The impact of background wastewater constituents on the selectivity and capacity of a hybrid ion exchange resin for phosphorus removal from wastewater.

Conventional sorption media are inefficient for phosphorus removal from wastewater due to preference for competing species such as sulphate, nitrate and organics. This work investigates whether the use of hybrid ion exchange resins effectively negates such concerns. Trials were conducted with a hybrid anion exchange (HAIX) media which was preloaded with different background constituents and operated over multiple regeneration cycles to ascertain the likely impacts. The work revealed that whilst the impact of the other constituents was seen in regards to direct competition, the major impact was on reduction of the rate of intraparticle mass transfer through sorption of the constituents onto the base resin thereby reducing the Donnan membrane effect. Comparison of the impact of the background water constituents on the individual components (hybrid resin, base resin, nanoparticles) revealed the importance of the nanoparticle whereby they effectively transform the ion exchange media into a mono component absorber for phosphorus that enables sustained removal even in complex wastewaters.

Immobilized FhuD2 Siderophore-Binding Protein Enables Purification of Salmycin Sideromycins from Streptomyces violaceus DSM 8286.

Siderophores are a structurally diverse class of natural products common to most bacteria and fungi as iron(III)-chelating ligands. Siderophores, including trihydroxamate ferrioxamines, are used clinically to treat iron overload diseases and show promising activity against many other iron-related human diseases. Here, we present a new method for the isolation of ferrioxamine siderophores from complex mixtures using affinity chromatography based on resin-immobilized FhuD2, a siderophore-binding protein (SBP) from Staphylococcus aureus. The SBP-resin enabled purification of charge positive, charge negative, and neutral ferrioxamine siderophores. Treatment of culture supernatants from Streptomyces violaceus DSM 8286 with SBP-resin provided an analytically pure sample of the salmycins, a mixture of structurally complex glycosylated sideromycins (siderophore-antibiotic conjugates) with potent antibacterial activity toward human pathogenic Staphylococcus aureus (minimum inhibitory concentration (MIC) = 7 nM). Siderophore affinity chromatography could enable the rapid discovery of new siderophore and sideromycin natural products from complex mixtures to aid drug discovery and metabolite identification efforts in a broad range of therapeutic areas.

The Antioxidant and Safety Properties of Spent Coffee Ground Extracts Impacted by the Combined Hot Pressurized Liquid Extraction-Resin Purification Process.

Hot pressurized liquid extraction has been used to obtain polyphenols; however, its operating conditions can generate hydroxymethylfurfural, a potential human carcinogen. The addition of ethanol can reduce process temperatures and retain extraction efficiencies, but the ethanol may reduce the recovery of polyphenols in the subsequent purification stage, affecting the antioxidant properties of the extracts. This study evaluates a combined hot pressurized liquid extraction-resin purification process to obtain polyphenol extracts from spent ground coffee reduced in hydroxymethylfurfural. A multifactorial design was developed to determine the combined effect of the extraction (ethanol content: 0-16% and temperature: 60-90 °C) and purification (ethanol: 60-80%) conditions on some chemical properties of the extracts. The highest recovery of polyphenols (~8 mg GAE/g dry coffee solids) and reduction of hydroxymethylfurfural (95%) were obtained at 90 °C and 16% of ethanol during extraction and 80% of ethanol during purification. These operating conditions retained the antioxidant capacity of the crude extract between 60% and 88% depending on the determination method and recovered 90, 98, and 100% of 4-feruloylquinic acid, epicatechin, and 5-feruloylquinic acid, respectively after purification. The combined process allows differential polyphenols' recovery and enhances the safety of the extracts. Our computational chemistry results ruled out that the overall selectivity of the integrated process was correlated with the size of the polyphenols.

Enrichment of antioxidants in black garlic juice using macroporous resins and their protective effects on oxidation-damaged human erythrocytes.

The black garlic juice is popular for its nutritive value. Enrichment of antioxidants is needed to make black garlic extract an effective functional ingredient. Five macroporous resins were evaluated for their capacity in adsorbing antioxidants in black garlic juice. XAD-16 resin was chosen for further study due to its high adsorption and desorption ratios. Pseudo-second-order kinetics (qe=625µmol Trolox equiv/g dry resin, k2=0.0001463) and Freundlich isotherm models (ΔH=-10.1547kJ/mol) were suitable for describing the whole exothermic and physical adsorption processes of the antioxidants from black garlic juice on XAD-16 resin. The antioxidants and phenolics were mostly enriched in 40% ethanol fraction by XAD-16 resin column chromatography. The black garlic extract and its fractions could protect erythrocytes against AAPH-induced hemolysis in dose-dependent manners. The pretreatment of AAPH-damaged erythrocytes with 40% ethanol fractions (2.5mg/mL) significantly decreased the hemolysis ratios from 53.58% to 3.79%. The 40% ethanol fraction possessing strong intracellular antioxidant activity could be used as a functional food ingredient.

Vanadium removal and recovery from bauxite residue leachates by ion exchange.

Bauxite residue is an important by-product of the alumina industry, and current management practices do not allow their full valorisation, especially with regard to the recovery of critical metals. This work aims to test the efficiency of ion exchange resins for vanadium (V) removal and recovery from bauxite residue leachates at alkaline pH (11.5 and 13). As an environmental pollutant, removal of V from leachates may be an obligation of bauxite residue disposal areas (BRDA) long-term management requirements. Vanadium removal from the leachate can be coupled with the recovery, and potentially can be used to offset long-term legacy treatment costs in legacy sites. Kinetics studies were performed to understand the adsorption process. The rate kinetics for the V adsorption was consistent with the pseudo-first-order kinetic model, with a higher adsorption rate for pH 11.5 (1.2 min-1). Adsorption isotherm data fitted better to Freundlich equations than to the Langmuir model. The maximum adsorption capacity (Langmuir value q max) was greatest for pH 13 (9.8 mg V g-1 resin). In column tests, breakthrough was reached at 70 bed volumes with the red mud leachate at pH 13, while no breakthrough was achieved with the effluent at pH 11.5. In regeneration, 42 and 76 % of V were eluted from the resin with 2 M NaOH from the red mud leachate at pH 13 and 11.5, respectively. Further optimization will be needed to upscale the treatment.

A total analytical system featuring a novel solid-liquid extraction chamber for solid sample flow analysis.

In this work, a total flow analysis system based on a novel solid-liquid extraction chamber is presented. This strategy enables all the main experimental procedures for the analysis of a solid sample to be performed automatically: enrichment of the liquid extract, sample treatment, filtration of the liquid extract from the solid sample, directing the extract towards detection, and finally cleansing of the chamber for the following solid sample to be analyzed. The chamber designed to be incorporated in the flow manifold presents two main features: it accommodates stirring bars for enhancing the extraction process, and it presents replaceable solid sample containers (a spare part of the solid-liquid extraction chamber) to easily replace the solid sample and therefore enhance sample analysis throughput. The chamber performance was assessed using two different solid samples, an ion exchanger resin and vegetable samples, focussing on proton and nitrate ion extraction, respectively. The main figures of merit achieved were relative standard deviation (RSD) and relative error values below 7 % for all determinations. The determination rate for vegetable samples was ca. 12 samples h-1. The proposed strategy may be exploited to perform automatically the analysis of solid samples as it embodies a simple automatic strategy of a very important but time-consuming and laborious analytical operation. Graphical abstract TAS for solid liquid extraction and nitrate potentiometric determination of vegetable samples.

High-rate MIEX filtration for simultaneous removal of phosphorus and membrane foulants from secondary effluent.

This work was designed to evaluate the effectiveness of magnetic ion exchange (MIEX) resin under the best possible conditions, passage through a fixed-bed of resin as opposed to the alternative of directly adding resin into a flowing stream. The possibility of using a very small amount of alum in addition to MIEX treatment was also investigated not only to adsorb residual EfOM in the effluent from a bed of MIEX but also to produce a porous cake layer that would keep away foulants from the surface of membrane or its pore walls. The MIEX treatment alone reduced fouling, but to a much lesser extent than for MIEX combined with an under-dosing coagulation (which uses a considerably low amount of alum). Almost all of colloids and organic acids were removed and the nearly complete removal of phosphorus was achieved by MIEX in a fixed-bed even for an extremely short hydraulic retention time of wastewater in the resin bed. MIEX resin removed phosphorus, but organic acids in EfOM were preferentially removed and the effects of competing anions on the removal of EfOM were insignificant. The MIEX treatment with added alum (only 0.5 mg Al L(-1)) dramatically improved the performance of MF and UF membranes and the subsequent membrane filtration also achieved ≤0.01 mg L(-1) of residual phosphorous. This condition also allowed good flux recovery after hydraulic flushing.

Preparation and quality assessment of high-purity ginseng total saponins by ion exchange resin combined with macroporous adsorption resin separation.

AIM: To prepare high-purity ginseng total saponins from a water decoction of Chinese ginseng root. METHOD: Total saponins were efficiently purified by dynamic anion-cation exchange following the removal of hydrophilic impurities by macroporous resin D101. For quality control, ultrahigh-performance liquid chromatography with a charged aerosol detector (CAD) was applied to quantify marker components. The total saponin content was estimated by a colorimetric method using a vanillin-vitriol system and CAD response. RESULTS: D201, which consisted of a cross-linked polystyrene matrix and -N(+)(CH3)3 functional groups, was the best of the four anion exchange resins tested. However, no significant difference in cation exchange ability was observed between D001 (strong acid) and D113 (weak acid), although they have different functional groups and matrices. After purification in combination with D101, D201, and D113, the estimated contents of total saponins were 107% and 90% according to the colorimetric method and CAD response, respectively. The total amount of representative ginsenosides Re, Rd, Rg1, and compound K was approximately 22% based on ultrahigh-performance liquid chromatography-CAD quantitative analysis. CONCLUSION: These findings suggest that an ion exchange resin, combined with macroporous adsorption resin separation, is a promising and feasible purification procedure for neutral natural polar components.

Biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge.) seed oil using ion exchange resin as heterogeneous catalyst.

In this study, biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge.) seed oil using ion exchange resin as heterogeneous catalyst was investigated. After illustration of the mechanisms of transesterification reactions catalyzed by typical ion exchange resins, the factors affecting microwave-assisted transesterification process were studied. A high conversion yield of about 96% was achieved under optimal conditions using high alkaline anion exchange resins as catalyst. Analyzing the FAMEs composition by GC-MS and main physical-chemical properties demonstrated that the biodiesel product prepared from yellow horn seed oil was of high quality. Compared with conventional alkali catalyst, the outstanding characteristics of reusability and operational stability made the resin catalyst more predominant for biodiesel production. In addition, a comprehensive kinetic model was established for analyzing the reaction. The results of present research showed that microwave-assisted transesterification process catalyzed by high alkaline anion exchange resin was a green, effective and economic technology for biodiesel industry.

Comparison of sorption behavior of Th(IV) and U(VI) on modified impregnated resin containing quinizarin with that conventional prepared impregnated resin.

This paper reports the results obtained by studying the ion-exchange properties of a new solvent impregnated resin (SIR), which was prepared by impregnation of quinizarin (1,4-dihydroxyanthraquinone, QNZ) on Amberlite XAD-16 after nitration of the benzene rings present in its structure. The sorption behavior of Th(IV) and U(VI) on/in the modified SIR was compared with that of the SIR prepared via the conventional method. It was observed that sorption capacity and sorption rate of the modified SIR are significantly greater than the conventional one. The modified SIR was then applied to the extraction of Th(IV) and U(VI) ions at the presence of many co-existence metal ions. The results obtained denote on successful application of this new SIR to analysis of natural water samples spiked to Th(IV) and U(VI) ions.

High selective purification of flavonoids from natural plants based on polymeric adsorbent with hydrogen-bonding interaction.

The efficient purification method of high purity flavonoids from natural plants was reported. A series of polymeric adsorbents with novel structure were synthesized based on the copolymerization of methyl acrylate (MA) and ethylene glycol dimethacrylate (EDGMA). Functional groups, such as ester, amino or amide group, were introduced into the adsorbent matrix, respectively, to produce the hydrogen-bonding interaction and enhance the adsorption selectivity towards flavone compounds. The influences of matrix structure and functional groups of synthesized adsorbents on the adsorption selectivity were investigated. The resins were applied to purify flavonoids in natural plants. It was illuminated that the adsorbent No. 3B with 15% EGDMA content and amide groups performed optimal selectivity to flavone compounds in Scutellaria barbata D.Don, from which the purity of flavonoids in extracts was obtained more than 50%, obviously higher than that from commercial adsorbents. The result of adsorption thermodynamics experiment showed that the isosteric adsorption enthalpy of No. 3B was in the range of 25-30 kJ/mol, which testified that the adsorption mechanism was related to hydrogen-bonding interaction. The method showed its universality via good effects on the purification of total flavonoids from Ginkgo biloba L., Radix puerariae and Hypericum perforatum L.

Expanded bed adsorption of an alkaline lipase from Pseudomona cepacia.

An extracellular lipase was isolated from Pseudomona cepacia by expanded bed adsorption on an Amberlite 410 ion-exchange resin. Enzyme characterization and hydrodynamic study of a chromatography column were done. Enzyme purification was done at three condition of expanded bed height (H): at one and half (6cm), at two (8cm) and at three (12cm) times the fixed bed height (H(0)=4cm). The results showed that the experimental data was fitted to the Richardson and Zaki equation, and the comparison between the experimental and calculated terminal velocities showed low relative error. In enzyme purification for better condition, a purification factor of about 80 times was found at 6cm of expanded bed height, or 1.5 times of expansion degree. Purified lipase had an optimal pH and a temperature of 8 and 37 degrees C, respectively.

[Decolorization and purification of total leaves saponins of panax notoginseng with ion exchange resins].

The total leaves saponins of panax notoginseng decoloring by adsorption with exchange resins was studied and the decoloring capacity of six anions resins as adsorbent material was evaluated. The decoloring capacity of the selected resins (D296 and Dt) was compared by the dynamic adsorption decolorization experiments. Removel of coloured compounds in rew solution takes place in two serially coupled different ionic exchange columns, one packed column was D72 cation resin, another anion resin. The results showed that macroporous anion exchange resin Dt was the best resin to decolorization of the total leaves saponins of panax notoginseng. The total saponin products with higher purity and quality were obtained. The results of this work shows that the method proposed is convenient, high efficcient and steady one.

Uranium removal from contaminated groundwater by synthetic resins.

Synthetic resins are shown to be effective in removing uranium from contaminated groundwater. Batch and field column tests showed that strong-base anion-exchange resins were more effective in removing uranium from both near-neutral-pH (6.5)- and high-pH (8)-low-nitrate-containing groundwaters, than metal-chelating resins, which removed more uranium from acidic-pH (5)-high-nitrate-containing groundwater from the Oak Ridge Reservation (ORR) Y-12 S-3 Ponds area in Tennessee, USA. Dowex 1-X8 and Purolite A-520E anion-exchange resins removed more uranium from high-pH (8)-low-nitrate-containing synthetic groundwater in batch tests than metal-chelating resins. The Dowex 21K anion-exchange resin achieved a cumulative loading capacity of 49.8 mg g(-1) before breakthrough in a field column test using near-neutral-pH (6.5)-low-nitrate-containing groundwater. However, in an acidic-pH (5)-high-nitrate-containing groundwater, metal-chelating resins Diphonix and Chelex-100 removed more uranium than anion-exchange resins. In 15 m L of acidic-pH (5)-high-nitrate-containing groundwater spiked with 20 mg L(-1) uranium, the uranium concentrations ranged from 0.95 mg L(-1) at 1-h equilibrium to 0.08 mg L(-1) at 24-h equilibrium for Diphonix and 0.17 mg L(-1) at 1-h equilibrium to 0.03 mg L(-1) at 24-h equilibrium for Chelex-100. Chelex-100 removed more uranium in the first 10 min in the 100mL of acidic-(pH 5)-high-nitrate-containing groundwater ( approximately 5 mg L(-1) uranium); however, after 10 min, Diphonix equaled or out-performed Chelex-100. This study presents an improved understanding of the selectivity and sorption kenetics of a range of ion-exchange resins that remove uranium from both low- and high-nitrate-containing groundwaters with varying pHs.

Selenium speciation by high-performance anion-exchange chromatography-post-column UV irradiation coupled with atomic fluorescence spectrometry.

A technique for the speciation of selenomethylcysteine (SeMeCys), selenocystine (SeCys), selenite [Se(IV)] and selenomethionine (SeMet) was established in this paper using high-performance anion-exchange chromatography coupled with atomic fluorescence spectrometry (HPAEC-AFS). Analytes were separated on an AminoPac PA10 column and then digested by on-line ultraviolet (UV) irradiation, which destroyed organic compound structure. Hydride generation was used as an available sample introduction technique for atomic fluorescence detection. The detection limits of four compounds were 1-5 microg/L (250 microL injection, 10 times of the baseline noise). The relative standard deviations (RSDs), calculated from seven consecutive injections of 100 microg/L standard mixtures, were from 2 to 4%. Selenious yeast tablet, which had been proposed as selenium supplement, and human urine collected from a volunteer were analyzed. Good spiked recoveries from 86 to 103% were obtained.

Methodological approach to the study of the formation and physicochemical properties of phosphate-metal-humic complexes in solution.

The aim of this work is to study the suitability of the complementary use of ultrafiltration (UF) and the interaction with an anion-exchange resin (AR) to characterize of phosphate-metal-humic complexes in solution. The results indicate that a methodological approach consisting of the validation and calibration of the AR method by the UF method and the further use of the AR method is suitable for characterizing phosphate-metal complexes. Such an approach has proven to be useful for calculating the phosphate maximum binding capacity of iron-humic complexes and stability constants. It might also be used to obtain valuable purified phosphate-metal-humic complexes for further structural characterization.

Determination of stability constants of U(VI)-Fe(III)-citrate complexes.

Ion-exchange experiments were performed to evaluate the formation of the uranium-citrate and uranium-iron-citrate complexes over a wide concentration range; i.e., environmentally relevant concentrations (e.g., 10(-6) M in metal and ligand) and concentrations useful for spectroscopic investigations (e.g., 10(-4) M in metal and ligand). The stability of the well-known uranium-citrate complex was determined to validate the computational and experimental methods applied to the more complex system. Values of the conditional stability constants for these species were obtained using a chemical equilibrium model in FITEQL. At a pH of 4.0, the stability constant for uranium-citrate complex (log beta1,1) was determined to be 8.71+/-0.6 at I = 0. Analysis of the results of ion-exchange experiments for the U-Fe-citric acid system indicates the formation of the 1:1:1 and 1:1:2 ternary species with stability constants (log beta) of 17.10+/-0.41 and 20.47+/-0.31, respectively, at I= 0.

Performance of three resin-based materials for treating uranium-contaminated groundwater within a PRB.

Three materials that are designed to treat uranium-contaminated water were investigated. These are a cation exchange resin, IRN 77; an anion exchange resin, Varion AP; and a recently developed material called PANSIL (quartz sand coated with 2% amidoxime resin by weight). The reaction rate, capacity, and effective pH range of the three materials are reported. The capacity and conditional distribution coefficient in neutral, uranyl-contaminated synthetic groundwater containing carbonate are also reported. The suitability of each material for treating uranium-contaminated groundwater using a permeable reactive barrier (PRB) approach is then discussed. All three materials react rapidly in the pH range 5-7, reaching equilibrium in less than 4h at approximately 23 degrees C. The unconditioned cation exchange resin removed 8 g UO2 2+ per kg of resin from neutral synthetic groundwater containing 30 mg/l of UO2 2+, but a lower capacity is anticipated in groundwater with either higher ionic strength or lower UO2 2 concentrations. It operates by first acidifying the solution, then sorbing UO2 2, and can release UO2 2 when its buffering capacity has been exhausted. The anion exchange resin is very effective at removing anionic uranyl carbonate species from solutions with a pH above 5, with good specificity. Up to 50 g/kg of uranium is removed from contaminated groundwater at neutral pH. PANSIL is effective at sequestering cationic and neutral uranyl species from solutions in the pH range 4.5-7.5, with very good specificity. The capacity of PANSIL is pH-dependent, increasing from about 0.4 g/kg at pH 4.5, to about 1 g/kg at pH 6, and 1.5 g/kg around pH 7.5. In neutral groundwater containing carbonate, both the anion exchange resin and PANSIL exhibit conditional distribution coefficients exceeding 1470 ml/g, which is about an order of magnitude higher than comparable reactive barrier materials reported in the literature.

Compatibility of column inlet and adsorbent designs for processing of corn endosperm extract by expanded bed adsorption.

Corn has emerged as a viable host for expression of recombinant proteins; targeted expression to the endosperm has received particular attention. The protein extracts from corn endosperm differ from those of traditional hosts in regard to the nature of residual solids and extracted matrix contaminants. Each of these differences presents reasons for considering expanded bed adsorption for product capture and new considerations for limitations of the method. In this work three inlet-flow distribution devices (mesh, glass ballotini, and localized mixing) and six adsorbents with different physical (size and density), chemical (ligand), and base matrix properties were evaluated to determine conditions compatible with processing of crude corn endosperm extract by expanded bed adsorption. Of the inlet devices evaluated, the design with localized mixing at the inlet (as produced commercially by UpFront Chromatography A/S, Copenhagen, DK) allowed solids up to 550 microm into the column without clogging for all flow rates evaluated. A mesh at the inlet with size restriction of either 50 microm or 80 microm became clogged with very small corn particles (< 44 microm). When glass ballotini was used, large particles (550 microm) passed through for high flow rates (570 cm/h), but even small (< 44 microm) particles became trapped at a lower flow rate (180 cm/h). The physical and chemical properties of the resin determined whether solids could be eluted. The denser UpFront adsorbents allowed for complete elution of larger and more concentrated corn solids than the currently available Amersham Streamline adsorbents (Amersham Biosciences, Piscataway, NJ) as a result of the former's higher flow rate for the desired 2x expansion (570 cm/h for UpFront vs. 180 cm/h for Streamline). All corn solids < 162 microm eluted through nonderivatized UpFront resin. Larger corn solids began to accumulate due to their elevated sedimentation velocities. Feeds of < 44 microm solids at 0.45% and 2.0% dry weight successfully eluted through ion exchange adsorbents (DEAE and SP) from UpFront. However, significant accumulation occurred when the solids size increased to a feed of < 96 microm solids, thus indicating a weak interaction between corn solids and both forms of ion exchange ligands. Expanded beds operated with Streamline ion exchange adsorbents (DEAE and SP) did not allow full elution of corn solids of < 44 microm. A hyperdiffuse style EBA resin produced by Biosepra (Ciphergen Biosystems, Fremont, CA) with CM functionality showed a severe interaction with corn solids that collapsed the expanded bed and could not be eliminated with elevated flow rates or higher salt concentration.

Sorption and binary exchange of nitrate, sulfate, and uranium on an anion-exchange resin.

Competitive ion-exchange reactions were studied on a strong-base anion-exchange resin to remove NO3- and uranium from a contaminated groundwater containing high levels of NO3- (approximately 140 mM), SO4(2-) (approximately 10 mM), and U(VI) (approximately 0.2 mM). Results indicate that although SO4(2-) carries divalent negative charges, it showed the least selectivity for sorption by the Purolite A-520E resin, which is functionalized with triethylamine exchange sites. Nitrate was the most strongly sorbed. Sorption selectivity followed the order of NO3- > Cl- > SO4(2-) under the experimental conditions. Nitrate competitively sorbed and displaced previously sorbed SO4(2-) in a column flow-through experiment and resulted in a high elution front of SO4(2-) in the effluent. Although the concentration of uranium in groundwater is orders of magnitude lower than that of NO3- or SO4(2-), it was found to be strongly sorbed by the anion-exchange resin. Because the most stable uranium species in oxic and suboxic environments is the UO2(2+) cation, its strong sorption by anion-exchange resins is hypothesized to be the result of the co-ion effect of NO3- by forming anionic UO2(NO3)3- complexes in the resin matrix. These observations point out a potential alternative remediation strategy that uses strong-base anion-exchange resins to remove uranium from this site-specific groundwater, which has a low pH and a relatively high NO3- concentration.