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...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.展开更多
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...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）.展开更多
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 m...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.展开更多
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 standardi...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.展开更多
A new method was developed in this work to account for inorganic Sb species interconversion during soil sample preparation and subsequent separation steps. The Sb(III) and Sb(V) concentrations at each investigated ste...A new method was developed in this work to account for inorganic Sb species interconversion during soil sample preparation and subsequent separation steps. The Sb(III) and Sb(V) concentrations at each investigated step in the analytical procedure were determined using species specific spikes (121Sb(III) with 81.18% and 123Sb(V) with 74.04% enrichment). The spiking of these enriched isotopes species solutions was done separately before soil sample extraction and before HPLC separation. Simply by subtracting the final concentration of each species done by on-line isotope dilution (ID) from its concentration at different stages of the analytical procedure done by species specific ID, the influence of each step on species transformation can be estimated. After optimization, the extraction procedure for inorganic Sb species 6% Sb(III) (1.3 RSD, n = 3) and 43.2% Sb(V) (2.9% RSD, n = 3) as percent of total Sb were detected in the examined soil sample using online ID. Using the above described methodology we found that there was no reduction of Sb(V) to Sb(III) during sample preparation or species separation. While about 9.3% of extractable Sb (4.6% of total) was converted from Sb(III) to Sb(V) during the extraction step, no conversion during HPLC separation step was observed. By compensating for Sb(III) transformation during the sample preparation step;the extractable Sb(III) and Sb(V) as percent of total Sb yielded 10.6% and 38.7%, respectively.展开更多
Isotope dilution(ID)method has been widely applied to studies of elemental speciation and certification of the concentrations of geological reference materials.One of the key factors restricting the application of the...Isotope dilution(ID)method has been widely applied to studies of elemental speciation and certification of the concentrations of geological reference materials.One of the key factors restricting the application of the ID method is the difficulty in identifying the optimal ratios of the isotope tracer(spike)to sample(S/N)and in estimating the error propagation.Here,using Se isotope as an example and employing a Monte Carlo method,we found that the optimal choice of spike and S/N are^(77)Se(spike)and 0.7,respectively.The S/N in the range from 0.1 to 4 can produce sufficiently low errors(<0.4%).Extending this method to other elements such as Cr,Fe,Ni,Sr,Cd and etc.,their optimal spike and S/N were also presented.According to the optimized parameters of Se,we determined the Se concentrations of geological reference materials(GRMs)by thiol cotton fiber(TCF)-hydride generation ID-MC-ICP-MS.The relative standard deviation is<5%,and the detection limit is reduced to0.1 ng/g.Most of the measured concentrations are consistent with those recommended by IGGE or reported previously.For some GRMs,discrepancies(e.g.6.90%for GSS-5)exist between our measurements and previous ones,which can be explained by the inhomogeneity of GRMs and/or the different digestion,purification and measurement methods among laboratories.展开更多
基金The National Natural Science Foundation of China under contract Nos 41921006,41890801 and 42076227the Impact and Response of Antarctic Seas to Climate Change,Grant 583 under contract No.IRASCC 1-02-01B。
文摘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.
基金Supported by the Project of Chinese Academy of Inspection and Quanrantine(No.2010JK001)the Project of Xinjiang Entry-exit Inspection and Quarantine Bureau, China(No.2010XK0033)
文摘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）.
文摘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.
基金Science and Technology Project of Dongguan,Grant/Award Number:20211800905072Graduate Education Innovation Program Project of Guangdong Province,Grant/Award Number:2022KCXTD010+6 种基金Discipline Construction Project of Guangdong Medical University,Grant/Award Numbers:4SG22098G,4SG22259G,4SG23030G,4SG23143GNational Natural Science Foundation of China,Grant/Award Numbers:81870016,82270013Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2022A1515010525Guangdong Medical UniversityShenzhen YHLO Biotech Co.,Ltd.Huazhong University of Science and TechnologyShenzhen Maternal and Child Health Care Hospital。
文摘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.
文摘A new method was developed in this work to account for inorganic Sb species interconversion during soil sample preparation and subsequent separation steps. The Sb(III) and Sb(V) concentrations at each investigated step in the analytical procedure were determined using species specific spikes (121Sb(III) with 81.18% and 123Sb(V) with 74.04% enrichment). The spiking of these enriched isotopes species solutions was done separately before soil sample extraction and before HPLC separation. Simply by subtracting the final concentration of each species done by on-line isotope dilution (ID) from its concentration at different stages of the analytical procedure done by species specific ID, the influence of each step on species transformation can be estimated. After optimization, the extraction procedure for inorganic Sb species 6% Sb(III) (1.3 RSD, n = 3) and 43.2% Sb(V) (2.9% RSD, n = 3) as percent of total Sb were detected in the examined soil sample using online ID. Using the above described methodology we found that there was no reduction of Sb(V) to Sb(III) during sample preparation or species separation. While about 9.3% of extractable Sb (4.6% of total) was converted from Sb(III) to Sb(V) during the extraction step, no conversion during HPLC separation step was observed. By compensating for Sb(III) transformation during the sample preparation step;the extractable Sb(III) and Sb(V) as percent of total Sb yielded 10.6% and 38.7%, respectively.
基金supported by Natural Science Foundation of China(No.U1612441,41673017)。
文摘Isotope dilution(ID)method has been widely applied to studies of elemental speciation and certification of the concentrations of geological reference materials.One of the key factors restricting the application of the ID method is the difficulty in identifying the optimal ratios of the isotope tracer(spike)to sample(S/N)and in estimating the error propagation.Here,using Se isotope as an example and employing a Monte Carlo method,we found that the optimal choice of spike and S/N are^(77)Se(spike)and 0.7,respectively.The S/N in the range from 0.1 to 4 can produce sufficiently low errors(<0.4%).Extending this method to other elements such as Cr,Fe,Ni,Sr,Cd and etc.,their optimal spike and S/N were also presented.According to the optimized parameters of Se,we determined the Se concentrations of geological reference materials(GRMs)by thiol cotton fiber(TCF)-hydride generation ID-MC-ICP-MS.The relative standard deviation is<5%,and the detection limit is reduced to0.1 ng/g.Most of the measured concentrations are consistent with those recommended by IGGE or reported previously.For some GRMs,discrepancies(e.g.6.90%for GSS-5)exist between our measurements and previous ones,which can be explained by the inhomogeneity of GRMs and/or the different digestion,purification and measurement methods among laboratories.
文摘提出了同位素稀释-液相色谱-串联质谱法测定鱼、虾、蟹、贝4类水产品中甲霜灵残留量的方法。取样品(5±0.05)g,加入10 ng的内标甲霜灵-d 6,静置10 min,用10 mL含1%(体积分数)乙酸的乙腈溶液涡旋混合、离心。取上清液,于45℃氮吹至0.5 mL以下,加入7.5 mL 20%(体积分数,下同)乙腈溶液混匀,用7.5 mL正己烷去脂,Agela Cleanert S C_(18)固相萃取柱富集净化。所得溶液于45℃氮吹至干,用1 mL 20%乙腈溶液复溶,混匀后过0.22μm针式水相尼龙滤膜,滤液收集至进样小瓶中。以SHISEIDO CAPCELL PAK C_(18)色谱柱为固定相,以不同体积比的0.1%(体积分数)甲酸溶液和乙腈的混合液为流动相进行梯度洗脱,内标法定量。结果表明,甲霜灵标准曲线的线性范围为1.0~100.0μg·L^(-1),检出限(3S/N)为0.5μg·kg^(-1)。以不同品种水产品为空白基质,在1.0,2.0,10.0μg·kg^(-1)等3个浓度水平下,甲霜灵的回收率为93.8%~105%,测定值的相对标准偏差(n=6)均小于13%。
