Observation of surface precipitation of arsenate on ferrihydrite

X-ray diffraction and Raman spectroscopy were used in this study to characterize arsenate phases in the arsenate-ferrihydrite sorption system. Evidence has been obtained for surface precipitation of ferric arsenate on synthetic ferrihydrite at acidic pH (3-5) underthe following experimental conditions: sorption density of As/Fe approximately 0.125-0.49 and arsenic equilibrium concentration of <0.02-440 mg/L. Surface precipitation occurred under apparently undersaturated (in the bulk solution phase) conditions, and probably involved initial uptake of arsenate by surface complexation followed by transition to ferric arsenate formation on the surface as indicated by XRD analysis. At basic pH (i.e., pH 8), however, no ferric arsenate was observed in arsenate-ferrihydrite samples at a sorption density of As/Fe approximately 0.125-0.30 and an arsenic equilibrium concentration of 2.0-1100 mg/ L. At pH 8, arsenate is sorbed on ferrihydrite predominantly via surface adsorption, and the XRD patterns resemble basically that of ferrihydrite.     

Photoinduced oxidation of arsenite to arsenate on ferrihydrite

The photochemistry of an aqueous suspension of the iron oxyhydroxide, ferrihydrite, in the presence of arsenite has been investigated using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray absorption near edge structure (XANES), and solution phase analysis. Both ATR-FTIR and XANES show that the exposure of ferrihydrite to arsenite in the dark leads to no change in the As oxidation state, but the exposure of this arsenite-bearing surface, which is in contact with pH 5 water, to light leads to the conversion of the majority of the adsorbed arsenite to the As(V) bearing species, arsenate. Analysis of the solution phase shows that ferrous iron is released into solution during the oxidation of arsenite. The photochemical reaction, however, shows the characteristics of a self-terminating reaction in that there is a significant suppression of this redox chemistry before 10% of the total iron making up the ferrihydrite partitions into solution as ferrous iron. The self-terminating behavior exhibited by this photochemical arsenite/ferrihydrite system is likely due to the passivation of the ferrihydrite surface by the strongly bound arsenate product.     

Low temperature XAFS investigation on the lutetium binding changes during the 2-line ferrihydrite alteration process

The time dependent changes of Lu speciation (used as Am(III) homologue), initially sorbed onto 2-line ferrihydrite at pH 5.9, during tempering (70 degrees C) to stable crystalline transformation products, goethite and hematite, is studied. Microscopies (AFM, SEM), XRD and FTIR spectroscopy confirm transformation to both goethite and hematite, with a predominance of hematite. XRD investigation of another transformation series at pH 8.0 (75 degrees C, [Lu(III)initial] 7 times higher) shows that the cell volume of hematite increases, suggesting the incorporation of Lu in the crystal structure. Extended X-ray absorption fine structure (EXAFS) (pH 5.9 series, 70 degrees C) reveals a shortening of the Lu-O bond distance and an increase in asymmetry of the first shell with increasing tempering time in the intermediate temper time samples. The intensity of the second peak in the Fourier transform (FT) of the EXAFS increases and splits into two components. The EXAFS data of the end product can be modeled well using a hematite-like cluster, with an isotropic expansion of distances to account for incorporation of Lu into the hematite structure. These results demonstrate that the Lu is incorporated in the crystal lattice of the transformation product, as opposed to being occluded or remaining a sorbed species on the surface.     

Influence of arsenate adsorption to ferrihydrite, goethite, and boehmite on the kinetics of arsenate reduction by Shewanella putrefaciens strain CN-32

The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 μM) and lactate (25 μM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (～5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.     

Adsorption of arsenate onto ferrihydrite from aqueous solution: influence of media (sulfate vs nitrate), added gypsum, and pH alteration

Mineral processing effluents generated in hydrometallurgical industrial operations are sulfate based; hence it is of interest to investigate the effect sulfate matrix solution ("sulfate media") has on arsenate adsorption onto ferrihydrite. In this work, in particular, the influence of media (SO4(2-) vs NO3-), added gypsum, and pH alteration on the adsorption of arsenate onto ferrihydrite has been studied. The ferrihydrite precipitated from sulfate solution incorporated a significant amount of sulfate ions and showed a much higher adsorption capacityfor arsenate compared to nitrateferrihydrite at pH 3-8 and initial Fe/As molar ratios of 2, 4, and 8. Adsorption of arsenate onto sulfate-ferrihydrite involved ligand exchange with SO4(2-) ions that were found to be more easily exchangeable with increasing pH. Added gypsum to the adsorption system significantly enhanced the uptake of arsenate by ferrihydrite at pH 8. Equilibration treatment at acidic pH and addition of gypsum markedly improved the stability of adsorbed arsenate on ferrihydrite when pH was elevated. Comparison of arsenate adsorption onto ferrihydrite to coprecipitation of arsenate with iron(III) showed the latter process to lead to higher arsenic removal.     

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite--water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [P(CO2) = 10(-3.5) atm and approximately 0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L(-1), [As(V)]0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L(-1), [As(V)]0 = 0.5 mM and I = 0.01 M NaCI], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (P(CO2) = 10(-3.5) atm) than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear ( 2.8 A) and bidentate binuclear (approximately equal to 3.3 A) bonding at pH 4.5-8 and loading levels of 0.46-3.10 microM m(-2). Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P(CO2) = 10(-3.5) atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).     

Impact of ferrihydrite and anthraquinone-2,6-disulfonate on the reductive transformation of 2,4,6-trinitrotoluene by a gram-positive fermenting bacterium

Batch studies were conducted to explore differences in the transformation pathways of 2,4,6-trinitrotoluene (TNT) reduction by a Gram-positive fermenting bacterium (Cellulomonas sp. strain ES6) in the presence and absence of ferrihydrite and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Strain ES6 was capable of TNT and ferrihydrite reduction with increased reduction rates in the presence of AQDS. Hydroxylaminodinitrotoluenes, 2,4-dihydroxylamino-6-nitrotoluene (2,4-DHANT), and tetranitroazoxytoluenes were the major metabolites observed in ferrihydrite- and AQDS-free systems in the presence of pure cell cultures. Ferrihydrite enhanced the production of amino derivatives because of reactions with microbially produced surface-associated Fe(ll). The presence of AQDS in the absence of ferrihydrite promoted the fast initial formation of arylhydroxylamines such as 2,4-DHANT. However, unlike in pure cell systems, these arylhydroxylamines were transformed into several unidentified polar products. When both microbially reduced ferrihydrite and AQDS were present simultaneously, the reduction of TNT was more rapid and complete via pathways thatwould have been difficult to infer solely from single component studies. This study demonstrates the complexity of TNT degradation patterns in model systems where the interactions among bacteria, Fe minerals, and organic matter have a pronounced effect on the degradation pathway of TNT.     

Stability and transformation of products formed from dimeric dehydroascorbic acid at low pH

Dehydroascorbic acid dimer (DDHA) is the commercially available form of oxidised vitamin C. When DDHA enters an aqueous environment, it will interact with water, but the details of this process are not well defined. Hydration of DDHA was analyzed as a function of concentration, pH and temperature. Above pH 5 only hydrated dehydroascorbic acid monomer (DHA) and its degradation product 2,3-diketogulonic acid (DKG) were observed. At pH lower than 4 and in MilliQ water, relatively stable hydrated dimeric species were additionally detected. They are intermediates formed from DDHA and transformed into DKG, either directly or through DHA. A lower temperature of dissolution favours the formation of hydrated dimeric products, while the concentration of DDHA has no effect on their yield. All products were separated chromatographically and analyzed by three detectors: diode array, refractive index and electrospray ionisation mass spectrometry. The stability and transformations of products were studied in the mixture and in the isolated fractions. Two initially formed monohydrated products are transformed to a dihydrated product that is degraded to DHA and DKG. Once formed, the dihydrated product and one of the monohydrated products are sufficiently stable to be identified at neutral pH. All three hydrated products are interconvertible and can be also formed after dissolution of dried DHA.     

Effects of Temperature and Oxygen on the Growth of Listeria monocytogenes at pH 4.5

Growth effects were studied using tryptose phosphate broth adjusted with hydrochloric acid. The microorganism survived for extended periods at low incubation temperatures (5 and 10°C), and grew at intermediate temperatures (19 and 28°C). Aerobic incubation at 37°C resulted in relatively rapid inactivation of the organism; however, when oxygen was restricted the organism recovered and survived for extended periods. Oxygen restriction enhanced the growth rate at 19°C. Results demonstrated temperature and oxygen availability interacted to influence survival of L. monocytogenes in low pH environment.     

Coordination structure of adsorbed Zn(II) at water-TiO2 interfaces

The local structure of aqueous metal ions on solid surfaces is central to understanding many chemical and biological processes in soil and aquatic environments. Here, the local coordination structure of hydrated Zn(II) at water-TiO(2) interfaces was identified by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopy combined with density functional theory (DFT) calculations. A nonintegral coordination number of average ～4.5 O atoms around a central Zn atom was obtained by EXAFS analysis. DFT calculations indicated that this coordination structure was consistent with the mixture of 4-coordinated bidentate binuclear (BB) and 5-coordinated bidentate mononuclear (BM) metastable equilibrium adsorption (MEA) states. The BB complex has 4-coordinated Zn, while the monodentate mononuclear (MM) complex has 6-coordinated Zn, and a 5-coordinated adsorbed Zn was found in the BM adsorption mode. DFT calculated energies showed that the lower-coordinated BB and BM modes were thermodynamically more favorable than the higher-coordinated MM MEA state. The experimentally observed XANES fingerprinting provided additional direct spectral evidence of 4- and 5-coordinated Zn-O modes. The overall spectral and computational evidence indicated that Zn(II) can occur in 4-, 5-, and 6-oxygen coordinated sites in different MEA states due to steric hindrance effects, and the coexistence of different MEA states formed the multiple coordination environments.     

Effects of pH, chloride, and bicarbonate on Cu(I) oxidation kinetics at circumneutral pH

The oxidation kinetics of nanomolar concentrations of Cu(I) in NaCl solutions have been investigated over the pH range 6.5-8.0. The overall apparent oxidation rate constant was strongly affected by chloride, moderately by bicarbonate, and to a lesser extent by pH. In the absence of bicarbonate, an equilibrium-based speciation model indicated that Cu(+) and CuClOH(-) were the most kinetically reactive species, while the contribution of other Cu(I) species to the overall oxidation rate was minor. A kinetic model based on recognized key redox reactions for these two species further indicated that oxidation of Cu(I) by oxygen and superoxide were important reactions at all pH values and chloride concentrations considered, but back reduction of Cu(II) by superoxide only became important at relatively low chloride concentrations. Bicarbonate concentrations from 2 to 5 mM substantially accelerated Cu(I) oxidation. Kinetic analysis over a range of bicarbonate concentrations revealed that this was due to formation of CuCO(3)(-), which reacts relatively rapidly with oxygen, and not due to inhibition of the back reduction of Cu(II) by formation of Cu(II)-carbonate complexes. We conclude that the simultaneous oxygenation of Cu(+), CuClOH(-), and CuCO(3)(-) is the rate-limiting step in the overall oxidation of Cu(I) under these conditions.     

Oxidative dissolution of chromium(III) hydroxide at pH 9, 3, and 2 with product inhibition at pH 2

Hexavalent chromium, Cr(VI), can be immobilized under neutral to alkaline conditions by reduction to Cr(III); similarly, the mobility of naturally occurring Cr in soils and sediments can be limited by its occurrence in the +III oxidation state. Conversely, the oxidation of Cr(IIi) to Cr(VI) increases both its toxicity and often its mobility. Dissolution of Cr-(OH)3(s) in 0.01 M NaNO3 suspensions was examined in batch experiments in the presence and absence of the strong oxidant sodium hypochlorite (NaOCI). Dissolution of Cr(OH)3(s) (1.0 g/L) was accelerated in the presence of excess strong oxidant (20 mM) at pH 9 by a factor of ca. 200 and to a lesser extent at pH 2 and 3. Linear kinetics of oxidative dissolution was observed at pH 9 and 3. In contrast, the rate of Cr release at pH 2 decreased rapidly with time, and within 2.5 h, the dissolution reaction was completely inhibited. Under oxidizing conditions, Cr released into solution is expected to be present as Cr(VI), which sorbs strongly to Cr(OH)3(s) at low pH. Cr(VI) sorption followed a Langmuir isotherm and reached maximum sorption densities of 308 +/- 8 and 271 +/- 10 micromol/g at pH 3 and 2, respectively. However, sorption of Cr(VI) (putatively formed during oxidative dissolution) cannot explain the observed inhibition of the reaction because (1) sorption occurs at both pH 2 and 3 but inhibition only at pH 2 and (2) preequilibration of Cr(OH)3(s) with Cr(VI) did not affectthe rate of dissolution observed upon the addition of the oxidant. Thus, we hypothesize that the inhibition of (net) oxidative dissolution at pH 2 may be the result of secondary precipitation of a chromic hydroxy chromate phase.     

2种检测方法对弯曲菌检出率的影响

目的 比较国标法和双孔滤膜法在生禽肉中弯曲菌的检测率,探索生禽肉中弯曲菌分离鉴定的有效检测方法.方法 随机采集冷冻和新鲜禽肉产品共102份,通过国标法和双孔滤膜法2种方法检测,观察2种方法从样品处理、增菌和分离培养过程中的不同,并比较2种方法检测弯曲菌检出率的差异.结果 102份样品中国标法检出弯曲菌的检出率为28.4...     

超临界CO2流体流速对涤纶织物染色的影响

超临界CO2流体的流速会影响染料在超临界CO2介质中对涤纶织物的上染性能和染色均匀性。通过研究在不同超临界CO2流速下的C．I．分散红60对涤纶织物的上染性能和匀染性的影响，得出其影响规律。     

Effects of FeS on the transformation kinetics of gamma-hexachlorcyclohexane

Distinctly different rates and pathways were observed for abiotic transformation of gamma-hexachlorocyclohexane (gamma-HCH) between homogeneous systems and systems containing FeS solid. The observed half-lives of gamma-HCH decrease from about 1136 and 126 d in homogeneous systems to about 55 and 50 d in heterogeneous systems at pH approximately 6.9 and pH approximately 8.3, respectively. While no appreciable difference in the measured rate was found between the two tested heterogeneous systems of pH 6.9 and pH 8.3, the observed hydrolysis rate constant for the homogeneous systems is highly pH dependent, being constant at approximately 0.0005 d(-1) in pH 2.26-6.73, and increased by an order of magnitude per pH unit from pH 6.73 to pH 12.02. A dehydrohalogenation pathway from gamma-HCH to pentachlorocyclohexene followed by parallel reactions to three trichlorobenzenes is proposed for the hydrolysis reaction in the homogeneous systems. For the heterogeneous systems, the reactions likely follow both the hydrolysis pathway and pathways from gamma-HCH to tetrachlorocyclohexene (TeCCH) and to dichlorocyclohexadiene (DCCD) via dichloroelimination followed by dehydrohalogenation from TeCCH to dichlorobenzenes or from DCCD to chlorobenzene. This study suggests that environmental modeling using hydrolysis rate data measured in homogeneous systems may bear significant inaccuracy for the predicted fate and transport of HCH isomers in highly heterogeneous ecosystems at the regional or mega scales.     

Effects of time at suboptimal pH on rumen fermentation in a dual-flow continuous culture system

Ruminal pH varies considerably during the day, achieving values below 6.0 when cows consume large amounts of concentrates. Low ruminal pH has negative effects on ruminal fermentation. However, previous studies have indicated that rumen bacteria may resist short periods of low ruminal pH, and it is not clear how long this period may be before rumen microbial fermentation is negatively affected. Seven dual-flow continuous culture fermenters (1,320 mL) were used in 3 replicated periods with the same diet (97 g of dry matter/d of a 60:40 forage-to-concentrate diet, 18.3% crude protein, 35.9% neutral detergent fiber), temperature (39°C), and solid (5%/h) and liquid (10%/h) dilution rates to study the effects of increasing time at suboptimal pH on rumen microbial fermentation and nutrient flow. Treatments were a constant pH of 6.4 and 6 different intervals of time during the day (4, 8, 12, 16, 20, 24 h) at suboptimal pH (5.5), with the rest of the day being at pH 6.4. Polynomial equations were derived using the Mixed procedure of SAS, and linear, quadratic and cubic terms were left in the equation if P < 0.10. True organic matter digestion decreased with increasing time at suboptimal pH and was best described by a cubic regression (TOMD = 58.5 − 2.15x + 0.16x² −0.0037x³; R² = 0.74). Digestion of NDF (DNDF = 55.1 − 1.00x; R² = 0.75) and digestion of ADF (DADF = 56.2 − 1.33x; R² = 0.78) decreased linearly with increasing time at suboptimal pH. Total VFA had a cubic response (VFA = 112.7 − 2.09x + 0.17x² − 0.0054x³; R² = 0.82). The proportion of acetate decreased linearly (acetate = 58.7 − 0.61x; R² = 0.79). The propionate proportion increased (propionate = 17.6 + 2.09 × −0.044x²; R² = 0.85) and branched-chain VFA decreased (BCVFA = 4.45 −0.51x + 0.014x²; R² = 0.75) quadratically. The ammonia N concentration (NH₃-N = 5.85 − 0.13x; R² = 0.46) and flow (NH₃-N flow = 0.18 − 0.0039x; R² = 0.43) decreased linearly as the time at suboptimal pH increased. Crude protein degradation (CPd = 41.9 − 1.60x + 0.060x²; R² = 0.71), efficiency of microbial protein synthesis (EMPS = 26.6 − 0.33x + 0.021x²; R² = 0.77), microbial N flow (MN flow = 1.38 − 0.036x + 0.0015x²; R² = 0.77), and dietary N flow (DN flow = 1.49 + 0.041x − 0.0015x²; R² = 0.65) had a quadratic response. The flow of essential, nonessential, and most individual AA increased linearly with increasing time at suboptimal pH. The effects of pH on rumen fermentation appear to start as soon as pH drops to suboptimal pH.     

TiO2-based photocatalytic degradation of 2-chlorophenol adsorbed on hydrophobic clay

The combination of adsorption and heterogeneous photocatalysis has been investigated as a promising technology for the removal of organic water pollutants. A laboratory study of the removal and decomposition of 2-chlorophenol (2-CP) as a toxic organic pollutant was carried out under various conditions with an organophilized clay mineral (hexadecylpyridinium chloride-modified montmorillonite; HDPM) as adsorbent and Degussa P25 TiO2 as photocatalyst. Three different oxidation processes leading to the degradation of 2-CP were compared: direct photolysis, heterogeneous photocatalysis in a TiO2 suspension, and the decomposition of substrate adsorbed on HDPM in the presence of TiO2. Both the degradation of 2-CP and the formation of intermediates were analyzed by HPLC, the total organic carbon content and the total organic and inorganic chloride contents were measured to monitor the mineralization process, and X-ray diffraction and thermoanalytical measurements were made to characterize the hydrophobic clay adsorbent. The heterogeneous photocatalytic degradation of dissolved (2-CP/UV/TiO2) and desorbed 2-CP (2-CP/HDPM/UV/TiO2) appeared to be equally efficient, whereas direct photolysis of 2-CP was far less efficient in the oxidative destruction. HDPM proved to be a suitable adsorbent, capable of adsorbing toxic organics from water. It was demonstrated that the adsorbent (at relatively high concentration) did not decrease the rate of mineralization of 2-CP. The results confirmed that the adsorbent retains its structure and composition during the mineralization process, and thus it can be reused without regeneration. The combination of adsorption and heterogeneous photocatalysis studied may be an efficient and economical means of accumulating, removing, and oxidizing organic water contaminants, and its application is in accordance with the growing environmental demands.     

Effects of pepsin hydrolysis on the soy β‐conglycinin aggregates formed by heat treatment at different pH

The effects of pepsin hydrolysis on the β‐conglycinin aggregates formed by heat treatment at different pH were investigated. Results showed that fibrils were still observed, whereas the random aggregates were easily to be digested in the simulated gastric fluid. Electrophoresis and molecular weight analysis indicated that large aggregates still existed after pepsin treatment for fibrils. Hydrolysis resulted in changes in the apparent viscosity (ηapp) of 6% fibril solutions. The ηapp at the shear rate range (0–30 s^?1) increased in the order of fibrils < fibrils with pepsin for 60 min < fibrils with pepsin for 30 min. Smaller peptide/fibril fragments were generated, and additional aggregates were reformed during the hydrolysis process, as evidenced by thioflavin T and atomic force microscopy images. The native β‐conglycinin hydrolysates comprised a mixture of polypeptides enriched in about 47 kDa. These findings would provide valuable information about effects of enzymatic hydrolysis on plant oligometric globulin aggregates.     

pH值对钝顶螺旋藻生长的影响

pH值不但影响培养液中营养基质的离解程度，而且对螺旋藻的生长、代谢乃至细胞形态都造成显著的影响。本文得出：钝顶螺旋藻生长的pH范围为8.5～10．0，最适生长pH为9．0～9．6，pH值超过10．5时，对螺旋藻的生长产生抑制作用。混合营养培养时，通过对螺旋藻生长过程中pH值变化的研究，得出：与无机碳源相比，有机碳源作为营养源更易被螺旋藻利用并合成细胞物质。