Primary Speciation Analysis on 6 Kinds of Microelements in Glycyrrhiza uralensis Fisch.

[Objective]The aim was to analyze the primary speciation of 6 microelements in Glycyrrhiza uralensis Fisch. and provide theoretical basis for explaining pharmacodynamic principle of liquorice and discussing quality control of liquorice planting. [Method]The 6 elements Cu,Zn,Ca,Fe,Mg and Mn in roots of G.uralensis were extracted based on traditional decoction method and were separated into water-soluble state and suspension state by micro porous filtering film. The elements in water-soluble state were detected by flame atomic adsorption spectrophotometry （FAAS）. [Result]The results showed that extractive rates of the elements were in the range of 1.71%-60.06%,and immerse-residue ratio in 0.018 3-1.682 0; the results also indicated that the immerse-residue ratio of Zn was biggest （1.68）,Zn played an important medical role and might be considered as the best characteristic element in G.uralensis; the recoveries of the elements were ranged from 95.72% to 103.15% and relative standard deviations （RSD） were less than 2.38%. [Conclusion]Because of its high accuracy,FAAS method is feasible for analyzing primary speciation of microelements in G.uralensis.

Application of ultrasonic to speciation analysis of heavy metals in soil

In order to reduce the operation time and improve the extraction efficiency, ultrasonic energy by means of ultrasonic bath was used to the modified Tessier sequential extraction for speciation analysis of heavy metals in soil. Extractable contents of Cu, Fe, Mn, Ni, Pb and Zn were measured by atomic absorption spectroscopy(AAS). The merit of the ultrasonic extraction(UE) applied to the modified Tessier method is not only that the operation time for the first 4 fractions was reduced from ca.18 h to 8 h, comparing with conventional extraction(CE), but also the extraction efficiency was higher. The results for both of UE and CE were consistent. The extractable Cu, Ni and Zn in the sample No.1 were mainly associated with the third fraction(Fe-Mn oxides fraction), and fourth fraction(organic matter fraction) in the sample No.2. The extractable Fe and Mn were all mainly associated with the third fraction, and Pb the fourth fraction in both of the samples. The effects of concentration of hydroxylamine chloride on the capability for the extraction of studied metals were also studied.

Sequential Speciation Analysis of Heavy Metals in Drinking Water Pipe Scales by Mass Spectrometry

An electrochemical mass spectrometry technique was developed based on a homemade analytical device for sequential analysis of the heavy metals with various speciations in the scales.Four speciations(e.g.,water-soluble speciation,organic speciation,indissoluble speciation and elemental speciation)of heavy metals are sequentially extracted by H_(2)O,CH_(3)OH,EDTA-2Na and electrolysis for online electrospray ionization mass spectrometry(ESI-MS)detection.The method takes significant advantages,such as requiring no tedious offline sample pretreatment,high speed of analysis(20 min),high throughput(multi-metals),good sensitivity(0.5µg/L)and rich chemical information(four speciations).As a result,the rapid comprehensive characterization of four speciations of Pb,Ni,Cu,Zn,Fe,Ba,Mn,Cr and Ca in water pipe scales has been qualitatively achieved.It demonstrated that the present method is a powerful tool for the effective assessment of potential hazards in drinking water,which provides a new analytical idea for evaluating water quality.

Speciation analysis of aluminium in plant parts of Betula pendula and in soil

The research presents the first results of aluminium speciation analysis in aqueous extracts of individual plant parts of Betula pendula and soil samples, using High Performance Ion Chromatography with Diode Array Detection（HPIC-DAD）. The applied method allowed us to carry out a full speciation analysis of aluminium in the form of predominant aluminium–fluoride complexes： AlF（（x = 2,3,4））^（（3-x））（first analytical signal）, AlF^（2＋）（second analytical signal） and Al^（3＋）（third analytical signal） in samples of lateral roots, tap roots, twigs, stem, leaf and soil collected under roots of B. pendula. Concentrations of aluminium and its complexes were determined for two types of environment characterised by different degree of human impact：contaminated site of the Chemical Plant in Luboń and protected area of the Wielkopolski National Park. For all the analysed samples of B. pendula and soil, AlF（（x = 2,3,4））^（（3-x））had the largest contribution, followed by Al^（3＋）and AlF^（2＋）. Significant differences in concentration and contribution of Al–F complexes and Al^（3＋）form, depending on the place of sampling（different anthropogenic pressure） and plant part of B. pendula were observed. Based on the obtained results, it was found that transport of aluminium is ＂blocked＂ by lateral roots, and is closely related to Al content of soil.

Study of heavy metal speciation in branch sediments of Poyang Lake

This study concentrates on the environmental pollution level of sediments in the six branches of Poyang Lake, the biggest fresh water lake in China. This is the first systematic report on the speciation analysis of heavy metals （Cu, Co, Cd, Pb, and Ni） in the six branches of the lake. A reported analytical procedure involving a five-step sequential extraction is used for the partition of particulating heavy metals. The sediment samples are analyzed using flame atomic absorption spectroscopy （FAAS）. Experimental results obtained from five replicate samples of fluvial bottom surface sediments at the sampling points demonstrated that the relative standard deviation of the sequential extraction procedure was generally better than 10% （Cd except）. The average extracted contents of the five elements, analyzed after all five steps, are found to be （mg/kg） for Cu： 26.89, Co： 16.25, Cd： 1.08, Pb： 37.98, and Ni： 20.46. The content of the exchangeable species was generally lower. Except Cu, the percentage of the species bond to organic matter was lower than 20%. The fractions containing the most metal for Cu, Co, and Ni were the residues （52.26%, 45.28%, and 74.82%, respectively）.

Chemical degradation of platinum oncolytics in urine and speciation of the inorganic contaminants cisplatin and carboplatin relevant in waste water

Understanding the prevalent form of platinum(Pt)based antineoplastic agents,used in chemotherapy,is of importance to develop a remediation strategy that restricts aquatic exposure.The speciation of Pt-based compounds was measured in actual patients’urine using hydrophobic interaction liquid chromatography(HILIC)equipped with an ICP-MS detector.Carboplatin showed poor metabolization and intact excretion 11 h after administration,whereas cisplatin underwent a rapid aquation in the first 7 h.To compare,the in vitro degradation rate of cisplatin,carboplatin and oxaliplatin was determined in synthetic human urine,mimicking true environmental conditions.The fraction of intact molecules was measured at regular intervals following incubation at 37°C,resulting in degradation rate constants.The chemical stability was highest for carboplatin(k=0.0143±0.0012 min−1),versus faster degradation of oxaliplatin and cisplatin by exponential decay with k1 of 0.0026±0.0001 min−1 and k_(2)=5.59±0.46×10^(−6) min−1,respectively.These kinetic parameters can serve as input to further expand modelling databases and improve the predictive power of speciation software to estimate eco-toxicity risks.Considering the strong residual cytotoxicity of the platinum antineoplastic molecules following renal clearance and human excretion,the contaminants are of high environmental concern and offer potential for metal recovery using advanced treatment steps.In such water treatment processes,especially carboplatin,above all cancerostatic platinum compounds,should be addressed since it is more persistent in the aquatic environment.

Studies on the Simultaneous Determination of Cr(Ⅲ)and Cr(Ⅵ)by Ion Chromatography(IC)

The research aimed to develop and validate an ion chromatography method for the simultaneous analysis of Cr(Ⅲ) and Cr(Ⅵ)from pumpkin. A new analytical method based on ion chromatography techniques was developed by the Cr(Ⅲ) pre-column derivatization and Cr(Ⅵ) post-column derivatization. The ion chromatography condition was optimized and the detection sensitivity was improved. Cr(Ⅲ) and Cr(Ⅵ) were determined by 365 and 530 nm,respectively. The temperature of water bath,the heating time for pre-column derivatization,and the flow rate of post-column derivative liquid were screened on the basis of single factor experiment,the effects of various factors were determined by the method of L16( 43) orthogonal experiment design. Considering the results of orthogonal experiments and the variation tendency of peak area under different factors,the optimum derivatization conditions were chose as follows: the flow rate of post-column derivative liquid is0. 5 m L/min,the temperature of water bath for pre-column derivatization is 100 ℃ and the heating time is 5 min. The conditions were optimized by means of orthogonal experiments under the p H of leacheate ranged from 6. 5 to 6. 8 and the I-concentration of 5 mmol/L. Under optimized derivatization conditions,the detection limits for Cr(Ⅲ) and Cr(Ⅵ) were 0. 17 and 0. 019 mg,respectively. And the average recoveries of Cr(Ⅲ) in pumpkin were in the range of 82%-85%. Results indicated that pumpkin does not contain Cr(Ⅵ) according to this ion chromatography method of simultaneously determination for Cr(Ⅲ) and Cr(Ⅵ).

Selenium nanoparticles in aquaculture:Unique advantages in the production of Se-enriched grass carp(Ctenopharyngodon idella)

The production of selenium-enriched fish can contribute to alleviating selenium deficiency in human diets.However,it is still unclear which selenium source,as an additive,can efficiently and costeffectively produce high-quality selenium-enriched fish.This study evaluated the effects of selenium nanoparticles(SeNP),selenite,and selenomethionine(SeMet)on the growth,antioxidant capacity,selenium content,selenium speciation,and meat quality of grass carp.Ten diets were prepared,including a basal diet(BD)and three concentrations(0.1,0.3,and 0.9 mg/kg)of SeNP,selenite,and SeMet.A total of600 fish(250.79±1.57 g)were randomly assigned to 30 tanks(3 tanks/group).Fish were fed the experimental diet three times daily for 60 d.In this study,SeNP most significantly promoted the growth and antioxidant capacity of grass carp,with 0.3 mg/kg SeNP identified as the optimal additive concentration.Additionally,SeNP demonstrated equally excellent bioavailability as SeMet and significantly increased the content of SeMet in grass carp(Ctenopharyngodon idella)muscle.Furthermore,compared to SeMet and selenite,dietary SeNP could more significantly enhance the content of selenocysteine(SeCys2)and methylselenocysteine(MeSeCys)in grass carp muscle tissue.In addition,we have demonstrated that SeCys2and MeSeCys promote apoptosis of cancer cells(HeLa)through the mitochondrial apoptotic pathway(involving Bax and Bcl-2).Furthermore,as an additive,0.3 mg/kg SeNP significantly improved the flesh quality of grass carp by reducing crude fat and heavy metal content,as well as increasing the levels of eicosapentaenoic acid(EPA)and docosahexaenoic acid(DHA)and the ratio of n-3/n-6 polyunsaturated fatty acid(PUFA).In summary,SeNP is the most suitable additive for producing selenium-enriched fish.

Oxidation state specific analysis of arsenic species in tissues of wild-type and arsenic(+3 oxidation state)methyltransferase-knockout mice

Arsenic methyltransferase（As3mt） catalyzes the conversion of inorganic arsenic（i As） to its methylated metabolites, including toxic methylarsonite（MAs~Ⅲ） and dimethylarsinite（DMAs~Ⅲ）. Knockout（KO） of As3 mt was shown to reduce the capacity to methylate i As in mice. However, no data are available on the oxidation states of As species in tissues of these mice. Here, we compare the oxidation states of As species in tissues of male C57BL/6 As3mt-KO and wild-type（WT） mice exposed to arsenite（iA s~Ⅲ） in drinking water. WT mice were exposed to50 mg/L As and As3mt-KO mice that cannot tolerate 50 mg/L As were exposed to 0, 15, 20, 25 or30 mg/L As. iA s~Ⅲaccounted for 53% to 74% of total As in liver, pancreas, adipose, lung, heart, and kidney of As3mt-KO mice; tri- and pentavalent methylated arsenicals did not exceed 10% of total As. Tissues of WT mice retained iA s and methylated arsenicals： iA s~Ⅲ, MAs~Ⅲand DMAs~Ⅲ represented 55%‐68% of the total As in the liver, pancreas, and brain. High levels of methylated species, particularly MAs~Ⅲ, were found in the intestine of WT, but not As3mt-KO mice,suggesting that intestinal bacteria are not a major source of methylated As. Blood of WT mice contained significantly higher levels of As than blood of As3mt-KO mice. This study is the first to determine oxidation states of As species in tissues of As3mt-KO mice. Results will help to design studies using WT and As3mt-KO mice to examine the role of iA s methylation in adverse effects of iA s exposure.

Pisco grape pomace:Iron/copper speciation and antioxidant properties,towards their comprehensive utilization

The pisco and wine industry produces hundreds of tons of grape pomace each year in Chile,generating environmental problems,and demanding urgent strategies for its management.The aim of this work was to study the pisco grape pomace based on a physicochemical characterization,an iron/copper speciation analysis,and the optimization for polyphenols recovery,establishing the polyphenolic profile,antioxidant properties,and the Fe^(2+)/Cu^(2+) chelating activity,to promote their revalorization as an ingredient with potential application in the food industry.The chemical characterization showed mainly high values for crude protein(15.36%dw)and potassium(9240.66 mg/kg).The Fe/Cu speciation depicted that iron and copper soluble forms in pisco pomace flour represented 70.57%and 52.18%,respectively,regarding total content.The optimized extract showed mainly pyrogallol,catechin and epicatechin,with concentrations of 1078.43±60.14μg/g,883.20±7.57μg/g and,751.76±23.04μg/g,respectively,with a relevant antioxidant capacity by Oxygen Radical Absorbance Capacity(ORAC)of 1402.15μmol TE/g dw GPE and,a better chelating ability to complex Fe^(2+) than Cu^(2+).The pisco pomace was for the first time chemically characterize,showing it as a potential source of minerals and antioxidant biocompounds,making it a good candidate for nutritional applications,as a rich source of organic matter or even could be potentially utilized to produce value-added commodities,toward a circular economy.

Advances in selenium supplementation:From selenium-enriched yeast to potential selenium-enriched insects,and selenium nanoparticles

Selenium(Se)is an essential micronutrient that plays an important role in animal and human development and physiological homoeostasis.This review surveys the role of Se in the environment,plants and animal bodies,and discusses data on Se biofortification with different sources of supplementation,from inorganic to organic forms,with special focus on Se-enriched yeast(Se-yeast).Although Se-yeast remains one of the main sources of organic Se,other emerging and innovative sources are reviewed,such as Se-enriched insects and Se-nanoparticles and their potential use in animal nutrition.Se-enriched insects are discussed as an option for supplying Se in organic form to livestock diets.Se-nanoparticles are also discussed,as they represent a more biocompatible and less toxic source of inorganic Se for animal organisms,compared to selenite and selenate.We also provide up to date information on the legal framework in the EU,USA,and Canada of Se that is contained in feed additives.From the scientific evidence available in the literature,it can be concluded that among the inorganic forms,sodium selenite is still one of the main options,whereas Se-yeast remains the primary organic form.However,other potential sources such as Se-enriched insects and Se-nanoparticles are being investigated as they could potentially combine a high bioavailability and reduced Se emissions in the environment.

Formation Mechanism of High Quality Marine Source Rocks-Coupled Control Mechanism of Geological Environment and Organism Evolution

High quality marine source rock （HQMSR） is the key prerequisite for medium to large hydrocarbon accumulations. However, the forming mechanism remains unclear. On the basis of the in-vestigation for the geodynamic setting of the Middle-Upper Yangtze during the Early Cambrian in dif-ferent spatial scales and the analysis of trace elements, the main controlling factors of the development of high quality marine source rock are discussed, with specific consideration of the burial rate of the organic matter. The formation of high quality marine source rocks is suggested to be the result of a co-ordinated development and the interaction between geological environments and organism evolution during the major geological transition periods. We perceived that the burial rate of organic matter was influenced by the primary productivity and its burial conditions. The abundance of autogenetic molyb-denum gained directly by the chemical speciation analysis of rocks could be used as a proxy for the burial organic matter. The burial rate of autogenetic molybdenum and the sedimentary organics in modern marine environments could be used to estimate the sedimentary organics in ancient environ-ments effectively.

Methylated and thiolated arsenic species for environmental and health research——A review on synthesis and characterization

Hundreds of millions of people around the world are exposed to elevated concentrations of inorganic and organic arsenic compounds, increasing the risk of a wide range of health effects. Studies of the environmental fate and human health effects of arsenic require authentic arsenic compounds. We summarize here the synthesis and characterization of more than a dozen methylated and thiolated arsenic compounds that are not commercially available. We discuss the methods of synthesis for the following14 trivalent（Ⅲ） and pentavalent（） arsenic compounds： monomethylarsonous acid（MMA~Ⅲ）, dicysteinylmethyldithioarsenite（MMA~Ⅲ（Cys）_2）, monomethylarsonic acid（MMA~Ⅴ）,monomethylmonothioarsonic acid（MMMTAⅤ） or monothio-MMA~Ⅴ, monomethyldithioarsonic acid（MMDTA~Ⅴ） or dithio-MMA~Ⅴ, monomethyltrithioarsonate（MMTTA~Ⅴ） or trithio-MMA~Ⅴ,dimethylarsinous acid（DMA~Ⅲ）, dimethylarsino-glutathione（DMA~Ⅲ（SG））, dimethylarsinic acid（DMA~Ⅴ）, dimethylmonothioarsinic acid（DMMTA~Ⅴ） or monothio-DMAⅤ, dimethyldithioarsinic acid（DMDTA~Ⅴ） or dithio-DMA~Ⅴ, trimethylarsine oxide（TMAO~Ⅴ）, arsenobetaine（AsB）, and an arsenicin-A model compound. We have reviewed and compared the available methods,synthesized the arsenic compounds in our laboratories, and provided characterization information. On the basis of reaction yield, ease of synthesis and purification of product, safety considerations, and our experience, we recommend a method for the synthesis of each of these arsenic compounds.