A study of lipid- and water-soluble arsenic species in liver of Northeast Arctic cod (Gadus morhua) containing high levels of total arsenic

In the present study liver samples (n = 26) of Northeast Arctic cod (Gadus morhua), ranging in total arsenic concentrations from 2.1 to 240 mg/kg liver wet weight (ww), were analysed for their content of total arsenic and arsenic species in the lipid-soluble and water-soluble fractions. The arsenic concentrations in the lipid fractions ranged from 1.8 to 16.4 mg As/kg oil of liver, and a linear correlation (r² = 0.80, p < 0.001) was observed between the total arsenic concentrations in liver and the total arsenic concentrations in the respective lipid fractions of the same livers. The relative proportion of arsenolipids was considerably lower in liver samples with high total arsenic levels (33–240 mg/kg ww), which contained from 3 to 7% of the total arsenic in the lipid-soluble fraction. In contrast liver samples with low arsenic concentrations (2.1–33 mg/kg ww) contained up to 50% of the total arsenic as lipid-soluble species. Arsenic speciation analysis of the lipid-soluble fractions of the livers, using reversed-phase high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC–ICP-MS), revealed the presence of several arsenolipids. Three major arsenic-containing hydrocarbons (C₁₇H₃₉AsO, C₁₉H₄₁AsO and C₂₃H₃₇AsO) and five arsenic-containing fatty acids (C₁₇H₃₅AsO₃, C₁₉H₃₉AO₃, C₁₉H₃₇AsO₃, C₂₃H₃₇AsO₃ and C₂₄H₃₇AsO₃) were identified using HPLC coupled to quadrupole time-of-flight mass spectrometry (qTOF-MS). Arsenobetaine was the major arsenic species in the water-soluble fraction of the livers, while dimethylarsinate, arsenocholine and inorganic arsenic were minor constituents. Inorganic arsenic accounted for less than 0.1% of the total arsenic in the liver samples.     

The sensitivity of water chemistry to climate in a forested,nitrogen-saturated catchment recovering from acidification

Fluxes of major ions and nutrients were measured in the N-saturated mountain forest catchment-lake system of Čertovo Lake (Czech Republic) from 1998 to 2014. The lake has been rapidly recovering from atmospheric acidification due to a 90% decrease in sulphate (SO₄²⁻) deposition since the late 1980s and nitrate (NO₃⁻) contribution to the pool of strong acid anion and leaching of dissolved organic carbon (DOC) have increased. Present concentrations of base cations, phosphorus (P), total organic N (TON), and ionic (Al_i) and organically bound (Al_o) aluminium in tributaries are thus predominantly governed by NO₃⁻ and DOC leaching. Despite a continuing recovery lasting 25 years, the Čertovo catchment is still a net source of protons (H⁺), producing 44 mmol m⁻² yr⁻¹ H⁺ on a catchment-area basis (corresponding to 35 μmol L⁻¹ on a concentration basis). Retention of the deposited inorganic N in the catchment averages 20%, and ammonium consumption (51 mmol m⁻² yr⁻¹) and net NO₃⁻ production (28 mol m⁻² yr⁻¹) are together the dominant terrestrial H⁺ generating processes. In contrast, the importance of SO₄²⁻ release from the soils on terrestrial H⁺ production is continuously decreasing, with an average of 47 mmol m⁻² yr⁻¹ during the study. The in-lake biogeochemical processes reduce the incoming acidity by ∼40%, neutralizing 23 μmol L⁻¹ H⁺ (i.e., 225 mmol m⁻² yr⁻¹ on a lake-area basis). Denitrification and photochemical and microbial decomposition of DOC are the most important in-lake H⁺ consuming processes (50 and 39%, respectively), while hydrolysis of Al_i (from tributaries and photochemically liberated from Al_o) is the dominant in-lake H⁺ generating process. Because the trends in water chemistry and H⁺ balance in the catchment-lake system are increasingly related to variability in NO₃⁻ and DOC leaching, they have become sensitive to climate-related factors (drought, elevated runoff) and forest damage that significantly modify the leaching of these anions. During the study period, increased exports of NO₃⁻ (accompanied by Al_i and base cations) from the Čertovo catchment occurred after a dry and hot summer, after forest damage, and during elevated winter runoff. Increasing DOC export due to decreasing acid deposition was further elevated during years with higher runoff (and especially during events with lateral flow), and was accompanied by P, TON, and Al_o leaching. The climate-related processes, which originally “only” confounded chemical trends in waters recovering from acidification, may soon become the dominant variables controlling water composition in N-saturated catchments.     

Stimuli responsive polymorphism of C12NO/DOPE/DNA complexes: Effect of pH,temperature and composition

N,N-dimethyldodecylamine-N-oxide (C₁₂NO) is a surfactant that may exist either in a neutral or cationic protonated form depending on the pH of aqueous solutions. Using small angle X-ray diffraction (SAXD) we observe the rich structural polymorphism of pH responsive complexes prepared due to DNA interaction with C₁₂NO/dioleoylphosphatidylethanolamine (DOPE) vesicles and discuss it in view of utilizing the surfactant for the gene delivery vector of a pH sensitive system. In neutral solutions, the DNA uptake is low, and a lamellar L_α phase formed by C₁₂NO/DOPE is prevailing in the complexes at 0.2 ≤ C₁₂NO/DOPE < 0.6 mol/mol. A maximum of ~ 30% of the total DNA volume in the sample is bound in a condensed lamellar phase L_α^C at C₁₂NO/DOPE = 1 mol/mol and pH 7.2. In acidic conditions, a condensed inverted hexagonal phase H_II^C was observed at C₁₂NO/DOPE = 0.2 mol/mol. Commensurate lattice parameters, a_HC ≈ d_LC, were detected at 0.3 ≤ C₁₂NO/DOPE ≤ 0.4 mol/mol and pH = 4.9–6.4 suggesting that L_α^C and H_II^C phases were epitaxially related. While at the same composition but pH ~ 7, the mixture forms a cubic phase (Pn3m) when the complexes were heated to 80 °C and cooled down to 20 °C. Finally, a large portion of the surfactant (C₁₂NO/DOPE > 0.5) stabilizes the L_α^C phase in C₁₂NO/DOPE/DNA complexes and the distance between DNA strands (d_DNA) is modulated by the pH value. Both the composition and pH affect the DNA binding in the complexes reaching up to ~ 95% of the DNA total amount at acidic conditions.     

Low pH (6, 5 and 4) sulfate reduction during the acidification of sucrose under thermophilic (55 °C) conditions

The effect of a low pH (6, 5 and 4) and different COD/SO₄²⁻ ratios (9 and 3.5) on thermophilic (55 °C) sulfate reduction and acidification of sucrose was investigated using three upflow anaerobic sludge bed reactors fed with sucrose at an organic loading rate of 3.5 gCOD (l_reactor d)⁻¹. The three reactors showed nearly 100% acidification of sucrose for all pH values and COD/SO₄²⁻ ratios investigated. Sulfate reduction was complete at pH 6 and a COD/SO₄²⁻ ratio of 9. At pH 5, sulfate reduction efficiencies were 80–95% for both COD/SO₄²⁻ ratios (9 and 3.5). At pH 4, sulfate reduction efficiencies further dropped to 55–65% at a COD/SO₄²⁻ ratio of 9 and 30–40% at a COD/SO₄²⁻ ratio of 3.5. The pH decrease from 6 to 5 or 4 caused a shift in the acidification products from mainly acetate to butyrate, as well as a higher production of ethanol, especially at pH 4. At pH 4, propionate and methane were not formed and hydrogen concentrations in the biogas reached 50%, equivalent to a hydrogen yield of 1.3 mol H₂ (mol glucose)⁻¹. This study shows that sulfate reduction is possible in the acidification phase of anaerobic wastewater treatment at pH values as low as 6 till 4 and that the pH strongly affects both the acidification pathways and the sulfate reduction efficiencies.     

Biological removal of pharmaceutical and personal care products by a mixed microbial culture: Sorption,desorption and biodegradation

The performance of a mixed-culture on the removal of caffeine (CFN), sulfamethoxazole (SMX), ranitidine (RNT), carbamazepine (CZP) and ibuprofen (IBP) in a suspended growth reactor has been studied. The sorption and biodegradation of these compounds were examined when they were individually or simultaneously tested. The sorption of individual compounds was significantly low except from RNT (K_d = 0.42 L/g). In contrast, the sorption of SMX and CFN increased in detriment of RNT when all the pharmaceutical compounds were simultaneously present. The biodegradation removal also exhibited significant differences. Thus, the simultaneous treatment showed higher biodegradation rates (K_b up to 97.55 × 10⁻⁶ L/mg h) than the individual treatment (K_b up to 8.13 × 10⁻⁶ L/mg h) of the pharmaceuticals. In general, the simultaneous treatment leads to increased sorption distribution coefficients and biodegradation rates. Results seem to reveal that the enhanced biomass efficiency on the simultaneous elimination process was due to the synergistic effects of pharmaceutical compounds onto mixed-culture. During the simultaneous removal, CFN, SMX and CZP were removed consistently (5.3 ± 4.4%, 73.2 ± 21.3% and 4.2 ± 2.3%, respectively), whereas RNT and IBP showed an unsteady removal over time. Finally, a kinetic model capable of describing the influence of biomass growth and nutrients utilization on the sorption and biodegradation of the pollutants was successfully demonstrated.     

Comparison of CSTR and UASB reactor configuration for the treatment of sulfate rich wastewaters under acidifying conditions

The effects of lowering the operational pH from 6 to 5 on mesophilic (30 °C) sulfate reduction during the acidification of sucrose at an organic loading rate of 5 gCOD (l_reactor d)⁻¹ and at a COD/SO₄²⁻ ratio of 4 were evaluated in a CSTR and in a UASB reactor. The HRT was 24 h and 10 h, respectively. Acidification was complete in both reactors at pH 6 and the lowering of the operational pH to 5 did not affect the acidification efficiency in the CSTR but decreased the acidification efficiency of the UASB to 72%. The decrease to pH 5 caused an increase in the effluent butyrate and ethanol concentrations in both reactors. Lowering the pH from 6 to 5 caused a decrease in sulfate reduction efficiencies in both reactors, from 43% to 25% in the CSTR and from 95% to 34% in the UASB reactor. The acidification and sulfate reduction efficiencies at pH 5 could be increased to 94% and 67%, respectively, by increasing the HRT of the UASB reactor to 24 h.     

Profiling oestrogens and testosterone in human urine by stable isotope dilution/benchtop gas chromatography–mass spectrometry

Oestrogens, such as oestrone (E₁), 17β-oestradiol (E₂), oestriol (E₃) and their biologically active metabolites 2-methoxyoestrone (2-MeOE₁), 2-hydroxyoestradiol (2-OHE₂) 16-ketooestradiol (16-OE₂), 16-epioestriol (16-epiE₃), as well as testosterone (T) play an important role in physiological and pathological developmental processes during human development. We therefore aimed at developing an isotope dilution/bench top gas chromatography–mass spectrometry (ID/GC–MS) method, based on benchtop GC–MS, for the simultaneous determination (‘profiling’) of the above analytes in children. The method consisted of equilibration of urine (5 ml) with a cocktail containing stable isotope-labelled analogues of the analytes as internal standards ([2,4-²H₂]E₁, [2,4,16,16-²H₄]E₂, [2,4,17-²H₃]E₃, [16,16,17-²H₃]T, [1,4,16,16-²H₄]2-MeOE₁, [1,4,16,16,17-²H₅]2-OHE₂, [2,4,15,15,17-²H₅]16-OE₂ and [2,4-²H₂]16-epiE₃). Then, solid-phase extraction (C₁₈ cartridges), enzymatic hydrolysis (sulphatase from Helix pomatia (type H-1)), re-extraction, purification by anion exchange chromatography and derivatisation to trimethylsilyl ethers followed. The samples were analysed by GC–MS (Agilent GC 6890N/5975MSD; fused silica capillary column 25 m × 0.2 mm i.d., film 0.10 μm). Calibration plots were linear and showed excellent reproducibility with coefficients of determination (r²) between 0.999 and 1.000. Intra- and inter-assay coefficients of variation (CV) were <2.21% for all quantified metabolites. Sensitivity was highest for 2-OHE₂ (0.25 pg per absolute injection: signal-to-noise ratio (S/N) = 3) and lowest for 16-epiE₃ (2 pg per absolute injection: S/N = 2.6), translating into corresponding urine sample analyte concentrations of 0.025 ng ml^?1 and 0.2 ng ml^?1, respectively. Accuracy – determined in a two-level spike experiment – showed relative errors ranging between 0.15% for 16-OE₂ and 11.63% for 2-OHE₂. Chromatography showed clear peak shapes for the components analysed. In summary, we describe a practical, sensitive and specific ID/GC–MS assay capable of profiling the above-mentioned steroids in human urine from childhood onwards.     

Methylnickel compounds containing 2-phosphinylethanolato ligands – Syntheses,properties, and ethene coupling reactions

Combining dimethylphosphinylethanols HO(R¹R²)CCH₂PMe₂ (1: R¹ = R² = C₆H₅; 2: R¹ = R² = 4-OMe–C₆H₄; 5: R¹ = R² = 4-NMe₂–C₆H₄) with methyl(methoxo)(trimethylphosphine)nickel gave mononuclear methyl(trimethylphosphine)nickel(chelate) compounds 7–9. Ligand 6 (R¹ = Me, R² = 4-OMe–C₆H₅) afforded a dinuclear methylnickel compound 14. By reacting (TMEDA)lithium-dimethylphosphinylmethanide with ketones OC(R¹R²), the dimethylphosphinylethanols HO(R¹R²)CCH₂PMe₂ (3: R¹R² = 9-fluorenyl; 4: R¹ = H, R² = C₆H₅) were synthesized as prechelate ligands. Under otherwise similar conditions, the fluorenyl substituted anion in 3 gave rise to a mononuclear complex 10 which was found to act as a source of trimethylphosphine forming dinuclear 11 and at the same time to act as an acceptor of trimethylphosphine forming pentacoordinate 10 · PMe₃. Ni(COD)(PMe₃)₂ was used as a scavenger of PMe₃ in converting 8 or 9 to the dinuclear methylnickel compounds 12 and 13, respectively. Modifying the P,O chelating unit of a methyl nickel compound by introducing 2-phosphinylethanolato ligands leads to novel single-component catalysts for ethene oligomerization showing moderate reactivity and thermal stability.     

Production of hemicellulosic sugars and glucose from residual corrugated cardboard

Corrugated cardboard samples were subjected to two-step saccharification. A first prehydrolysis stage was carried out to solubilise the hemicellulosic fraction as hemicellulosic sugars, and the solid phase from prehydrolysis was used as a substrate for the enzymic hydrolysis of cellulose. The prehydrolysis step was carried out for 0–180 min in media containing 1–3 wt.% of H₂SO₄ and the fraction of solid recovered after treatments and the compositions of solid and liquid phases from treatments were measured. The susceptibility of prehydrolysed solids towards the enzymic hydrolysis was assessed in further experiments. Under selected prehydrolysis conditions (3% H₂SO₄, 180 min), 78.2% of initial hemicelluloses was saccharified, leading to liquors containing up to 10 g hemicellulosic sugars/l and 9.2 g glucose/l. The corresponding solid phase, enriched in cellulose, showed good susceptibility towards enzymatic hydrolysis, leading to solutions containing up to 17.9 g glucose/l (conversion yield=63.6%) and a glucose/total sugar ratio of 0.93 g/g. Mathematical models assessing the effects of the operational conditions on both the prehydrolysis stage and the susceptibility of substrates towards enzymic hydrolysis have been developed.     

Hydrogen fermentation of food waste without inoculum addition

A novel batch process that produces H₂ without inoculum addition was devised based on two facts: (1) the abundant indigenous microflora found within organic solid wastes and (2) batch H₂ production completion times being in the same range with hydraulic retention times at continuous processes. Food waste successfully served not only as a substrate but also as a source of H₂-producing microflora when heat (90 °C for 20 min), acid (pH 1.0 for 1 d), or alkali (pH 13.0 for 1 d) treatment was applied. Among the three pretreatments, the heat treatment showed the best performance. The role of the pretreatment was the selection of microbial population rather than the enhancement of hydrolysis. Polymerase chain reaction-denaturing gradient gel electrophoresis analysis showed that lactic acid bacteria were the most abundant species in untreated food waste while H₂-producing bacteria were dominant in the pretreated food wastes. The increase of pretreatment temperature depressed the lactate production while increased the H₂/butyrate production. Repeated batch operation performances were impressive and reliable, achieving a very high H₂ yield of 2.05 mol H₂/mol hexose_consumed with a margin of 17% error. As this invented method is simpler than those of existing continuous systems, and does not require a start-up period, this method is thought to be practically applicable.     

Enzymatic hydrolysis of corncob and ethanol production from cellulosic hydrolysate

 Enzymatic hydrolysis of corncob and ethanol fermentation from cellulosic hydrolysate were investigated. After corncob was pretreated by 1% H₂SO₄ at 108 °C for 3 h, the cellulosic residue was hydrolyzed by cellulase from Trichoderma reesei ZU-02 and the hydrolysis yield was 67.5%. Poor cellobiase activity in T. reesei cellulase restricted the conversion of cellobiose to glucose, and the accumulation of cellobiose caused severe feedback inhibition to the activities of β-1,4-endoglucanase and β-1,4-exoglucanase in cellulase system. Supplementing cellobiase from Aspergillus niger ZU-07 greatly reduced the inhibitory effect caused by cellobiose, and the hydrolysis yield was improved to 83.9% with enhanced cellobiase activity of 6.5 CBU g⁻¹ substrate. Fed-batch hydrolysis process was started with a batch hydrolysis containing 100 g l⁻¹ substrate, with cellulosic residue added at 6 and 12 h twice to get a final substrate concentration of 200 g l⁻¹. After 60 h of reaction, the reducing sugar concentration reached 116.3 g l⁻¹ with a hydrolysis yield of 79.5%. Further fermentation of cellulosic hydrolysate containing 95.3 g l⁻¹ glucose was performed using Saccharomyces cerevisiae 316, and 45.7 g l⁻¹ ethanol was obtained within 18 h. The research results are meaningful in fuel ethanol production from agricultural residue instead of grain starch.     

Synthesis,characterization, structure and luminescence studies of dinuclear gold(I) alkynyls of bis(diphenylphosphino)alkyl- and aryl-amines

A series of alkynylgold(I) bis(diphenylphosphino)alkyl- and aryl-amine complexes, [{Ph₂PN(R)PPh₂}Au₂(CCR′)₂] [R = ⁿPr, R′ = Ph (1), C₆H₄OMe-p (2), C₆H₄Me-p (3), C₆H₄Cl-p (4); R = C₆H₄OMe-p, R′ = Ph (5)], has been synthesized. The X-ray crystal structures of 1 and 2 revealed the presence of short intramolecular Au⋯Au contacts with the distances of 2.8404(8) and 3.0708(7) Å. The luminescence behavior of the complexes were studied.     

Batch and continuous fermentative production of hydrogen with anaerobic sludge entrapped in a composite polymeric matrix

Cell immobilization techniques were adopted to biohydrogen production using immobilized anaerobic sludge as the seed culture. Sucrose-based synthetic wastewater was converted to H₂ using batch and continuous cultures. A novel composite polymeric material comprising polymethyl methacrylate (PMMA), collagen, and activated carbon was used to entrap biomass for H₂ production. Using the PMMA immobilized cells, the favorable conditions for batch H₂ fermentation were 35 °C, pH 6.0, and an 20 g COD l⁻¹ of sucrose, giving a H₂ production rate of 238 ml h⁻¹ l⁻¹ and a H₂ yield of 2.25 mol H₂ mol sucrose⁻¹. Under these optimal conditions, continuous H₂ fermentation was conducted at a hydraulic retention time (HRT) of 4–8 h, giving the best H₂-producing rate of 1.8 l h⁻¹ l⁻¹ (over seven-fold of the best batch result) at a HRT of 6 h and a H₂ yield of 2.0 mol H₂ mol sucrose⁻¹. The sucrose conversion was essentially over 90% in all runs. The biogas consisted of only H₂ and CO₂. The major soluble metabolites were butyric acid, acetic acid, and 2,3-butandiol, while a small amount of ethanol also detected. The PMMA-immobilized-cell system developed in this work seems to be a promising H₂-producing process due to the high stability in continuous operations and the capability of achieving a competitively high H₂ production rate under a relatively low organic loading rate.     

Nitrate removal and greenhouse gas production in a stream-bed denitrifying bioreactor

Denitrifying bioreactors are currently being tested as an option for treating nitrate (NO₃^?) contamination in groundwater and surface waters. However, a possible side effect of this technology is the production of greenhouse gases (GHG) including nitrous oxide (N₂O) and methane (CH₄). This study examines NO₃^? removal and GHG production in a stream-bed denitrifying bioreactor currently operating in Southern Ontario, Canada. The reactor contains organic carbon material (pine woodchips) intended to promote denitrification. Over a 1 year period, monthly averaged removal of influent (stream water) NO₃^? ranged from 18 to 100% (0.3–2.5 mg N L^?1). Concomitantly, reactor dissolved N₂O and CH₄ production, averaged 6.4 μg N L^?1 (2.4 mg N m^?2 d^?1), and 974 μg C L^?1 (297 mg C m^?2 d^?1) respectively, where production is calculated as the difference between inflow and effluent concentrations. Gas bubbles entrapped in sediments overlying the reactor had a composition ranging from 19 to 64% CH₄, 1 to 6% CO₂, and 0.5 to 2 ppmv N₂O; however, gas bubble emission rates were not quantified in this study. Dissolved N₂O production rates from the bioreactor were similar to emission rates reported for some agricultural croplands (e.g. 0.1–15 mg N m^?2 d^?1) and remained less than the highest rates observed in some N-polluted streams and rivers (e.g. 110 mg N m^?2 d^?1, Grand R., ON). Dissolved N₂O production represented only a small fraction (0.6%) of the observed NO₃^? removal over the monitoring period. Dissolved CH₄ production during summer months (up to 1236 mg C m^?2 d^?1), was higher than reported for some rivers and reservoirs (e.g. 6–66 mg C m^?2 d^?1) but remained lower than rates reported for some wastewater treatment facilities (e.g. sewage treatment plants and constructed wetlands, 19,500–38,000 mg C m^?2 d^?1).     

Biosynthesis of ethyl caproate and other short ethyl esters catalyzed by cutinase in organic solvent

The main objective of this work was to study the enzymatic synthesis of short chain ethyl esters, a group of relevant aroma molecules, by Fusarium solani pisi cutinase in an organic solvent media (iso-octane), and to assess the influence of different parameters on the reaction yield.Cutinase displayed high initial esterification rates in iso-octane, which amounted to 1.15 μmol min⁻¹ mg⁻¹ for ethyl butyrate (C₄ acid chain) and 1.06 μmol min⁻¹ mg⁻¹ for ethyl valerate (C₅ acid chain). High product yields, 84% for ethyl butyrate and 96% for ethyl valerate, were observed after 6 h of reaction, for an initial equimolar concentration of substrates (0.1 M).The highest product yield (97%) was observed for ethyl caproate (C₆) synthesis, a compound which is a part of natural apple and pineapple flavour, for an alcohol:acid molar ratio of 2 (0.2 M ethanol concentration).Cutinase affinity for short chain length carboxylic acids (C₄–C₆) in ester synthesis in iso-octane confirmed previous observations in reversed micellar system.     

Sulfate reduction from phosphogypsum using a mixed culture of sulfate-reducing bacteria

Phosphogypsum (CaSO₄), a primary by-product of phosphoric acid production, is accumulated in large stockpiles and occupies vast areas of land. It poses a severe threat to the quality of water and land in countries producing phosphoric acid. In this study, the potential of sulfate-reducing bacteria for biodegradation of this sulfur-rich industrial solid waste was assessed. The effect of phosphogypsum concentration, carbon and nitrogen sources, temperature, pH and stirring on the growth of sulfate-reducing bacteria was investigated. Growth of sulfate-reducing bacteria was monitored by measuring sulfide production. Phosphogypsum was shown to be a good source of sulfate, albeit that the addition of organic carbon was necessary for bacterial growth. Biogenic sulfide production occurred with phosphogypsum up to a concentration of 40 g L⁻¹, above which no growth of sulfate-reducing bacteria was observed. Optimal growth was obtained at 10 g L⁻¹ phosphogypsum. Both the gas mixture H₂/CO₂ and lactate supported high amounts of H₂S formation (19 and 11 mM, respectively). The best source of nitrogen for sulfate-reducing bacteria was yeast extract, followed by ammonium chloride. The presence of nitrate had an inhibitory effect on the process of sulfate reduction. Stirring the culture at 150 rpm slightly stimulated H₂S formation, probably by improving sulfate solubility.     

Mononuclear arene ruthenium complexes containing 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine as chelating ligand: Synthesis and molecular structure

The mononuclear cations of the general formula [(η⁶-arene)RuCl(pdpt)]⁺ (pdpt = 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine; arene = C₆H₆ (1); C₆H₅Me (2); p-PrⁱC₆H₄Me (3); C₆Me₆ (4)) have been synthesised from 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine (pdpt) and the corresponding chloro complexes [(η⁶-C₆H₆)Ru(μ-Cl)Cl]₂, [(η⁶-C₆H₅Me)Ru(μ-Cl)Cl]₂, [(η⁶p-PrⁱC₆H₄Me)Ru(μ-Cl)Cl]₂ and [(η⁶-C₆Me₆)Ru(μ-Cl)Cl]₂, respectively. The X-ray crystal structure analyses of [1][PF₆] · (C₆H₆)_2.5 and [2][PF₆] · (CH₃CN)₂ reveal a typical piano-stool geometry around the metal centre and in the crystal packing a complexed networks of intermolecular interactions.     

Impact of anaerobic digestion on organic matter quality in pig slurry

Changes in pig slurry organic matter (OM) during anaerobic digestion (AD) were studied in a reactor to characterize OM evolution through AD. OM maturity and stability were evaluated using different biological and physico-chemical methods. Germination and growth chamber experiments revealed a higher maturity of digested slurry (DS) than raw slurry (RS). Soil incubations showed that DS was more stable than RS with a C-mineralization of 12.0 g CO₂-C 100 g^?1 C_org after 49 days as compared to 17.6 g CO₂-C 100 g^?1 C_org. Biochemical fractionation showed a relative increase in stable compounds such as hemicellulose-like and lignin-like molecules. Fourier-transform infrared spectroscopy showed some changes in the chemical structures of OM with a reduction in the aliphatic chain, lipid and polysaccharide levels. A comparison between the evolution of OM during AD and the first weeks of a composting process showed almost identical changes. Finally a theoretical method called Fictitious Atomic-group Separation was applied to the elemental compositions of RS and DS. DS was less humified than RS and presented the properties of a fulvic acid, indicating that the observed stability in DS was mainly due to the biodegradation of the most labile compounds.     

Anaerobic treatment of low-strength wastewater with a high fraction of particulate matter in an unconventional two-phase ASBRs system

The results of a two-phase anaerobic system using anaerobic sequencing batch reactors (ASBRs), treating low-strength wastewater (COD ∼ 500 mg/L) with a high fraction of particulate organic matter (70%, COD basis), are presented. Two reactors in series were used; the first one was hydrolytic–acidogenic, while the second one was methanogenic. This configuration was proposed to promote high efficiency solids removal. During the experiment, 69% and 50% efficiencies of total COD removal were obtained for OLRs of 0.63 and 1.22 kgCOD/(m³ d), respectively. Values of the solubilized organic fraction (SOF) achieved in the hydrolytic–acidogenic reactor were within the range of 0.3–0.6 gCOD_solubilized/gpCOD_removed, and the average acidified organic fraction (AOF) was 0.6 gCOD_VFA-produced/gsCOD_fed. The methanogenic reactor had a VFA removal fraction (VFARF) between 0.4 and 0.6 gCOD_VFA-removed/gCOD_VFA-fed for the OLR of 0.63 and 1.22. The two-phase ASBR system is suitable, and can be implemented, for the anaerobic treatment of this kind of wastewater.     

Polyvinyl alcohol–silica nanohybrids: An efficient carrier matrix for amylase immobilization

Polyvinyl alcohol (PVA)–silica nanohybrids have been synthesized in a modified Stöber process. The bioactivities of the enzyme loaded hybrids were monitored and the optimum activity sample (H) was calcined at 300 °C in N₂ to obtain hybrid gel (H₃) with improved performance. The synthesized hybrids have been characterized by Fourier Transform Infra Red spectroscopy, X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and BET surface area analysis. Under the optimized conditions, the bioactivity of the enzyme impregnated H₃ (H₃-Enz) was 21.823 U/mg. On recycling, H₃-Enz retained 88% of its initial bioactivity in the sixth cycle. The kinetic parameters of soluble starch hydrolysis for the immobilized (K_M = 4.137 mg mL^?1; V_max = 5.95 mg mL^?1 min^?1) and free enzyme (K_M = 10.667 mg mL^?1; V_max = 6.0557 mg mL^?1 min^?1) indicated that the immobilization has nearly doubled the enzyme's affinity for the substrate, while the maximum rate of the enzymatic reaction at the saturation point was not much affected. The immobilized enzyme showed greater shelf life in comparison to the free enzyme.