Determination of differential heavy metal and trace element accumulation in liver, gills, intestine and muscle of sterlet (Acipenser ruthenus) from the Danube River in Serbia by ICP-OES

The accumulation of heavy metals in fish has been extensively studied and well documented. However, the research has been mainly focused on the muscle tissue, while the distribution patterns among other tissues, such as liver and gills, have been mostly neglected. Within the present study, the concentrations of Ag, Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sr, Zn and Li in the muscle, gills, liver and intestine of the sterlet (Acipenser ruthenus) from the Danube River have been assessed by using the inductively-coupled plasma optical spectrometry. The analysis has revealed a high degree of differential accumulation of the studied heavy metals and trace elements in the tissues of the Danube sterlet. Liver appeared to be the main heavy metal storage tissue, while the lowest levels of analyzed metals were found in muscles. Heavy metal concentrations in the muscle were at acceptable levels for human consumption, except partly for cadmium. We conclude that, in order to enable a more efficient control of contaminants in fish products, there is an apparent need to resolve the problem of lack of legal limits for many metals in European legislation.     

The determination of heavy metal accumulation ratios in muscle, skin and gills of some migratory fish species by inductively coupled plasma-optical emission spectrometry (ICP-OES) in Beymelek Lagoon (Antalya/Turkey)

In this study, copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), magnesium (mg), nickel (Ni), chrome (Cr), cobalt (Co) and boron (B) accumulation ratios of muscle, skin and gill of Striped seabream (Sparidae, Lithognathus mormyrus), Golden grey mullet (Mugilidae, Liza aurata), Thicklip grey mullet (Mugilidae, Chelon labrasus), Flathead mullet (Mugilidae, Mugil cephalus), Gilthead seabream (Sparidae, Sparus aurata) and Thinlip mullet (Mugilidae, Liza ramada) in Beymelek Lagoon (Antalya/Turkey) were investigated. The analyses of elements were performed with inductively coupled plasma-optic emission spectroscopy (ICP-OES) by using microwave digestion techniques. There were significant variations among heavy metal accumulation levels of the species and their tissues. The heavy metal concentrations found in tissues varied for Cu: 0.28-5.11, Zn: 4.27-339.76, Mn: 0.0-12.81, Fe: 3.25-117.73, Cr: 0.0-1.40, Co: 0.0-3.29 and Mg: 168.73-659.16 mg/kg wet weight. Ni and B were not detected in any tissues of the species. The heavy metal concentrations of fish in Beymelek Lagoon were lower than those of fish from other contaminated Mediterranean regions of Turkey. This research showed that heavy metal concentrations in muscles of investigated species were also lower than the maximum levels set by law.     

Analysis of volatile compounds of wild gilthead sea bream (Sparus aurata) by simultaneous distillation–extraction (SDE) and GC–MS

The volatile compounds of wild gilthead sea bream (Sparus aurata) were analyzed by sensory and instrumental analyses. Simultaneous distillation and extraction (SDE) with dichloromethane were used for extraction of volatile components. According to sensory analysis, the aromatic extract obtained by SDE was representative of sea bream odour. A total of 46 compounds were identified and quantified in sea bream. Aldehydes and alcohols were the most dominant volatiles in sea bream, as they accounted for the largest proportion. Hexanal, heptanal, nonanal, (Z)-4-heptenal, octanal, (E)-2-nonenal, decanal, benzenacetaldehyde, (E,E)-2,4-decadienal, 1-octen-3-ol and (E)-1,5-octadien-3-ol were potent aroma compounds on the basis of odour activity values (OAVs). Within these, decanal (OAV: 1110) and (E)-2-nonenal (OAV: 447.5) were the most powerful contributors to the aroma of the sea bream.     

A study of trace element contamination in river sediments in Serbia using microwave-assisted aqua regia digestion and multivariate statistical analysis

The aim of this study was the evaluation of the trace element contamination level in sediments of the most important rivers in Serbia and their tributaries. The determination of the aqua regia soluble contents of 12 micro- and macro-elements (Ca, Cd, Co, Cr, Cu, Fe, Mn, Pb, Ni, Zn, Be and V) in sediments was developed by the microwave digestion technique combined with inductively coupled plasma atomic emission spectrometry. Correlation analysis and principal component analysis distinguishes factors of lithogenic and anthropogenic origins. The Fe, Mn, Be and V contents are controlled by a regional lithogenic high background factor, while Cd, Cr, Pb, Ni, Zn and Cu are recognized as tracer of pollution. For Co, mixed sources from both lithogenic and anthropogenic inputs were evidenced.The investigated sediment of the major rivers and their tributaries in Serbia showed high concentrations of metals, especially of Cd, Pb, Cu and Zn, which may cause serious environmental impacts. Rivers which flow into the Danube from its entrance into Serbia significantly influence the chemical load of the water and sediments.The experimental study was conducted using two BCR standard reference materials. The calculated accuracy and precision confirmed the good performance of the adopted procedures.     

Micro-column preconcentration/separation using thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO2 as packing materials on-line coupled to inductively coupled plasma optical emission spectrometry for the determination of trace heavy metals in environmental water samples

A novel adsorbent of thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO₂ was prepared and was used as a packing material for flow injection (FI) micro-column (20 mm × 4.0 mm i.d.) separation/preconcentration on-line coupled to inductively coupled plasma optical emission spectrometry (ICP-OES) simultaneous determination of trace metals (V, Cu, Pb, Cr) in environmental water samples. The experimental conditions for modified mesoporous TiO₂ packed micro-column separation/preconcentration of the target metals were optimized and the interference of commonly coexisting ions was examined. The adsorption capacities of thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO₂ for V, Cu, Pb and Cr were found to be 14.0, 11.7, 17.7 and 14.5 mg g^− 1, respectively. The detection limits of the method were 0.09, 0.23, 0.50 and 0.15 µg L^− 1 for V, Cu, Pb and Cr, respectively, with a preconcentration factor of 20. The precision of this method were 1.7% (V), 3.9% (Cu), 4.6% (Pb) and 2.9% (Cr) (n = 7, C = 5 µg L^− 1), respectively. The developed method was applied to the determination of trace heavy metals in real samples and the recoveries for spiked samples were found to be in the range of 88.7-107.1%. For validation, a certified reference material of GSBZ50009-88 environmental water sample was analyzed and the determined values were in good agreement with the certified values.     

Formation, structure and magnetism of the metastable defect fluorite phases AVO3.5+x (A=In, Sc)

We report the preparation and stability of ScVO_3.5+x and the novel phase InVO_3.5+x. AVO_3.5+x (A=Sc, In) defect fluorite structures are formed as metastable intermediates during the topotactic oxidation of AVO₃ bixbyites. The oxidation pathway has been studied in detail by means of thermogravimetric/differential thermal analysis and in-situ powder X-ray diffraction. The oxidation of the bixbyite phase follows a topotactic pathway at temperatures between 300 and 400 °C in air/carbon dioxide. The range of accessible oxygen stoichiometries for the AVO_3.5+x structures following this pathway are 0.00x0.22. Rietveld refinements against powder X-ray and neutron data revealed that InVO_3.54 and ScVO_3.70 crystallize in the defect fluorite structure in space group Fm-3 m (227) with a=4.9863(5) and 4.9697(3)Å, respectively with A³⁺/V⁴⁺ disorder on the (4a) cation site. Powder neutron diffraction experiments indicate clustering of oxide defects in all samples. Bulk magnetic measurements showed the presence of V⁴⁺ and the absence of magnetic ordering at low temperatures. Powder neutron diffraction experiments confirmed the absence of a long range ordered magnetic ground state.     

Use of an o-aminobenzoic acid-functionalized XAD-4 copolymer resin for the separation and preconcentration of heavy metal(II) ions

XAD copolymer resins may be functionalized with heavy metal ion-selective ligands either by covalent linkage to the polymer backbone or by impregnation. These resins may be tailored to be specific for certain heavy metals by adjusting the adsorption and elution parameters, thereby enabling simple and cost-effective spectrophotometric and flame atomic absorption spectrometry (FAAS) determinations of these metals without requiring the more sophisticated coupled instrumental techniques. For the synthesis of o-aminobenzoic acid (ABA)-immobilized XAD-4 copolymer resin that is expected to preconcentrate a number of transition and heavy metals, the azo-linkage method was chosen. For this purpose the copolymer was nitrated, reduced to the corresponding amine, converted to the diazonium salt with nitrite, and reacted with o-aminobenzoic acid to produce the XAD-ABA sorbent. This sorbent was capable of preconcentrating Pb(II), Cd(II), Ni(II), Co(II) and Zn(II) from weakly acidic or neutral aqueous solution. The retained metals were eluted with 1.0 M HNO₃ from the resin column, and were subsequently determinated with by flame atomic absorption spectrometry. The developed resin preconcentration and determination method was successfully applied to the analysis of a synthetic metal mixture solution, a certified reference material (CRM) of coal sample, and brackish lake water.     

FTIR and NMR study of poly(lactide-co-glycolide) and hydroxyapatite implant degradation under in vivo conditions

The influence of hydroxyapatite (HAP) addition on the rate and mechanism of lactide-co-glycolide copolymer (PGLA) degradation after implantation (in vivo study) was analyzed and compared with the process taking place during in vitro studies. Structural and phase changes of poly(lactide-co-glycolide) and its composite with hydroxyapatite were determined using IR and NMR spectroscopy.Degradation of PGLA and PGLA + HAP composite in biological environment proceeds faster than under in vitro condition. Concentration of glycolidyl units in the copolymer chain decreases and that of lactidyl units increases during in vivo degradation both, in PGLA and in PGLA + HAP composite. However, in the case of the composite the decrease of glycolidyl units concentration is slower and after 6 weeks of degradation the contents of lactidyl and glycolidyl units remain stable. On the other hand, PGLA + HAP composite degrades faster than pure PGLA. The addition of HAP nanoparticles distinctly accelerates degradation of PGLA copolymer which is probably connected with the increase of hydrophilicity of the composite and inhibition of semi-crystalline lactidyl domains formation during the degradation process. Observation of the bone tissue after implantation of PGLA + HAP allows to conclude that the degradation of the composite occurs simultaneously with the implant replacement by the bone cells.     

Potential of ethylenediaminedi(o-hydroxyphenylacetic acid) and N,N′-bis(hydroxybenzyl)ethylenediamine-N,N′-diacetic acid for the determination of metal ions by capillary electrophoresis

Two aromatic polyaminocarboxylate ligands, ethylenediaminedi(o-hydroxyphenylacetic acid) (EDDHA) and N,N′-bis(hydroxybenzyl)ethylenediamine-N,N′-diacetic acid (HBED), were applied for the separation of transition and heavy metal ions by the ion-exchange variant of electrokinetic chromatography. EDDHA structure contains two chiral carbon centers. It makes it impossible to use the commercially available ligand. All the studied metal ions showed two peaks, which correspond to meso and rac forms of the ligand. The separation of metal–HBED chelates was performed using poly(diallyldimethylammonium) polycations in mixed acetate–hydroxide form. Simultaneous separation of nine single- and nine double-charged HBED chelates, including In(III), Ga(III), Co(II)–(III) and Mn(II)–(III) pairs demonstrated the efficiency of 40 000–400 000 theoretical plates. The separation of Co(III), Fe(III) complexes with different arrangements of donor groups and oxidation of Co(II), Mn(II), Fe(II) ions in reaction with HBED have been discussed.     

Activation of peroxyl and molecular oxygen using bis -benzimidazole diamide copper (II) compounds

New tetradentatebis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied and an attempt has been made to identify the “active copper species”. Activation of molecular oxygen has also been observed and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20–25% and 10–12 fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones, in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di-t-butylcatechol. The activity of these copper (II) —bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol oxidase.     

Detection of Phakopsora pachyrhizi by polymerase chain reaction (PCR) and use of germination test and DNA comet assay after e-beam processing in soybean

Soybean harvest is the main agribusiness in Brazil, which is the second largest exporter in the world and has a revenue of billions of dollars. Asian dust is caused by the fungus Phakopsora pachyrhizi and its dissemination is difficult to control, since it occurs through wind dispersion. Actually P. pachyrhizi is found in different parts of the world. Electron beam treatment could be an alternative process to minimize these losses, especially for the grains exportation industry. Besides the possibility of being disconnected when not in use, this source does not need to be reloaded, is easily available and, streamlines the process and reduces logistics costs. The present work aims to identify, by the polymerase chain reaction technique (PCR), the P. pachyrhizi fungus presence in the irradiated soybeans and the possibility to use radiation treatment as a sanitary alternative. Doses 0, 1.0, 2.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 kGy (IPEN-CNEN/SP Electron Accelerator) were applied and two fast-screening methods were performed: DNA comet assay (for the detection of DNA damage) and germination test (for the measurement of roots inhibition). These tests are very easy to carry out and measure damage response depending on radiation dose.     

Synthetic and structural studies of some trivalent lanthanide metal complexes of o -hydroxyacetophenone (N-benzoyl)glycyl hydrazone

o-Hydroxyacetophenone (N-benzoyl)glycyl hydrazone (o-HABzGH) forms complexes of the types [M(o-HABzGH)Cl₂(H₂O)₂]Cl and [M(o-HABzGH-2H)OH(H₂O)₂], where M = Y(III), Gd(III), Tb(III) and Dy(III). The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility, infrared, electronic,¹H NMR and¹³C NMR spectral techniques. The nephelauxetic ratio (β), covalency (δ), bonding parameter (b ^1/2) and angular overlap parameter (η) have been calculated from Dy(III) complexes. Infrared and NMR spectral studies show thato-HABzGH acts as a neutral bidentate ligand in the adduct complexes and as a dinegative tridentate one in the neutral complexes. A coordination number of six has been proposed for the metal ion in all the complexes.     

Synthesis of (3S,6RS)- and (3RS,6RS)-Analogs of Component AI of the Aonidiella aurantii Sex Pheromone by Stepwise Alkylation of Acetoacetic Ester

Synthetic approaches to (±)- and (3S)-analogs of the AI component of the Aonidiella aurantii sex pheromone (3S)-methyl-6R-isopropenyldec-9-en-1-ylacetate based on stepwise alkylation of acetoacetic ester by 3-butenylbromide and 1,5-bifunctional 3-methylpentanes were investigated. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 589–591, November–December, 2005.     

Selective and efficient oxidation of sulfides to sulfoxides using ammonium cerium (IV) nitrate in the presence of a catalytic amount of KBr or NaBr

A wide range of aliphatic or aromatic sulfides are selectively oxidized to the corresponding sulfoxides using ammonium cerium (IV) nitrate (CAN) and a catalytic amount of KBr or NaBr in the presence of wet SiO₂ in CH₂Cl₂ under heterogeneous conditions in moderate to high yields. Correspondence: Mohammad Ali Zolfigol, Faculty of Chemistry, Bu-Ali Sina University, P.O. Box 6517838683, Hamadan, Iran; Kamal Amani, Department of Chemistry, Faculty of Science, University of Kurdistan, P.O. Box 6617715175, Sanandaj, Iran.     

Spectrofluorometric determination and chemical speciation of trace concentrations of chromium (III & VI) species in water using the ion pairing reagent tetraphenyl-phosphonium bromide

A highly selective, and low cost extractive spectrofluorometric method has been developed for determination of trace concentrations of chromium (III & VI) in water samples using the fluorescent reagent tetraphenylphosphonium bromide (TPP⁺·Br⁻). The method was based upon solvent extraction of the produced ion associate [TPP⁺·CrO₃Cl⁻] of TPP⁺·Br⁻ and halochromate in aqueous HCl and measuring the fluorescence quenching of TPP⁺·Br⁻ in chloroform at λ_ex/em = 242/305 nm. The fluorescence intensity of TPP⁺Br⁻ decreased linearly on increasing the chromium (VI) concentration in the range of 1-114 μg L⁻¹. The limits of detection (LOD) and quantification (LOQ) of chromium (VI) were 0.43 and 1.42 μg L⁻¹, respectively. Chromium (III) species after oxidation to chromium (VI) with H₂O₂ in alkaline solution were also determined. Chemical speciation of chromium (III & VI) species at trace levels was achieved. The method was applied for analysis of chromium in certified reference material (IAEA Soil-7) and in tap- and wastewater samples and compared successfully (>95%) with the inductively coupled plasma-mass spectrometry (ICP-MS) results.     

Sensitive and specific detection of potentially allergenic almond (Prunus dulcis) in complex food matrices by Taqman real-time polymerase chain reaction in comparison to commercially available protein-based enzyme-linked immunosorbent assay

Currently, causative immunotherapies are lacking in food allergy. The only option to prevent allergic reactions in susceptible individuals is to strictly avoid the offending food. Thus, reliable labelling of allergenic constituents is of major importance, but can only be achieved if appropriate specific and sensitive detection techniques for foods with allergenic potential are available. Almond is an allergenic food that requires mandatory labelling on prepackaged foods and belongs to the genus Prunus. Species of this genus are phylogenetically closely related. We observed commercially available almond specific ELISA being highly cross-reactive with other foods of the Prunoideae family, resulting in a false-positive detection of up to 500,000 mg kg⁻¹ almond. Previously published PCR methods were reported to be cross-reactive with false positive results >1200 mg kg⁻¹.We describe the development of a novel almond specific real-time PCR, based on mutated mismatch primers and sequence specific Taqman^® probe detection, in comparison with two quantitative commercially available ELISA. PCR sensitivity was investigated with chocolate, chocolate coating and cookies spiked between 5 and 100,000 mg kg⁻¹ almond. In all matrices almond was reproducibly detected by real-time PCR at the lowest spike level of 5 mg kg⁻¹. Further, between 100 and 100,000 mg kg⁻¹ spiked almond, the method featured good correlation between quantified copy numbers and the amount of spiked almond. Within this range a similar relation between detectable signal and amount of almond was observed for both PCR and ELISA. In contrast to ELISA the Taqman^® real-time PCR method was highly specific in 59 food items with negligible cross-reactivity for a very limited number of Prunoideae foods. The real-time PCR analysis of 24 retail samples was in concordance with ELISA results: 21% (n = 5) contained undeclared almond. This is the first completely disclosed real-time PCR method for a specific and potentially quantitative almond detection. This PCR method detects almond at a level where severe allergic reactions should not be expected for the majority of the almond allergic individuals.     

Trace metals distribution in surface and deep seawater from the Ría de Arousa estuary (north-western Spain): Study before and after the Prestige oil tanker sinking

Cu, Ni, Pb, Mn, Sn, Fe, Al and Zn in surface and deep seawater samples from Ría de Arousa estuary (Galicia, north-western Spain) collected before and after the Prestige spillage were determined. Data were then used to evaluate the impact of the Prestige accident in the Ría de Arousa by applying principal component analysis (PCA) and cluster analysis (CA). Surface water from Sar River and Ulla River was also analysed for the same elements. Determinations were performed by inductively coupled plasma–optical emission spectrometry (ICP–OES) after solid phase extraction (SPE) of element-8-hydroxyquinoline complexes onto commercial C18 cartridges. The highest concentrations were found in sampling stations along Ulla River, while Al, Fe and Sn offered the highest values in surface and deep seawater from the inner part of the estuary, area where the main villages and sport harbours are located. PCA and CA have shown an independent group formed by surface seawater from the East margin of the mouth of the estuary collected after the Prestige oil spill. However, independent groups were not observed when using deep seawater data, and the effect of the Prestige accident appears to be less evident.     

Bioaccumulation study of acrylates in algae (<Emphasis Type="Italic">Chlorella kessleri</Emphasis>) by Py-GC and Py-GC/MS

Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the pyrolytical cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2-, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied.     

Solid phase microextraction for the determination of volatile organics in the foliage of Fraser fir (Abies fraseri)

Solid phase micro extraction (SPME) was investigated for the determination of volatile chemicals in the foliage of Fraser fir (Abies fraseri). Advantages of SPME include its speed, sensitivity, and ability to determine volatiles without chemical solvents. In this study, qualitative comparisons were performed of the volatiles emitted from living foliage (in situ), damaged living foliage (in situ damaged), and severed foliage (ex situ). These studies suggest that β-phellandrene and γ-terpinene may be emitted as a response to foliar injury. Comparisons were made of the volatiles collected by SPME with ex situ sampling to previous studies in our laboratory using methylene chloride extraction. Similar results were obtained by the two extraction methods.     

Zr(WMo)1-x/2VxO8-x/2：多元素同/低价取代立方ZrW2O8结构类型热收缩固溶体的合成、结构与性质

利用酸蒸气水热法合成了Zr(WMo)1-x/2VxO7-x/2(OH)2·2H2O(x=0.04,0.08,0.10,0.14,0.20,0.22,0.26,0.32)四方晶相固溶体。以此为前驱体,通过高温脱水和相转变法合成了立方相Zr(WMo)1-x/2VxO8-x/2(x=0.04,0.08,0.10,0.14,0.20,0.22)固溶体。立方Zr(WMo)1-x/2VxO8-x/2固溶体具有Pa3空间群。Zr(WMo)1-x/2VxO8-x/2的平均晶体结构描述为按照化学计量的ZrV2O7结构与β-ZrWMoO8结构的叠加。ZrV2O7在立方ZrWMoO8中的固溶度为11mol%;立方Zr(WMo)1-x/2VxO8-x/2固溶体的相变温度低于200 K;在200 K～573 K温度范围内具有负热膨胀系数;线热膨胀系数近似为常数。