Determination of Fe,Ni,Cu,Zn,Cd and Pb in seawater by isotope dilution automatic solid-phase extraction—ICP-MS

A thorough understanding of the biogeochemical cycling of trace metals in the ocean is crucial because of the important role these elements play in regulating metabolism in marine biotas and thus,the climate.However,a precise and accurate analysis of trace metals in seawater is difficult because they are present at extremely low concentrations in a high salt matrix.In this study,we report an analytical method for the preconcentration and separation of six trace metals,Fe,Ni,Cu,Zn,Cd and Pb,in seawater using a sea FAST automatic solid-phase extraction device,analysis by a triple quadrupole collision/reaction technique with inductively coupled plasma mass spectrometry(ICP-MS),and quantification by the isotope dilution technique.A small volume(10 m L)of seawater sample was mixed with a multi-element isotope spike and subjected to sea FAST procedures.The preconcentrate solution was then analyzed using the optimized collision/reaction cell mode of ICP-MS,with NH_(3)gas for Fe and Cd with a flow rate of 0.22 m L/min and He for Ni,Cu,Zn and Pb with a flow rate of 4.0 m L/min.The procedure blanks were 130 pmol/L,3.0 pmol/L,6.8 pmol/L,37 pmol/L,0.29 pmol/L and 0.42 pmol/L,for Fe,Ni,Cu,Zn,Cd and Pb,respectively.The method was validated using five reference materials(SLRs-6,SLEW-3,CASS-6,NASS-7 and GEOTRACE-GSC),and our results were consistent with the consensus values.The method was further validated by measuring full-water-column seawater samples from the subtropical Northwest Pacific Ocean,and our results demonstrated good oceanic consistency.

Stable Isotope Dilution Analysis of Gibberellin Residues in Tomato Paste by Liquid Chromatography-Tandem Mass Spectrometry

An accurate and sensitive method for the simultaneous determination of gibberellic acid（GA3）, gibberellin A4（GA4） and gibberellin A7（GA7） residues in tomato paste was developed by coupling solid phase extraction to high performance liquid chromatography-tandem mass spectrometry（LC-MS/MS） with electrospray ionization based stable isotope dilution analysis（SIDA）. The isotope labeled internal standard can compensate for the losses during the extraction and cleanup steps and for discrimination due to ion suppression. After extraction from methanol, hydrophile lipophilic balance（HLB） solid phase extraction（SPE） column was tested for the capacity of the cleanup of the tomato paste in compared with C18 SPE column which is the common way to the detection of GAs, and the former gained better result. Spiked experiments were performed in the non-contaminated tomato pastes and the recoveries of GA3, GA4 and GA7 were 42.6%―75.0% in external standard method（ESM） and 91.1%―103.8% in internal standard method（ISM） respectively. The validities of this method were investigated and good analytical performance for the three GAs was obtained, including low limits of method detection（2 ng/g for GA3 and GA4, 0.3 ng/g for GA7）, excellent linear dynamic ranges（5―500 ng/g for GA3 and GA4, 1―100 ng/g for GA7） and good relative standard deviation ranges（4.8%―9.4% for the intra-day test and 3.5%―11.9% for the inter-day test）.

Determination of CeO_2 , Dy_2O_3, CuO and PbO in Yttrium Oxide Reference Material by Isotope Dilution Spark Source Mass Spectrometry

This paper describes the quantitative determination of rare-earth elements cerium, dysprosium and non-rare-earth element copper, lead and the homogeneity examination of these four elements in yttrium oxide reference material by isotope dilution spark source mass spectrometry (ID-SSMS). The sensitivity of the meth- od is l0^(-5)～10^(-7%). The precision is better than 6%. The accuracy is better than 5%. The interferences of the spectra and the optimum amount of the spike added to the sample are discussed. The choice of the conducting material for the sample electrodes is studied.

Candidate reference measurement procedure for serum 17-hydroxyprogesterone quantification via isotope dilution liquid chromatography–tandem mass spectrometry

Background:Accurate quantification of 17-hydroxyprogesterone(17-OHP)in serum is vital for clinical and research applications.However,inter-laboratory variability in test results exists owing to the lack of a standardized reference measurement procedure(RMP).Therefore,in this study,we developed a highly accurate,cost-effective,and user-friendly candidate RMP(cRMP)for analyzing 17-OHP in serum.Methods:We quantified 17-OHP in serum using a one-step liquid–liquid extraction method with the addition of 17-OHP-^(13)C_(3),followed by liquid chromatography–tandem mass spectrometry.The ability of these methods to suppress interference was evaluated by chromatographic analysis.We assessed accuracy,specificity,the lower limit of quantitation,linearity,and matrix effects by following the standards specified by the Clinical and Laboratory Standards Institute.The consistency between the developed cRMP and the chemiluminescence method was evaluated through experiments with 120 clinical samples.Results:The developed cRMP required only 8 min for accurate quantification of serum 17-OHP without bias from matrix effects or interference from 19 metabolites added as potential interferents.The method exhibited favorable measurement performance,with a quantitation limit of 0.086 ng/mL,linear range of 0.1–400 ng/mL,a total imprecision of≤2.90%,spike recovery of 100.1%–100.6%,and relative deviations from assigned target values(RfB Institution)of−2.91%to 1.10%.The cRMP demonstrated good consistency with the conventional assay(chemiluminescence method),with a correlation coefficient R of 0.96977.Conclusion:A cRMP with high accuracy,cost-effectiveness,and convenient operation was developed for quantifying 17-OHP in serum.Its simplicity and robust performance make it an invaluable addition to the arsenal of analytical tools available for laboratories.This method can enhance the accuracy and reliability of 17-OHP measurements across various laboratories.

同位素稀释-HRGC-LRMS法测定环境样品中二噁英类多氯联苯

多氯联苯(PCBs)是一类具有209种同类物的高毒性、难降解、强脂溶性和生物累积性的持久性有机污染物,自从1996年Jensen首次在鹰和鲱鱼中发现PCBs后[1,2],现在已在世界各地不同的环境介质中都发现有PCBs的存在[3].……

LC-MS/MS同位素稀释法测定食品中地西泮和氯丙嗪残留量

This article concentrates on the method of the determination of diazepam and chlorpromazine residue in meat and kidney,by using HPLC-MS/MS.The D6-chlorpromazine was added to sample as an internal standard.Then extracted the sample with acetonitrile,cleaned up the extract through Oasis HLB cartridge.Determination and confirmation is made by means of liquid chromatography-tandem mass spectrometry,using internal standard method.The limit of quantitation of chlorpromazine and diazepam are all 1.0 μg/kg.

我国某城市市售食品中PCDD/Fs污染水平和人群二噁英膳食暴露量研究

The status of PCDDs and PCDFs content in retail foods from a certain area by Isotope Dilution HRGC-HRMS was surveyed and the local population PCDD/Fs exposure from diverse foods and health risk was evaluated.PCDD/Fs was extracted from samples by Soxhlet extraction,concentrated and purified by FMS column chromatograph,carbon column enrichment.Confirmation and quantitative analysis at pg/g level of PCDD/Fs was performed by HRGC/HRMS using multiple ion detection mode(MID).TEQ concentration was calculated by WHO-TEF multiplying by concentration of seventeen PCDD/Fs congener.Median of PCDD/Fs concentration for fish,livestock,poultry,egg,vegetable oil,milk,vegetable totally 100 samples for ten diverse foods didn’t exceed the limit standards by EU.The level of PCDD/Fs for different food in the certain area was lower or comparable to the data reported by developed country in the world.The total weekly intake and monthly intake for local population or national population was 3.44,14.8 WHO-TEQ/kg BW and 1.5,6.42 pg WHO-TEQ/kg BW respectively,the value was lower than the Tolerable Weekly Intake of 14 pg WHO TEQ/kg BW for PCDDs,PCDFs and dioxin-like PCBs established by EU Scientific Committee for Food.The dietary PCDD/Fs intake for local people was higher than national population.And animal food was the dominant contributor to the total dietary intake,which accounted for more than 70 percent.These levels of consumption of diverse food containing typical levels of PCDD/Fs doesn’t present a risk to the health of the local population.But integrative dietary intake could be evaluated including of PCBs intake for population in the future.

国际比对CCQM-P77a血清中氢化可的松测定

The concept of metrological traceability in laboratory medicine has increasingly received considerable recognition worldwide.The Consultative Committee for Amount of Substance (CCQM) which concerned international comparisons and establishment of international equivalence between national laboratories had organized international comparison CCQM-P77a: determination of serum cortisol in 2006.National Institute of Metrology (NIM) took part in the comparison as the representative of China and received good performance according to the results published by CCQM.

高效液相色谱-同位素稀释质谱法测定血清中的苯丙氨酸

Phenylalanine in serum was determined by HPLC isotope dilution mass spectrometry method with D8 labeled phenylalanine as internal standard.Phenylalanine and its isotope labeled analogue were monitored at the transitions m/z=166→120 and 172→126 in multiple reaction monitoring (MRM) mode,respectively,which effectively eliminated the matrix effect.The RSD for 5 repeats measurement of the same sample was 0.5%.Uncertainty was evaluated,which showed the main uncertainty was from the purity assessment of phenylalanine reference material and the variation of method.The presented method can be applied into value assessment of reference material of phenylalanine in serum,and it can be also used for traceability establishment of the measurement of phenylalanine in serum.

A Study of the Rhenium-Osmium Geochronometry of Molybdenites

This study deals with the first application of the isotope dilution - inductively coupled plasma mass spectrometry in the rhenium-osmium geochronometry in China. The chemical separation procedure included decomposition of samples by means of alkali fusion, extraction of rhenium by acetone and extraction of osmium by distillation. The recovery of both elements in the entire process was more than 90% . The blanks of analyses were 0.07 ng for rhenium and 0.01 ng for 187Os. The mineralization ages of molybdenites from four molybdenum deposits in China were determined by using this method, with a precision (2σ)of about ±3% . These results agree satisfactorily with their geological backgrounds. The Re-Os method can directly determine ages of metal deposits and reflect the true ages more reliably than other dating methods that only determine the ages of country rocks from which mineralization ages are inferred. As many hydrothermal sulphide deposits usually contain molybdenites, this method has bright prospects of wide application.

Trace-Level Analysis of Hexavalent Chromium in Lake Sediment Samples Using Ion Chromatography Tandem Mass Spectrometry

The analysis of hexavalent chromium, Cr(VI), in soil and sediment samples has been predominantly carried out in materials containing elevated levels. Reliable analysis of trace-level of Cr(VI) in sediment samples remains challenging. Cr(VI) analyses with multipoint calibration and speciated isotope dilution (SID) adapted from U.S. EPA method 6800 were used to measure lower-level Cr(VI) on an ion chromatograph coupled with a tandem mass spectrometer (IC-MS/MS). Lake sediment samples were collected from various locations in Northern Ontario and Cr(VI) was extracted using both alkaline digestion and ethylene diaminetetraacetic acid (EDTA) extraction. Certified reference materials were extracted and analyzed by IC-MS/MS and UV-VIS detection. The SID-MS approach allowed for the quantification of Cr(VI) in samples with concentration levels below 0.5 μg.g-1 wet weight.

Estimation of N_2 Fixation by Some Legumes Using ^（15）N－Labelled Soil in Greenhouse Experiment

Pot experimeats were carried out to estimate N2 fixation by vetch, milk vetch, sickle alfalfa and broadbean in pure stand using a 15N-labelled soil. Winter wheat was used as the non-fixing control. The 15N-labelled soil used was prepared by growing corn-wheat-corn successively on a nearly organic-matter-free Xiashu loess supplemented with adequate amounts of (15NH4)aSO4, P, K and micronutrients, then incorporating these 15N-labelled plant msterials into the soil after each harvest, and allowing the plant materials to be decomposed aerobically for 410 d after incorporation of the plant material of the third crop. The 15N enrichment of wheat plant-N varied slightly with organs,with a maximum difference of 9.8%. Based on 15N enrichment of soil N inferred from the mean value of the 15N enrichment in different organs of wheat 79%-91% of total N in the tops and 67%-74% of total N in the roots of legumes studied were derived from atmosphere. Estimate by isotope dilution method was in good agreement with that by the conventional difference method provided values obtained by the latter were corrected for seed N, and also with that from the measurement of N accumulated in the tops of the legumes.

Dietary glutamine,glutamic acid and nucleotide supplementation accelerate carbon turnover(δ^(13)C)on stomach of weaned piglets

The use of stable isotope analysis as a tool for characterization of carbon turnover(δ^(13)C) in piglet's tissues by tracing its feeding system has drawn attention. Thus, this study aimed at evaluating the influence of dietary glutamine, glutamic acid and nucleotides supplementation on carbon turnover in fundic-stomach region of weaned piglets at an average age of 21 days. The diets consisted of additive-free diet — control(C); 1% glutamine(G); 1% glutamic acid(GA) and 1% nucleotides(Nu). At weaning day(day 0: baseline), 3 piglets were slaughtered to quantify the δ^(13)C of stomach. The remaining 120 piglets were blocked by weight and sex, randomly assigned to pens with 3 piglets slaughtered per treatment at days 1,2,4, 5,7,9,13.20.27 and 49 after weaning in order to verify the fundic-stomach isotopic composition by treatments.Samples were analyzed in terms of ^(13)C/^(12)C ratio by mass spectrometry and converted to relative isotopic enrichment values(δ^(13)C ‰) used to plot the first order exponential curves over time using OriginPro 8.0 software. The inclusion of glutamine, glutamate and nucleotides in piglet's diets has accelerated the carbon turnover in stomach during the post-weaning period, demonstrating also that glutamate has guaranteed fastest 13 C incorporation rate on fundic-stomach region and pH-lowering. Besides that, stable isotopes technique(δ^(13)C) has proved to be an important methodology to determine the time-scales at which piglets shift among diets with different isotopic values, characterizing the trophic effects of additives and the phenotypic flexibility of stomach.