was effective in increasing seed germination. Low concentrations of salt depressed germination and growth. A definite light requirement was found, but photoperiod length had no effect on germination responses. Alternating temperatures promoted germination; the best overall response occurred with 35 C day/25 C night. Presence ofS. robustus within the marsh community is discussed in relation to germination and seedling establishment characteristics of the species.