High-throughput production of peroxidase and its biodegradation potential toward polymeric material

Plastics are polymeric materials, and their disposal is a great problem in today’s society. Large quantities of single-use plastics are used every minute throughout the world. Peroxidase enzymes play a significant role in the biodegradation of polymeric materials due to oxidoreductase capability. The objective is to determine which set of conditions optimize the production of peroxidase enzymes by Phanerochaete chrysosporium so as to degrade polymeric materials. The sequential order of parameters in terms of their relevant performance in the bioprocess was determined as urea > polyvinyl chloride > incubation time > polyethylene > veratryl alcohol > sucrose > ammonium sulfate > glucose > ferrous sulfate and polystyrene. Statistical analysis was performed by using analysis of variance which indicated the significance of model Plackett–Burman and components on the basis of F value and P value of 0.012678 < 0.05. The Fourier transform infrared spectroscopy of enzyme-treated polymer revealed structural changes at 1091, 1638 cm^?1. A new peak appeared at wave number 1029 and represented the aromatic ether and phenolic group as compared to control. Biosynthesis of lignin peroxidase at optimized conditions has the potential for biodegradation of recalcitrant polymeric waste, due to its oxidoreductase capability for chemically inert material in nature like lignin and can be used for waste treatment on a large scale.     

Biodegradation of polyvinyl alcohol-low linear density polyethylene-blended plastic film by consortium of marine benthic vibrios

Marine bacteria, Vibrio alginolyticus and Vibrio parahemolyticus isolated from sediments were evaluated for their ability as a consortia, to degrade polyvinyl alcohol-low linear density polyethylene (PVA-LLDPE)-blended plastic films in shake flask conditions at 120 rpm at 37 °C over 15 weeks. Results indicated that relatively 20 % decrease in tensile strength of the film could be achieved with 25 and 30 % blend of PVA in the PVA-LLDPE plastic film compared to other ratios. Micrographs obtained with scanning electron microscope showed visible cracks and grooves on the surface of the PVA-LLDPE blend film after 15 weeks of incubation with bacterial consortium. The decrease in tensile strength of the PVA-blended plastic films after treatment and the results of the scanning electron microscopic analysis evidence that the consortium could cause degradation of PVA-LLDPE plastic blends compared to suitable controls. This is the first report on polyvinyl alcohol degrading Vibrio sp. from marine sediments and its application in microbial degradation of polyvinyl alcohol-low linear density polyethylene plastic blends. The study indicated potential of marine benthic vibrios that have novel enzymes and unique characteristics for application in bioremediation and solid waste management particularly in handling synthetic polymers such as PVA-blended plastic films.     

Biosorption an innovative tool for bioremediation of metal-contaminated municipal solid waste leachate: optimization and mechanisms exploration

Municipal solid waste poses a risk on surrounding environment and public health, mainly because of unscientific disposal and shortage of facilities for proper handling and recycling of leachate. This research article objective is to pinpoint the indigenous fungal isolates of waste leachate samples. Therefore, we carried out biosorption of Cd²⁺ tested the applicability by applying indigenous fungal isolates. The limited number of fungal isolates was found based on their ability for biosorption of Cd²⁺ metal. The fungal strains Trichoderma sp., Aspergillus niger and Aspergillus flavus were reported as potential strains for metal exclusion ability from the leachate. Among them, the Trichoderma sp. was found as excellent fungal agent for Cd²⁺ absorption. The optimum pH was 5.5 ± 1, temperature 45 °C, and spore concentration 10^?5 to achieve the maximum biosorption, and 35 days of incubation period were required by three strains. The maximum metal biosorption achieved was comparable for the three isolates: 56.34% by Trichoderma sp., 44.74 and 42.04% by A. niger and A. flavus, respectively. Concluding, the further intending application to identified potentially fungal isolates is able to improve the efficiency of metal biosorption. These strains are recommended for development of consortia could become a best technique for MSW leachate treatment if its reliability and applicability should be verified prior to technology acceptance.     

Occurrence of phthalate esters around the major plastic industrial area in southern Taiwan

The increasing usage and disposal of plastic products could cause the wide distribution of phthalate esters (PAEs) in various environmental media. In this study, six PAE compounds, namely dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, benzyl butyl phthalate, di(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate, were analyzed in various samples collected from the major plastic industrial area of southern Taiwan, including soil, fertilizer and plastic products, for the purposes of identifying of the possible sources of PAEs and assessing the related health risk. The results show that PAEs in soil samples was dominated by DEHP, with the total concentrations in the range of 0.7?±?0.5, 0.2?±?0.1, and 0.3?±?0.2 mg kg^?1 for soil samples from farmland, household back gardens and the roadside, respectively. Contents of PAEs in chemical fertilizer (ND—0 0.87 mg kg^?1) were higher than that in organic fertilizer (ND—0.08 mg kg^?1), and PAEs concentrations (ND—316 mg kg^?1) in plastic mulching films were much less than those in the other types of plastic products (ND—1719 mg kg^?1), implying that major sources of PAEs in agricultural soil could be the use of chemical fertilizer and plastic products other than plastic mulching films. Health risk assessment suggested that, via the exposure to PAEs in soil, the potential non-cancer and carcinogenic risks for adults and children are minimal in most cases, except that a “moderate” carcinogenic risk for children exposure to DEHP. The results of this study can serve as a reference for further pollution prevention and environmental protection plans in relation to the industrial operation and discharge as well as the farming practices.     

Single-crystal polarized FTIR spectroscopy and neutron diffraction refinement of cancrinite

We relate a single-crystal FTIR (Fourier transform infrared) and neutron diffraction study of two natural cancrinites. The structural refinements show that the oxygen site of the H₂O molecule lies off the triad axis. The water molecule is almost symmetric and slightly tilted from the (0001) plane. It is involved in bifurcated hydrogen bridges, with Ow···O donor–acceptor distances >2.7 Å. The FTIR spectra show two main absorptions. The first at 3,602 cm^?1 is polarized for E ⊥ c and is assigned to the ν₃ mode. The second, at 3,531 cm^?1, is also polarized for E ⊥ c and is assigned to ν₁ mode. A weak component at 4,108 cm^?1 could possibly indicate the presence of additional OH groups in the structure of cancrinite. Several overlapping bands in the 1,300–1,500 cm^?1 range are strongly polarized for E ⊥ c, and are assigned to the vibrations of the CO₃ group.     

Raman spectroscopy of natural silica in Chicxulub impactite,MexicoSpectroscopie Raman de silices naturelles dans l'impactite de Chicxulub,Mexique

A series of natural silica impactite samples from Chicxulub (Mexico) was investigated by Raman microprobe (RMP) analysis. The data yield evidence for high-pressure shock metamorphism in the rock. The impactite contains three polymorphs of silica: the original α-quartz, and two high-pressure varieties – coesite and disordered quartz representing various degrees of crystallinity. We found systematic changes in frequencies and half-widths of the Raman bands, caused by increasing irregularities of bond-lengths and bond-angles and a general breaking-up of the structure as a result of impact events. Therefore, RMP is an adequate tool for measuring the crystallinity of disordered quartz. The half-width Γ and the frequency ω of the symmetric SiOSi stretching vibrational band (A₁ mode) of the SiO₄ tetrahedra are the most amenable parameters for estimating the degree of crystallinity. In well-crystallized quartz, Γ=5 cm^?1 and ω=464 cm^?1, while in highly disordered quartz this line shifts up to ω=455 cm^?1 and broadens up to Γ=30 cm^?1. The Raman lineshapes appear to depend strongly on the degree of lattice disorder subsequent to impact events. To cite this article: M. Ostroumov et al., C. R. Geoscience 334 (2002) 21–26     

Co-metabolic decolorization of a textile reactive dye by <Emphasis Type="Italic">Aspergillus fumigatus</Emphasis>

In the present study, a widely used reactive dye, Color Index (C.I.) Reactive Blue 268 was utilized for mycoremediation by Aspergillus fumigatus isolated from textile effluent. Complete decolorization of the test dye (0.1 g L^?1) was recorded within 6 days of static incubation at 27 °C in Czapek Dox broth (CDB). However, the isolate was unable to utilize the dye as a sole source of energy in Czapek Dox agar and CDB in absence of sucrose and obligate requirement of a labile carbon source, i.e., sucrose needed for induction of decolorization. Biosorption seems to play the pivotal role in decolorization as evident by coloring of the fungal biomass as that of dye color. The optimal conditions for the highest decolorization were found at 30 °C and pH 6.0 with 6-day-old inoculums supplemented with sucrose (10 g L^?1) and ammonium chloride (2 g L^?1) as a carbon and nitrogen source, respectively. The response of the isolate to increasing dye concentrations was found to be growth inhibitory. Surprisingly, about 65 % of dye decolorization was recorded with heat-inactivated biomass powder within 6 days of static incubation supporting the fact of fungal biosorption. Results of this study have established the candidature of the isolate for biotechnological removal of dyes from disreputable dying effluents.     

Stability and P–V–T equation of state of KAlSi3O8-hollandite determined by in situ X-ray observations and implications for dynamics of subducted continental crust material

In situ X-ray diffraction measurements of KAlSi₃O₈-hollandite (K-hollandite) were performed at pressures of 15–27 GPa and temperatures of 300–1,800 K using a Kawai-type apparatus. Unit-cell volumes obtained at various pressure and temperature conditions in a series of measurements were fitted to the high-temperature Birch-Murnaghan equation of state and a complete set of thermoelastic parameters was obtained with an assumed K′_300,0=4. The determined parameters are V _300,0=237.6(2) Å³, K _300,0=183(3) GPa, (?K _T,0/?T) _P =?0.033(2) GPa K^?1, a ₀=3.32(5)×10^?5 K^?1, and b ₀=1.09(1)×10^?8 K^?2, where a ₀ and b ₀ are coefficients describing the zero-pressure thermal expansion: α _T,0 = a ₀ + b ₀ T. We observed broadening and splitting of diffraction peaks of K-hollandite at pressures of 20–23 GPa and temperatures of 300–1,000 K. We attribute this to the phase transitions from hollandite to hollandite II that is an unquenchable high-pressure phase recently found. We determined the phase boundary to be P (GPa)=16.6 + 0.007 T (K). Using the equation of state parameters of K-hollandite determined in the present study, we calculated a density profile of a hypothetical continental crust (HCC), which consists only of K-hollandite, majorite garnet, and stishovite with 1:1:1 ratio in volume. Density of HCC is higher than the surrounding mantle by about 0.2 g cm^?3 in the mantle transition zone while this relation is reversed below 660-km depth and HCC becomes less dense than the surrounding mantle by about 0.15 g cm^?3 in the uppermost lower mantle. Thus the 660-km seismic discontinuity can be a barrier to prevent the transportation of subducted continental crust materials to the lower mantle and the subducted continental crust may reside at the bottom of the mantle transition zone.     

Chloride contamination in construction aggregates due to periodic saline water intrusion: a case study in the Kaluganga River Estuary, Sri Lanka

The Kaluganga River Estuary is one of the main sources of construction sand in Sri Lanka. Salt water intrusion along this estuary due to extensive sand mining has increased over the years. Thus, the focus of the current research is to understand the relationship between river sand mining, salt water intrusion, and the resultant effects on construction sand. Two surveys were conducted along the Kaluganga Estuary along an 11 km stretch from the river mouth at predetermined intervals to measure depth water quality profiles, and to collect sediment samples. These surveys were carried out during maximum spring tide; first in a dry period and then in a wet period, to understand hydrographic effects on the quality of river sands. Sand samples were analysed for absolute chloride content and grain size distribution. Results showed significant salt water intrusion during the dry period, averaging 2,307 μS cm^?1 in surface waters throughout the surveyed 11 km stretch along with 3,818 μS cm^?1 (average) in bottom waters up to 5.6 km upstream from the river mouth causing above normal chloride content in the bottom sandy sediments. The high chloride content in bottom sands was recorded up to 5.5 km from the river mouth making them unsuitable for construction purposes. However, during wet period, salt water intrusion levels in the bottom waters were insignificant (average 61 μS cm^?1) and the chloride content in bottom sediments was very low. This study highlighted the requirement for regulations on river estuary sandmining for construction purposes.     

Effective bioremoval of syntan using fungal laccase to reduce pollution from effluent

Syntans are synthetically prepared tanning agents from phenols that play an important role in leather making by enhancing the filling, grain characteristics and dyeing property. A considerable amount of syntan emanated in waste water contributes high pollution load with other heterocyclic aromatic compounds and causes serious environmental impact resulting in high oxygen demand. In order to overcome this, suitable biodegradation techniques have been developed using laccase from Penicillium chrysogenum. The influence of different environmental parameters on the biodegradation has also been studied which reveals that the maximum syntan degradation was obtained at pH 5.0, temperature at 32 °C for the duration of 48 h. Maximum biodegradation was found to be 96 and 94% for samples containing phenolic and melamine syntan. Ultraviolet spectra showed the peaks at around 280 nm for the presence of phenolic (DI) syntan and at 220 nm for melamine syntan which were disappeared later in the experimental sample indicating complete degradation of syntans. Fourier spectral analysis indicated that the peaks at the region between 1443–1574 and 1176 cm^?1 correspond to C=C stretching and C–H bending for aromatic region which were later disappeared in the experimental sample. Ultrapressure liquid chromatography elution profiles of syntans showed relatively shorter retention time indicating formation of oxidized products. Syntans, namely DI and FB6, showed reduction in chemical oxygen demand up to 87.71 ± 4 and 83.38 ± 5%, respectively, while total organic carbon reduction was achieved up to 82.37 and 80.72%, respectively. Toxicity studies revealed that seeds were well germinated using the treated (biodegradation) samples by crude laccase .     

Polarized electronic absorption spectra of colourless chalcocyanite,CuSO4, with a survey on crystal fields in Cu2+ minerals

Polarized electronic absorption spectra of colourless chalcocyanite, CuSO₄, have been measured using microscope-spectrometric techniques. The spectra are characterized by a structured and clearly polarized band system in the near-infrared spectral range with components centred at 11,720, 10,545, 9,100, and 7,320 cm^?1, which have been assigned to crystal field d–d transitions of Cu²⁺ cations in pseudo-tetragonally elongated CuO₆ polyhedra with point symmetry C _i ( \(\bar{1}\) ). The polarization behaviour is interpreted based on a D ₂(C ₂″) pseudo-symmetry. Crystal field calculations were performed for the actual triclinic point symmetry by applying the Superposition Model of crystal fields, as well as in terms of a ‘classic’ pseudo-tetragonal crystal field approach yielding the parameters Dq _(eq) = 910, Dt = 395, and Ds = 1,336 cm^?1, corresponding to a cubically averaged Dq _cub = 679 cm^?1. A comparative survey on crystal fields in Cu²⁺ minerals shows that the low overall crystal field strength in chalcocyanite, combined with a comparatively weak pseudo-tetragonal splitting of energy levels, is responsible for its unique colourless appearance among oxygen-based Cu²⁺ minerals. The weak crystal field in CuSO₄ can be related to the lower position of the SO₄ ^2? anion compared to, e.g. the H₂O molecule in the spectrochemical series of ligands.     

First-principles study of OH defects in zircon

The infrared spectroscopic properties of selected OH defects in zircon are investigated by first-principles calculations. The explicit treatment of the coupled nature of OH motions in the stretching modes, together with the calculation of the intensity and polarization of absorption bands, makes it possible to directly compare theoretical and experimental data. The bands observed at 3,420 cm^?1 (polarization parallel to c axis) and 3,385 cm^?1 (polarization perpendicular to c axis) in natural and synthetic samples correspond to the IR-active vibrational modes of the hydrozircon defect, that is, fully protonated Si vacancy. The broad band observed at 3,515 cm^?1 in the spectrum of zircon crystals grown in F-rich environments is consistent with the occurrence of composite (OH,F) tetrahedral defects. Calculations also show that the band observed at 3,200 cm^?1 in the spectrum of synthetic undoped samples can be ascribed to fully protonated Zr vacancies. The theoretical values of integrated absorption coefficients indicate that general correlations can be reasonably used to determine the concentration of OH groups in zircon.     

Degradation of polyvinyl alcohol in aqueous solutions using UV-365 nm/S2O8 2− process

This investigation evaluates the effectiveness of UV-365 nm/S₂O₈ ^2? process in degrading polyvinyl alcohol in aqueous solutions. The effects of pH, Na₂S₂O₈ dosage, and temperature on the degradation efficiency of polyvinyl alcohol were studied. Under acidic conditions, the degradation efficiency of polyvinyl alcohol exceeded that under alkaline conditions. Additionally, a higher Na₂S₂O₈ dosage and a higher temperature were associated with a higher degradation efficiency of polyvinyl alcohol. The degradation rates of polyvinyl alcohol followed a pseudo-first-order kinetic model. Moreover, the observed degradation rate coefficient increased from 0.0078 to 0.4081 min^?1 when the temperature was increased from 10 to 55 °C. Also, the activation energy estimated using the observed degradation rate coefficients and the Arrhenius equation was 64 kJ/mol. At UV-365 nm, pH 3, an Na₂S₂O₈ dosage of 0.06 g/L, a temperature of 55 °C, and an initial polyvinyl alcohol concentration of 20 mg/L, around 100 % of polyvinyl alcohol was degraded, indicating that UV-365 nm/S₂O₈ ^2? process has great potential in degrading polyvinyl alcohol in aqueous solutions.     

Influence of Infiltration of Sodium Chloride Solutions on SWCC of Compacted Bentonite–Sand Specimens

The degree of saturation of compacted bentonite buffer in deep geological repositories is subject to alterations from infiltration of groundwater and heat emanated from the waste canisters. The matric suction (ψ)–degree of saturation (S _r ) relations of unsaturated clays is represented by soil–water characteristics curves (SWCC) that are influenced by soil structure, initial compaction condition and stress history. Infiltration of groundwater besides increasing the degree of saturation can also alter the pore water chemistry; the associated changes in cation hydration and diffuse double layer thickness could impact the micro-structure and matric suction values. This study examines the influence of infiltrating sodium chloride solutions (1,000–5,000 mg/L) on the transient ψ–S _r relations of compacted bentonite–sand specimens. Analysis of the ψ–S _r plots, and X-ray diffraction measurements indicated that infiltration of sodium chloride solutions has progressively less influence on the micro-structure and SWCC relations of bentonite–sand specimens compacted to increasingly higher dry densities. The micro-structure and SWCC relations of specimens compacted to 1.5 Mg/m³ were most affected, specimens compacted to 1.75 Mg/m³ were less affected, while specimens compacted to 2 Mg/m³ remained unaffected upon infiltration with sodium chloride solutions.     

The potential for using the sycamore (Platus orientalis) leaves in manufacturing particleboard

Developing value-added products from any underutilized non-woody or woody material could play a critical role in economical development as well as forest resource management of any country. The objective of this research was to evaluate the potential of using the sycamore leaves in production of particleboard. Variable factors were as board density (0.6 and 0.7 g/cm³), press time (4 and 6 min), and press temperature (140 and 160 °C). Some chemical properties of the sycamore leaves (cellulose, holocellulose, lignin and ash contents, alcohol–benzene solubility, 1 % sodium hydroxide solubility, hot- and cold-water solubility), mechanical (modulus of rupture, modulus of elasticity, and internal bond strength) and physical properties (thickness swelling and water absorption) of the resulting particleboards were determined. Overall results showed that the mechanical properties of all the panels exceed the minimum requirements of European Norm for furniture manufacturing. The mechanical properties of particleboard were improved significantly as board density increased from 0.6 to 0.7 g/cm³ and press time increased from 4 to 6 min. However, the effect of press temperature was not significant (P < 0.05). Conclusively, sycamore leaves, an underutilized waste, can be an alternative raw material for particleboard industry and resulting value-added panels owing to their high mechanical properties and interesting design esthetics could be used for furniture and interior decoration.     

Evaluating the production and bio-stimulating effect of 5-methyl 1, hydroxy phenazine on microbial fuel cell performance

The role of endogenous redox mediators has considerable importance in electron shuttling reactions and associated performance of microbial fuel cell. Single-chamber microbial fuel cell-II with dual air-cathode assembly (area = 18.84 cm²) supported highest bacterial (Pseudomonas aeruginosa) density (6.7 × 10⁹) and active biomass [4.4 ± 0.3 mg cm^?2 (carbon content = 0.48 ± 0.1 mg cm^?2)] on anode thereby resulting in maximum production of redox metabolite, 5-methyl 1, hydroxy phenazine (301 ppm) and voltage (595 ± 5 mV) than similar cells with relatively less surface area of cathode. It was further revealed that 5-methyl 1, hydroxy phenazine production was positively correlated with chemical oxygen demand removal rate (77 ± 2.5%) and power generation (66.6 ± 2.2 mW cm^?2) efficiency of single-chamber microbial fuel cell-II. Maximum power density of 258 ± 4.5 mW cm^?2 was generated when reactor was supplemented with 2 ml crude extract of 5-methyl 1, hydroxy phenazine metabolite, whereas power output was about 229 ± 2.5 mW cm^?2 when reactor was bio-stimulated with 1 ml pure extract of 5-methyl 1, hydroxy phenazine. With this concentration, the electrochemical response of mixed culture biofilm (sediment) was enhanced by 99.3%. However, further increase in concentration of endogenous mediator proved to be limiting on reactor performance. Pyrosequencing and phylogenetic analysis on the basis of partial 16S rRNA sequences demonstrated both culturable and unculturable bacterial species in anodic biofilm and relative abundance of family Pseudomonadaceae was found to be maximum, i.e., 61.7% followed by Rhodocyclaceae 19.2%, Xanthomonadaceae 6.3% and Opitutaceae 3.18%.     

Static elasticity of cordierite I: Effect of heavy ion irradiation on the compressibility of hydrous cordierite

The effect of ion beam irradiations on the elastic properties of hydrous cordierite was investigated by means of Raman and X-ray diffraction experiments. Oriented single crystals were exposed to swift heavy ions (Au, Bi) of various specific energies (10.0–11.1 MeV/u and 80 MeV/u), applying fluences up to 5 × 10¹³ ions/cm². The determination of unit-cell constants yields a volume strain of 3.4 × 10^?3 up to the maximum fluence, which corresponds to a compression of non-irradiated cordierite at ~480 ± 10 MPa. The unit-cell contraction is anisotropic (e ₁ = 1.4 ± 0.1 × 10^?3, e ₂ = 1.5 ± 0.1 × 10^?3, and e ₃ = 7 ± 1 × 10^?4) with the c-axis to shrink only half as much as the axes within the ab-plane. The lattice elasticity for irradiated cordierite (? = 1 × 10¹² ions/cm²) was determined from single-crystal XRD measurements in the diamond anvil cell. The fitted third-order Birch–Murnaghan equation-of-state parameters of irradiated cordierite (V ₀ = 1548.41 ± 0.16 Å³, K ₀ = 117.1 ± 1.1 GPa, ?K/?P = ?0.6 ± 0.3) reveal a 10–11 % higher compressibility compared to non-irradiated cordierite. While the higher compressibility is attributed to the previously reported irradiation-induced loss of extra-framework H₂O, the anomalous elasticity as expressed by elastic softening (β _a ^?1 , β _b ^?1 , β _c ^?1  = 397 ± 9, 395 ± 28, 308 ± 11 GPa, ?(β ^?1)/?P = ?4.5 ± 2.7, ?6.6 ± 8.4, ?5.4 ± 3.0) appears to be related to the framework stability and to be independent of the water content in the channels and thus of the ion beam exposure.     

Enhancement of nickel biosorption on fungal biomass by enzymatic and alkali pretreatments

Enzymatic and alkali pretreatments were employed to improve nickel biosorption capacity of Rhizomucor pusillus biomass. Pretreatment with 0.002–80 g l^?1 NaOH and 0.0001–0.1 Anson Unit (AU) g^?1 protease enhanced the biosorption capacity of fungal biomass. Increasing the concentration of NaOH from 0.002 to 5 g l^?1 improved nickel removal from 93.2 to 100.0 % while untreated biomass showed 64.6 % Ni(II) removal. Pretreatment with higher concentrations of NaOH, 5–80 g l^?1 resulted in nearly complete removal of nickel ions. Pretreatment of the biomass with 0.0001 AU g^?1 protease improved the nickel removal to over 91 %, while increasing the enzyme loading to 0.1 AU g^?1 improved the removal to 93 %. Untreated biomass removed 78.4, 63.0, and 96.3 % of chromium, copper, and lead ions, respectively, from a mixture solution of the ions. Respective metal removals were increased to 100, 98.9, and 100 % after pretreatment with 0.2 g l^?1 NaOH solution and to 87.8, 86.7, and 100 % after the enzymatic pretreatment with 0.1 AU g^?1 protease. Scanning electron microscopy analysis indicated that alkali and enzymatic pretreatments enhanced the porosity of the biomass. Furthermore, compositional analysis showed that both of the pretreatments removed a major part of fungal proteins (2.1–95.8 % removal). Glucosamine, N-acetyl glucosamine, and phosphates were the major ingredients of the pretreated biomass.     

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300 °C

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D _Cl ^{olivine/fluid} varying between 10^?5 and 10^?3, whereas D _Cl ^{orthopyroxene/fluid} and D _Cl ^{clinopyroxene/fluid} are ~10^?4 and D _Cl ^{amphibole/fluid} is ~5 × 10^?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D ^amph/fluid ≈ D ^cpx/fluid > D ^opx/fluid > D ^ol/fluid but that D ^{mineral/fluid} for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm^?1. In F ± TiO₂-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm^?1. Absorption bands at ~3,530 and ~3,570 cm^?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.     

Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure

We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm^?1 display a small frequency lowering (<4 cm^?1) and a moderate broadening (<10 cm^?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm^?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm^?1 respectively) and broadening (~30 cm^?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm^?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm^?1, at ?194 °C. They exhibit significant frequency increase (~20 cm^?1) and broadening (~70 cm^?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)_Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm^?1 (type (2); 3,550 cm^?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)_Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.