EXAFS study of Sn(IV) immobilization by hardened cement paste and calcium silicate hydrates

In this study, the immobilization mechanisms of Sn(IV) onto calcium silicate hydrates (C-S-H) and hardened cement paste (HCP) have been investigated by combining wet chemistry experiments with X-ray absorption spectroscopy (XAS). Evidence is presented which demonstrates the formation of a Sn(IV) inner-sphere surface complex on C-S-H with a CaO/SiO2 weight ratio of 0.7. Two possible structural models, implying a corner sharing between the Sn octahedra and Q1 or Q2b Si tetrahedra, have been developed based on the experimentally determined structural parameters. In HCP, the formation of a different type of Sn(IV) inner-sphere complex has been observed, indicating that C-S-H may not be the uptake-controlling phase for Sn(IV) in the cement matrix. An alternative structural model for Sn(IV) binding in HCP has been developed, assuming that ettringite is the uptake-controlling phase. At high Sn(IV) concentrations, Sn(IV) immobilization in HCP occurs due to the formation of CaSn(OH)6.     

Application of a New Functionalized Nanoporous Silica for Simultaneous Trace Separation and Determination of Cd(II), Cu(II), Ni(II), and Pb(II) in Food and Agricultural Products

A novel sorbent for simultaneous separation of cadmium, copper, nickel, and lead was prepared by functionalizing SBA-15 nanoporous silica with dithizone. A solid-phase extraction method using the above sorbent was developed to separate and preconcentrate trace amounts of cadmium, copper, nickel, and lead ions from food and agricultural products by flame atomic absorption spectrometry measurements. The optimum experimental conditions such as pH; flow rates; type, concentration, and volume of the eluent; breakthrough volume; and effect of coexisting ions on the separation and determination of these heavy metals were evaluated. The extraction efficiencies for the mentioned heavy metals were greater than 97 %, and the limits of detection were 0.09, 0.16, 0.21, and 0.45 μg?L^?1 for cadmium, copper, nickel, and lead, respectively. The preconcentration factor for simultaneous analysis of the four heavy metals was found to be 100 approximately. The relative standard deviations of the method were <5 % for 10 separate column experiments for the determination of 5.0 μg of cadmium, copper, nickel, and lead ions. The adsorption capacity of the dithizone-SBA-15 was 189 mg?g^?1 for cadmium, 102 mg?g^?1 for copper, 91 mg?g^?1 for nickel, and 208 mg?g^?1 for lead.     

Determination of Trace Amounts of Cd(II), Cu(II), and Ni(II) in Food Samples Using a Novel Functionalized Magnetic Nanosorbent

This work describes a novel sorbent based on functionalization of magnetic nanoparticles by 2-aminobenzothiazole and its application in the extraction and preconcentration of trace amount of Cd(II), Cu(II), and Ni(II) ions. This nanosorbent was characterized by Fourier transfer infrared spectroscopy, thermal analysis, X-ray powder diffraction, elemental analysis, and scanning electron microscopy. The effects of various factors such as pH value, sorption time, sorbent dosage, type, volume, and concentration of the eluent as well as the elution time were investigated. Following the sorption and the elution of target analytes, the Cd(II), Cu(II), and Ni(II) ions were determined by flame atomic absorption spectrometry. Under the optimal conditions, the limits of detection (LODs) were 0.03, 0.009, and 0.1 μg L^?1 for Cd(II), Cu(II), and Ni(II), respectively. Linearity was within the range of 0.1–75 ng mL^?1 for Cd(II), 0.03–50 ng mL^?1 for Cu(II), and 0.5–100 ng mL^?1 for Ni(II) in the initial solution with r ² values greater than 0.9978. The relative standard deviations of the method were less than 8.4 %. The preconcentration factor of the method was 277. The sorption capacity of this new sorbent was 65, 78, and 49 mg g^?1 for Cd(II), Cu(II), and Ni(II), respectively. The proposed method was validated using two certified reference materials (LGC 6010 hard drinking water and NIST SRM 1515 apple leaves) in order to exhibit its applicability. Ultimately, this method was applied to the rapid extraction of the trace quantities of Cd(II), Cu(II), and Ni(II) ions in different food samples, and satisfactory results were obtained.     

Kinetic speciation of Co(II), Ni(II), Cu(II), and Zn(II) in model solutions and freshwaters: lability and the d electron configuration

The kinetic speciation of Co(II), Ni(II), Cu(II), and Zn(II) in model solutions of a well-characterized fulvic acid (Laurentian fulvic acid), freshwater samples from the Rideau River (Ottawa, Ontario), and freshwater samples from the Sudbury (Ontario) area were investigated by the competing ligand exchange method using Chelex 100 as the competing ligand and by inductively coupled plasma-mass spectrometry to measure the dissociation kinetics. The metal species were quantitatively characterized by the rate coefficient for the first-order dissociation of metal complex to free metal ion. This technique can be applied to almost all elements and represents an important advance in our ability to investigate the kinetic availability of metal species in the freshwater environment. The order of the lability of the metal complexes, Co(II) > Ni(II) > Cu(II) < Zn(II), follows the reverse order of the ligand field stabilization energy with the exception of Cu(II); the behavior of Cu(II) is also due to the Jahn-Teller effect, which shortens the equatorial bonds and lengthens the axial bonds of a tetragonally distorted Cu(II)-L6 complex. This study has demonstrated a relationship between the lability of metal-DOM complexes of the 3d transition metals in freshwaters and their d electron configuration. This is the first time that the importance of the d electron configuration on the lability of metal complexes in the freshwater environment has been demonstrated. The slow complexation kinetics of both Ni(II) and Cu(II) suggestthatthe usual equilibrium assumption for freshwaters may be invalid.     

Role of transition metals,Fe(II), Cr(II), Pb(II), and Cd(II) in lipid peroxidation

Cod liver oil was oxidized with Fenton-like systems containing transition metals Fe(II), Cr(II), Pb(II), and Cd(II). Malonaldehyde (MA) formed from 10 μl cod liver oil oxidized by a Fenton-like system containing each metal at levels of 0.25, 0.5, 1 and 4 μmol was analyzed by a gas chromatograph equipped with a nitrogen phosphorus detector. The MA production exhibited dose response and the greatest amount (837.0 ± 19.1 nmol) was obtained by the Fe(II) system at the level of l μmol. Generally, higher MA formation is observed in the lower the third ionization potential of the metal. The decreasing order of MA formed in the metal systems at the level of 1 μmol is Fe(II) > Cr(II)(274.1 ± 20.1 nmol) > Pb(II)(150.7 ± 13.0 nmol) > Cd(II)(95.4 ± 6.7 nmol). The amounts of MA formed in Cr(II), Pb(II), and Cd(II) systems were considerably lower than those in the Fe(II) system. The relative formations of MA in the Cr(II) and Pb(II) systems were similar to those in the Fe(II) system. The results suggest that trace amounts of metals contribute oxidative effects to lipid peroxidation followed by various diseases.     

Contents of vitamins B(1), B(2), B(6), and B(12) in pork and meat products

The concentration of B vitamins (B(1), B(2), B(6), and B(12)) was determined in three pork muscles (Longissimus dorsi, loin; Biceps femoris, ham; and Triceps brachii, shoulder) and in pork and other meat products (cooked, pickled, and cured), of importance because they are consumed in high quantities. The results were compared with values reported by other authors and their contribution to the daily intake of these vitamins estimated. This showed that pork provides, on average, 97, 25.8, 35/43.7 (men/women), and 37% of the RDA (Recommended Dietary Allowances) for vitamins B(1), B(2), B(6), and B(12), respectively.     

Monitoring of Zn(II), Cd(II), Pb(II) and Cu(II) During Refining of Some Vegetable Oils Using Differential Pulse Anodic Stripping Voltammetry

In this study, a novel approach has been developed using differential pulse anodic stripping voltammetry (DPASV) for the simultaneous determination of Zn(II), Cd(II), Pb(II) and Cu(II) in edible oils at hanging mercury drop electrode. The microwave digestion of oil samples was carried out with concentrated HNO₃ and H₂O₂. KNO₃ was used as a supporting electrolyte. The experimental conditions optimized such as deposition time, stirring rate and size of mercury drop were 300 s, 600 rpm and 10 mm², respectively. The method was applied to quantify Zn(II), Cd(II), Pb(II) and Cu(II) in crude and refined hazelnut, corn, sunflower and olive oils. During refining of different vegetable oils, the removal efficiencies of Zn(II), Cd(II), Pb(II) and Cu(II) were calculated as 98.20–99.91, 98.50–99.90, 95.26–99.76 and 95.93–99.92 %, respectively. The limits of detection for Zn(II), Cd(II), Pb(II) and Cu(II) were 2.1?×?10^?8, 8.7?×?10^?10, 7.1?×?10^?9 and 3.4?×?10^?9 and the limits of quantification were 6.8?×?10^?8, 2.9?×?10^?9, 2.3?×?10^?8 and 1.1?×?10^?8 M with linear regression coefficients (R ²) of 0.9930, 0.9928, 0.9893 and 0.9931, respectively. It was observed that the above metals in crude and refined vegetable oils could be determined simultaneously by the DPASV method.     

Antioxidant properties of methanolic extracts from Diospyros mespiliformis (jackal berry), Flacourtia indica (Batoka plum), Uapaca kirkiana (wild loquat) and Ziziphus mauritiana (yellow berry) fruits

Four wild fruits, Diospyros mespiliformis, Flacourtia indica, Uapaca kirkiana and Ziziphus mauritiana, were extracted with methanol and analysed for radical-scavenging effect of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, reducing power and anion radical effect on superoxide anion using colorimetric method. There was an increase in the radical-scavenging effect, reducing power and superoxide anion radical-scavenging effect as the concentration of sample increased. Diospyros mespiliformis had high DPPH radical-scavenging capacity. The peels of F. indica and U. kirkiana had higher DPPH radical-scavenging effects, reducing power and superoxide-scavenging effects compared with the pulp while the pulp of Z. mauritiana had high DPPH radical-scavenging effects, reducing power and superoxide-scavenging effects compared with the peel.     

高效液相色谱法测定山楂制品中苯甲酸、山梨酸、糖精钠

对液相色谱法测定山楂片中苯甲酸、山梨酸、糖精钠进行了方法优化,对色谱条件进行了调整,采用ODS-C<,18>型(150mmx4.6mm,5μm)色谱柱,流动相甲醇-0.02 mol/L乙酸铵(体积比5:95),流速为1.0 mL/min,采用紫外检测器,检测波长为230nm.该方法测定结果的相对标准偏差小于2%(n=4),平均回收率大于90%,该法满足实验要求.     

Differentiation of fresh and frozen/thawed fish, European sea bass (Dicentrarchus labrax), gilthead seabream (Sparus aurata), cod (Gadus morhua) and salmon (Salmo salar), using volatile compounds by SPME/GC/MS

BACKGROUND: A simple method based on solid phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS) was applied for studying the volatile profiles of whole fish samples of European sea bass (Dicentrarchus labrax) and gilthead seabream (Sparus aurata) and fillets of cod (Gadus morhua) and salmon (Salmo salar) during frozen storage in order to be able to differentiate a fresh product from one that has been frozen. Analysis of volatile compounds was performed on these two product types, fresh and after freezing/thawing following storage at ? 20 °C for 30 and 90 days. RESULTS: More than a hundred volatile compounds were found by SPME/GC/MS. Statistical processing by principal component analysis and ascending hierarchical classification was used to classify the samples into categories and verify the possibility of separating fresh samples from those that had been frozen and thawed. The compounds to be used as differentiators were identified. Four compounds were common to all species: dimethyl sulfide, 3‐methylbutanal, ethyl acetate and 2‐methylbutanal. Not only were they found in larger quantities after thawing but they also increased with the duration of storage at ? 20 °C. CONCLUSION: These four compounds can therefore be considered as potential markers of differentiation between a fresh product and one that has been frozen. Copyright © 2012 Society of Chemical Industry     

Real-time PCR for detection and quantification of red deer (Cervus elaphus), fallow deer (Dama dama), and roe deer (Capreolus capreolus) in meat mixtures

A rapid real-time polymerase chain reaction (PCR) technique using SYBR Green detection system, has been developed for the quantification of red deer, fallow deer, and roe deer DNAs in meat mixtures. The method combines the use of cervid-specific primers that amplify a 134, 169, and 120 bp of the 12S rRNA gene fragment of red deer, fallow deer and roe deer, respectively, and universal primers that amplify a 140 bp fragment on the nuclear 18S rRNA gene from eukaryotic DNA. The C_t (threshold cycle) values obtained with the 18S rRNA primers are used to normalize those obtained from each of the cervid-specific systems, serving as endogenous control for the total content of PCR-amplifiable DNA in the sample. Analysis of experimental raw and heat treated binary mixtures of red deer, fallow deer or roe deer meat in a swine meat matrix demonstrated the suitability of the assay for the detection and quantification of the target cervid DNAs in the range 0.1–0.8%, depending on the species and treatment of the meat samples analyzed.     

Determination of Lactose and Lactose Hydrolysis in Milk Using Cerium(IV)

Lactose and lactose hydrolysis in milk were determined using a novel method involving a measurement of the time for 0.39M Cerium(IV) [Ce(IV)] in 0.5M nitric acid to be reduced to Cerium(III) [Ce(III)] after an initial precipitation of milk protein and fat. The time for the absotbance at 445 nm to decrease to 0.4 could be directly correlated with standard curves to determine either the amount of lactose or the degree of lactose hydrolysis. This Ce(IV) oxidation method was rapid (15 min) and exhibited good agreement with infrared methods of determining lactose and enzymatic methods of determining percentage lactose hydrolysis. Recoveries of lactose found using the Ce(IV) oxidation method from a number of milk samples containing different amounts of fat were comparable to recoveries using the infrared method of lactose determination.     

PCR identification of meats from chamois (Rupicapra rupicapra), pyrenean ibex (Capra pyrenaica), and mouflon (Ovis ammon) targeting specific sequences from the mitochondrial D-loop region

A polymerase chain reaction (PCR) assay was developed for the identification of meats from chamois (Rupicapra rupicapra), pyrenean ibex (Capra pyrenaica), and mouflon (Ovis ammon) by using oligonucleotides targeting mitochondrial D-loop sequences. A D-loop region (700–1000 bp) was firstly amplified and sequenced from various game and domestic meat DNAs, and three primer sets were then designed on the basis of nucleotide multialignment of the generated D-loop sequences. As expected from sequence analysis, PCR amplification of the targeted D-loop fragments was successfully achieved from chamois (88 bp), pyrenean ibex (178 bp), and mouflon (155 bp) meats, showing adequate specificity and reproducibility against a number of game and domestic meats. Mouflon and sheep meats were amplified together in accordance to the high nucleotide identity of their mt D-loop sequences. In this work, satisfactory amplification was also accomplished in the analysis of experimentally pasteurized (72 °C for 30 min) and sterilized (121 °C for 20 min) meats, with a detection limit of 0.1% for each of the targeted species. The proposed PCR assay represents a rapid and straightforward method for the detection of possible adulterations in game meat products.     

Quantification of Antioxidants in Medicinal Plants and Foodstuffs Using Ce(IV) with Indigo Carmine as Chromogenic Probe

A simple, novel, sensitive and diversely applicable antioxidant assay method has been developed for the determination of total antioxidant capacity of some foodstuffs and medicinal plants. The method is based on the oxidation of antioxidants by a known amount of Ce(IV) sulphate under slightly acidic medium and subsequently allowing the unreacted Ce(IV) to react with a known amount of Indigo Carmine dye followed by measuring the unreacted blue-coloured Indigo Carmine dye solution at λ _max = 610 nm at room temperature. The antioxidant power was evaluated in terms of trolox equivalent antioxidant capacities and compared with those of ferric-reducing antioxidant power (FRAP–1.10 phenanthroline), Cu(II) reduction assay using bathocuproinedisulfonic acid disodim salt and 2, 2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid methods. A good correlation (R ² = 0.926) was found with the classical spectrophotometric FRAP assay. The proposed method is reproducible and successfully applied to assess the total antioxidant capacities in foodstuffs, vegetables and medicinal plants. The obtained results were compared with reference methods. Interference from other substances was also studied.     

Determination of Cd (II), Cu (II), and Pb (II) in Some Foods by FAAS after Preconcentration on Modified Silica Gels with Thiourea

Abstract: This study describes preconcentration method for determination of Cd (II), Cu (II), and Pb (II) in some food samples. Silica gel was modified with thiourea and characterized by IR and C, H, N, S elemental analysis. Modified silica gel was used as a solid phase extraction for determination of Cd (II), Cu (II) and Pb (II) in tuna fish, biscuit, black tea, rice, ka?ar cheese, honey, tomato paste, and margarine samples. The analytical conditions including eluent type, pH of sample solutions, flow rates of sample and eluent solutions, etc. were optimized. The influence of the matrix ions on the involvement of the Cd (II), Cu (II), and Pb (II) were also studied. GBW 07605 tea standard reference material was used for validation of method. The method was successfully applied for the determination of Cd (II), Cu (II), and Pb (II) ions in food samples. The detection limits were in the range of 0.81 μg/L, 0.38 μg/L, and 0.57 μg/L for cadmium, copper and lead, respectively. The relative standard deviations of the procedure were below 10%. The sorption capacities were found as 92 μmol/L Cd (II), 286 μmol/L Cu (II), and 121 μmol/L Pb (II).     

Determination of Synthetic Food Colorants in Water-Soluble Beverages Individually by HPLC and Totally by Ce(IV)-Oxidative Spectrophotometry

Food colorants are an important class of food additives that give the first impression to consumers about the quality of food. Ce(IV)-reducing antioxidant capacity assay originally developed in our laboratories was adapted to the determination of synthetic food colorants for the first time. This method allowing for total antioxidant capacity assay of dietary polyphenols, flavonoids, and ascorbic acid in plant extracts is based on the room temperature oxidation of antioxidant compounds with Ce(IV) sulfate in dilute H₂SO₄ solution and measurement of the absorbance of unreacted Ce(IV) at 320?nm. The results of the proposed method were correlated with high-performance liquid chromatography (HPLC) findings. Individual standard solutions, synthetic mixtures of synthetic colorants, and colorant extracts were identified and quantified with HPLC on a C₁₈ column equipped with a diode array detector, and slight modifications on the existing HPLC method were made to analyze synthetic colorant mixtures. This work proposes Ce(IV)-oxidative spectrophotometry as a complementary technique to HPLC in the analysis of food colorants.     

Disruption and functional analysis of six ORFs of chromosome IV: YDL103c (QRI1), YDL105w (QRI2), YDL112w (TRM3), YDL113c, YDL116w (NUP84) and YDL167c (NRP1)

We have disrupted six ORFs (YDL103c, YDL105w, YDL112w, YDL113c, YDL116w and YDL167c) located on the left arm of chromosome IV. Except for YDL112w, the short flanking homology strategy was used to construct disruption cassettes using the KanMX4 marker. For YDL112w, a disruption cassette including the LEU2 gene was made. YDL103c and YDL105w are essential genes for vegetative growth. Disruption of YDL112w, YDL113c and YDL167c does not result in any detectable phenotype with the tests we used, while disruption of YDL116w confers slow growth, cryosensitivity and thermosensitivity, and the disrupted diploid homozygotes for the disruption failed to sporulate.     

Interaction of Phytic Acid with the Metal Ions, Copper (II), Cobalt (II), Iron (III), Magnesium (II), and Manganese (II)

The combination of phytic acid with the metal ions of cobalt (II), magnesium (II), manganese (II), copper (II), and iron (III) has been investigated. With the experimental conditions used, in all cases, the products isolated were amorphous powders with nonstiochiometric atomic ratios.     

Simultaneous pre-concentration of Pb and Sn in food samples and determination by atomic absorption spectrometry

A cloud point extraction (CPE) method has been developed for the pre-concentration and simultaneous determination of lead [Pb(II)] and tin [Sn(II)] using Acridine Orange as complexing reagent and mediated by nonionic surfactant (Triton X-114) by flame atomic absorption spectrometry (FAAS). The main factors affecting analytical performance of CPE have been investigated in detail. The extracted surfactant-rich phase was diluted with (1.0 mol L^?1) nitric acid in methanol, prior to subjecting FAAS. The calibration graphs obtained from Pb(II) and Sn(II) were linear in the concentration ranges of 5–1,000 and 10–5,000 μg L^?1 with detection limits of 1.40 and 2.86 μg L^?1, respectively. The relative standard deviations for 10 replicates containing 25 μg L^?1 of Pb(II) and Sn(II) were 2.15 and 2.50 %, respectively. The analytical procedure was verified by the analysis of the standard reference materials NWTMDA-61.2 (water-trace elements) and NIST SRM 1548a (typical diet). The developed method has been applied to the simultaneous determination of total Pb and Sn in canned food samples including juices, tomato paste, corn, and green pea.