Effect of reactive bed mineralogy on arsenic retention and permeability of synthetic arsenic-containing acid mine drainage

Successive alkalinity producing systems (SAPSs) are widely used for treating acid mine drainage (AMD) and alleviating clogging commonly occurring in limestone systems due to an amorphous ferric precipitate. In this study, iron dust, bone char, micrite and their admixtures were used to treat arseniccontaining AMD. A particular interest was devoted to arsenic removal performance, mineralogical constraints on arsenic retention ability and permeability variation during column experiment for 140 days. The results showed that the sequence of the arsenic removal capacity was as follows: bone char > micrite > iron dust. The combination of 20% v/v iron dust and 80% v/v bone char/micrite columns can achieve better hydraulic conductivity and phosphorus-retention capacity than single micrite and bone char columns. The addition of iron dust created reductive environment and resulted in the transformation of coating material from colloidal phase to secondary mineral phase, such as green rust and phosphoerrite, which obviously ameliorates hydraulic conductivity of systems. The sequential extraction experiments indicated that the stable fractions of arsenic in columns were enhanced with help of iron dust compared to single bone char and micrite columns. A combination of iron dust and micrite/bone char represented a potential SAPS for treating As-containing AMD.

Degradation of simazine from aqueous solutions by diatomite-supported nanosized zero-valent iron composite materials

A novel composite material based on deposition of nanosized zero-valent iron (nZVI) particles on acid-leached diatomite was synthesised for the removal of a chlorinated contaminant in water. The nZVI /diatomite composites were characterized by X-ray diffraction, scanning electron microscopy, elemental analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Compared with the pure nZVI particles, better dispersion of nZVI particles on the surface or inside the pores of diatom shells was observed. The herbicide simazine was selected as the model chlorinated contaminant and the removal efficiency by nZVI /diatomite composite was compared with that of the pristine nZVI and commercial iron powder. It was found that the diatomite supported nZVI composite material prepared by centrifugation exhibits relatively better efficient activity in decomposition of simazine than commercial Fe, lab synthesized nZVI and composite material prepared via rotary evaporation, and the optimum experimental conditions were obtained based on a series of batch experiments. This study on immobilizing nZVI particles onto diatomite opens a new avenue for the practical application of nZVI and the diatomite-supported nanosized zero-valent iron composite materials have potential applications in environmental remediation.

Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives

RATIONALE Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required. METHODS Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M+Na]+ ions that can be mass-selected and subjected to laser irradiation (=266nm) on a modified linear ion-trap mass spectrometer. RESULTS Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carboncarbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M+NaI]center dot+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carboncarbon bond dissociation without scrambling of molecular information. CONCLUSIONS Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box. Copyright (c) 2013 John Wiley & Sons, Ltd.

Formation and Fragmentation of Unsaturated Fatty Acid M-2H+Na (-) Ions: Stabilized Carbanions for Charge-Directed Fragmentation

Fatty acids are long-chain carboxylic acids that readily produce \[M - H](-) ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely \[M - 2H + (FeCl)-Cl-II](-). In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., \[M - 2H + Na](-)). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an \[M - H + NaF](-) ion. Subsequent collision-induced dissociation (CID) results in the desired \[M - 2H + Na](-) ion via the neutral loss of HF. (2) Direct formation of the \[M - 2H + Na](-) ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of \[M - 2H + Na](-) ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

Effect of strong acids on red mud structural and fluoride adsorption properties

The removal of fluoride using red mud has been improved by acidifying red mud with hydrochloric, nitric and sulphuric acid. This investigation shows that the removal of fluoride using red mud is significantly improved if red mud is initially acidified. The acidification of red mud causes sodalite and cancrinite phases to dissociate, confirmed by the release of sodium and aluminium into solution as well as the disappearance of sodalite bands and peaks in infrared and X-ray diffraction data. The dissolution of these mineral phases increases the amount of available iron and aluminium oxide/hydroxide sites that are accessible for the adsorption of fluoride. The removal of fluoride is dependent on the charge of iron and aluminium oxide/hydroxides on the surface of red mud. Acidifying red mud with hydrochloric, nitric and sulphuric acid resulted in surface sites of the form ≡ SOH2+ and ≡ SOH. Optimum removal is obtained when the majority of surface sites are in the form ≡ SOH2+ as the substitution of a fluoride ion doesn’t cause a significant increase in pH. This investigation shows the importance of having a low and consistent pH for the removal of fluoride from aqueous solutions using red mud.

The use of phospholipid fatty acid analysis to measure impact of acid rock drainage on microbial communities in sediments

The impact of acid rock drainage (ARD) and eutrophication on microbial communities in stream sediments above and below an abandoned mine site in the Adelaide Hills, South Australia, was quantified by PLFA analysis. Multivariate analysis of water quality parameters, including anions, soluble heavy metals, pH, and conductivity, as well as total extractable metal concentrations in sediments, produced clustering of sample sites into three distinct groups. These groups corresponded with levels of nutrient enrichment and/or concentration of pollutants associated with ARD. Total PLFA concentration, which is indicative of microbial biomass, was reduced by >70% at sites along the stream between the mine site and as far as 18 km downstream. Further downstream, however, recovery of the microbial abundance was apparent, possibly reflecting dilution effect by downstream tributaries. Total PLFA was >40% higher at, and immediately below, the mine site (0-0.1 km), compared with sites further downstream (2.5-18 km), even after accounting for differences in specific surface area of different sediment samples. The increased microbial population in the proximity of the mine source may be associated with the presence of a thriving iron-oxidizing bacteria community as a consequence of optimal conditions for these organisms while the lower microbial population further downstream corresponded with greater sediments' metal concentrations. PCA of relative abundance revealed a number of PLFAs which were most influential in discriminating between ARD-polluted sites and the rest of the sites. These PLFA included the hydroxy fatty acids: 2OH12:0, 3OH12:0, 2OH16:0; the fungal marker: 18:2ω6; the sulfate-reducing bacteria marker 10Me16:1ω7; and the saturated fatty acids 12:0, 16:0, 18:0. Partial constrained ordination revealed that the environmental parameters with the greatest bearing on the PLFA profiles included pH, soluble aluminum, total extractable iron, and zinc. The study demonstrated the successful application of PLFA analysis to rapidly assess the toxicity of ARD-affected waters and sediments and to differentiate this response from the effects of other pollutants, such as increased nutrients and salinity.

Degradation of hydroxycinnamic acid mixtures in aqueous sucrose solutions by the Fenton process

The degradation efficiencies and behaviors of caffeic acid (CaA), p-coumaric acid (pCoA) and ferulic acid (FeA) in aqueous sucrose solutions containing the mixture of these hydroxycinnamic acids (HCAs) mixtures were studied by the Fenton oxidation process. Central composite design and multi-response surface methodology were used to evaluate and optimize the interactive effects of process parameters. Four quadratic polynomial models were developed for the degradation of each individual acid in the mixture and the total HCAs degraded. Sucrose was the most influential parameter that significantly affected the total amount of HCA degraded. Under the conditions studied there was < 0.01% loss of sucrose in all reactions. The optimal values of the process parameters for a 200 mg/L HCA mixture in water (pH 4.73, 25.15 °C) and sucrose solution (13 mass%, pH 5.39, 35.98 °C) were 77% and 57% respectively. Regression analysis showed goodness of fit between the experimental results and the predicted values. The degradation behavior of CaA differed from those of pCoA and FeA, where further CaA degradation is observed at increasing sucrose and decreasing solution pH. The differences (established using UV/Vis and ATR-FTIR spectroscopy) were because, unlike the other acids, CaA formed a complex with Fe(III) or with Fe(III) hydrogen-bonded to sucrose, and coprecipitated with lepidocrocite, an iron oxyhydroxide.

Novel loci affecting iron homeostasis and their effects in individuals at risk for hemochromatosis

Variation in body iron is associated with or causes diseases, including anaemia and iron overload. Here, we analyse genetic association data on biochemical markers of iron status from 11 European-population studies, with replication in eight additional cohorts (total up to 48,972 subjects). We find 11 genome-wide-significant (P<5 × 10−8) loci, some including known iron-related genes (​HFE, ​SLC40A1, ​TF, ​TFR2, ​TFRC, ​TMPRSS6) and others novel (​ABO, ​ARNTL, ​FADS2, ​NAT2, ​TEX14). SNPs at ​ARNTL, ​TF, and ​TFR2 affect iron markers in ​HFE C282Y homozygotes at risk for hemochromatosis. There is substantial overlap between our iron loci and loci affecting erythrocyte and lipid phenotypes. These results will facilitate investigation of the roles of iron in disease.

Ion exchange treatment of saline solutions using lanxess S108H strong acid cation resin

Common to many types of water and wastewater is the presence of sodium ions which can be removed by desalination technologies, such as reverse osmosis and ion exchange. The focus of this investigation was ion exchange as it potentially offered several advantages compared to competing methods. The equilibrium and column behaviour of a strong acid cation (SAC) resin was examined for the removal of sodium ions from aqueous sodium chloride solutions of varying normality as well as a coal seam gas water sample. The influence of the bottle-point method to generate the sorption isotherms was evaluated and data interpreted with the Langmuir Vageler, Competitive Langmuir, Freundlich, and Dubinin-Astakhov models. With the constant concentration bottle point method, the predicted maximum exchange levels of sodium ions on the resin ranged from 61.7 to 67.5 g Na/kg resin. The general trend was that the lower the initial concentration of sodium ions in the solution, the lower the maximum capacity of the resin for sodium ions. In contrast, the constant mass bottle point method was found to be problematic in that the isotherm profiles may not be complete, if experimental parameters were not chosen carefully. Column studies supported the observations of the equilibrium studies, with maximum sodium loading of ca. 62.9 g Na/kg resin measured, which was in excellent agreement with the predictions of the data from the constant concentration bottle point method. Equilibria involving coal seam gas water were more complex due to the presence of sodium bicarbonate in solution, albeit the maximum loading capacity for sodium ions was in agreement with the results from the more simple sodium chloride solutions.

Cloning and gastrointestinal expression of rat hephaestin: Relationship to other iron transport proteins

The membrane-bound ceruloplasmin homolog hephaestin plays a critical role in intestinal iron absorption. The aims of this study were to clone the rat hephaestin gene and to examine its expression in the gastrointestinal tract in relation to other genes encoding iron transport proteins. The rat hephaestin gene was isolated from intestinal mRNA and was found to encode a protein 96% identical to mouse hephaestin. Analysis by ribonuclease protection assay and Western blotting showed that hephaestin was expressed at high levels throughout the small intestine and colon. Immunofluorescence localized the hephaestin protein to the mature villus enterocytes with little or no expression in the crypts. Variations in iron status had a small but nonsignificant effect on hephaestin expression in the duodenum. The high sequence conservation between rat and mouse hephaestin is consistent with this protein playing a central role in intestinal iron absorption, although its precise function remains to be determined.

Ultrasonic Degradation of Poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water-soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent Mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates-potassium persulfate, ammonium persulfate, and sodium persulfate-were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator.

Acid-catalysed cyclisations: structures of novel products isolated in the reaction of 2-[3-(2,6-dimethoxyphenyl)but-2-enyl]-2-methylcyclopentane-1,3-dione with MeOH-HCl

Reaction of the title compound (1a) with anhydrous MeOH-HCl gave 2-endo-(2,6-dimethoxyphenyl)-2-exo-methyl-5-methylbicyclo[3.2.1]octane-6,8-dione (3a), 1,5,14-timethoxy-5,8-seco-6,7-dinorestra-1,3,5(10),9(11)-tetraen-17-one (4), 1,5-dimethoxy-5,8-seco-6,7-dinorestra-1,3,5(10),8,14-pentaen-17-one (5), and 3,4,5,6-tetrahydro-2,7-dimethoxy-3,6-dimethyl-3,2,6-(13-oxopropan[1]yI[3]ylidene)-2H-1-benzoxocin (6). Structures assigned to compounds (3a), (4), and (6) are based on spectral data. The exo-tricyclic acetal structure (6) was further confirmed by the analysis of the 1H n.m.r. spectra of the isomeric alcohols (11) and (12), obtained by sodium borohydride reduction of (6).

Anthranilate Hydroxylase from Aspergillus niger: New Type of NADPH-Linked Nonheme Iron Monooxygenase

Anthranilate hydroxylase from Aspergillus niger catalyzes the oxidative deamination and dihydroxylation of anthranilic acid to 2,3-dihydroxybenzoic acid. This enzyme has been purified to homogeneity and has a molecular weight of 89,000. The enzyme is composed of two subunits of 42,000 with 2 gram-atoms of nonheme iron per mol. Fe2+-chelators like alpha,alpha'-dipyridyl and o-phenanthroline are potent inhibitors of the enzyme activity. Absorption and fluorescence spectra of the enzyme offer no evidence for the presence of other cofactors like flavin. Flavins and flavin-specific inhibitors like atebrin have no effect on the activity of the enzyme. The enzyme incorporates one atom of oxygen each from 18O2 and H218O into the product 2,3-dihydroxybenzoic acid. Based on these studies, it is concluded that anthranilate hydroxylase from A. niger is a new type of NADPH-linked nonheme iron monooxygenase.

Kinetics of Extraction of Iron(II1) by Bis(2-ethylhexyl Phosphate in a Laminar Liquid-Liquid Jet Reactor

The kinetics of iron(II1) extraction by bis(Zethylhexy1) phosphate (HDEHP, HA) in kerosene from sulfuric acid solutions has been studied in a liquid-liquid laminar jet reactor. The contact time of the interface in this reacting device is of the same order of magnitude as the surface renewal time in dispersion mixing and much less than that obtained in the relatively quiescent condition of the Lewis cell. Yet the analysis of the data in this study suggested a rate-controlling step involving surface saturation quite in conformity with that obtained in the Lewis cell and not with that in dispersion mixing as reported in the literature. Further, the mechanism suggested a weaker dependence of the rate on hydrogen ion concentration which was reported by other workers.

Identification of a mutation in the para-sodium channel gene of the cattle tick Rhipicephalus (Boophilus) microplus associated with resistance to synthetic pyrethroid acaricides

Resistance against synthetic pyrethroid (SP) products for the control of cattle ticks in Australia was detected in the field in 1984, within a very short time of commercial introduction. We have identified a mutation in the domain II S4-5 linker of the para-sodium channel that is associated with resistance to SPs in the cattle tick Rhipicephalus (Boophilus) microplus from Australia. The cytosine to adenine mutation at position 190 in the R. microplus sequence AF134216, results in an amino acid substitution from leucine in the susceptible strain to isoleucine in the resistant strain. A similar mutation has been shown to confer SP resistance in the whitefly, Bemisia tabaci, but has not been described previously in ticks. A diagnostic quantitative PCR assay has been developed using allele-specific Taqman® minor groove-binding (MGB) probes. Using the assay to screen field and laboratory populations of ticks showed that homozygote allelic frequencies correlated highly with the survival percentage at the discriminating concentration of cypermethrin.