Progress 02/22/09 to 02/21/14
Outputs
Progress Report Objectives (from AD-416): Objective 1: Evaluate existing measurement systems and determine the need for improved measurements for water and lipid soluble vitamins (e.g., vitamins D and E and selected B vitamins), for which significant public health concern and inadequate composition data exists in foods and dietary supplements. Sub-Objective 1.A: Systematically evaluate public health concerns and adequacy of food composition data for vitamins and matrices to prioritize improved measurement needs, including methods and available Reference Materials. Sub-Objective 1.B. Develop detailed evaluations of measurement systems for priority analytes and matrices. Sub-Objective 1.C. Develop specific purpose statements for development and/or updating of methods for measurements of single or multiple vitamins. Objective 2: Develop and validate new or updated analytical methods using current technology to determine the levels of water-soluble vitamins (WSV), lipid soluble vitamins (LSV) and/or other components for foods and dietary supplements. Sub-Objective 2.A: Develop/update and optimize measurement procedures to establish validated capability for simultaneous measurements of multiple WSV (SimWSV). Sub-Objective 2.B: Develop and validate analytical methods for the determination and quantification of LSV (A, D, E, and K) and lipids in food matrices and dietary supplements. Sub-Objective 2.C Develop/update and optimize measurement procedures to establish validated capability for measurements of vitamin B12 in dietary supplements and foods. Sub-Objective 2.D Develop multivariate calibration methods for simultaneous determination of multiple vitamins in extracts with no prior chromatographic separations. Objective 3: Develop and validate sample preparation procedures to optimize extraction, remove interferences, and/or to concentrate difficult to analyze vitamins in foods and dietary supplements. Objective 4: Catalyze cooperative activities to identify and provide improved measurement systems and essential Reference Materials for vitamins in foods and dietary supplements. Provide analytical data to characterize the vitamin content of selected Reference Materials. Sub-Objective 4.A: Generate information with developed and validated methods to assign value-added information on vitamin content to available Reference Materials. Sub-Objective 4.B: Catalyze development of overall measurement systems for vitamins in foods and dietary supplements. Approach (from AD-416): Objective 1: Evidence-based reviews will provide priorities for specific vitamins, define adequacy of existing data, and define quality of data required for future needs. The present state of the performance of individual labs and the adequacy of analysis of specific vitamin measurement systems will be evaluated from extensive data available from the USDA contract analyses conducted as part of NFNAP and DSID. Clearly defined purpose statements will be developed for specific applications. Objective 2: Improved procedures will be developed to simultaneously measure water soluble vitamins (SIMWSV) [thiamin, riboflavin, niacin, pyridoxine, folic acid, pantothenic acid, biotin, choline, and ascorbic acid] in foods and dietary supplements (DS). SIMWSV and LC-IDMS methods for DS will be extended to fortified foods. The additional challenges of natural levels of vitamins in unfortified foods require different approaches or compromise conditions to obtain acceptable analytical results. We will examine newer chromatographic separation modes such as hydrophilic interaction liquid chromatography (HILIC) and aqueous normal phase (ANP) chromatography to improve these separations. A defined protocol of intra-laboratory validation will be carried out following AOAC guidelines. The FCMDLVitamin D method is implemented for analysis of food samples, and additional foods, dietary supplements and reference materials will be analyzed. IDMS methods will be initiated for other lipid soluble vitamins A, E, and K. The FCMDL method to determine the low levels of B12 in vitamin supplements using dual column LC/UV will be extended to fortified foods using sensitive LC/MS techniques and collaboratively cross-validated to the microbiological method. The possibility to calibrate spectral fingerprints (information with no chromatographic separation) of extracts of various types of food and dietary supplement materials to obtain quantitative information about vitamin content will be explored. Calibration models will be developed and validated. Objective 3: Multiple extractions for WSV with different buffers, pHs, and multiple extraction approaches (including classical and modern methods such as pressurized liquid extraction [PLE], microwave-assisted extraction [MAE], ultrasonic irradiation, stirring, shaking, and Soxhlet) will be systematically explored to ensure complete extraction and compare extraction efficiencies of different procedures. The lipid soluble vitamins (LSV) (A, D, E, K) would be similarily extracted with a organic solvents of different polarities. Objective 4: FCMDL capability for high quality vitamin determinations will be applied to provide reference measurements to value to NIST SRMs such as the Adult/Infant Formula SRM and Fortified Cereal SRM. Through initiating and providing guidance for a number of nutrition metrology- related activities, FCMDL will catalyze improvement of the overall measurement system for vitamins. FCMDL will participate as collaborators in method validation studies as appropriate. FCMDL will continue to organize and advise the development and conduct of symposia, and other appropriate workshops. Progress was made for all objectives of this NP 107 plan supporting Components 2: Monitoring food composition and nutrient intake of the nation, Problem Statement 2A: Provide U.S. food composition data. This project terminated this year and was replaced by project 1235-52000- 063-00D. Over the lifetime of this project, significant advances were made for the analysis of water-soluble and lipid soluble vitamins. A method was developed for the determination of multiple water-soluble vitamins (WSVs) using high performance liquid chromatography (HPLC) and ultra high performance liquid chromatography (UHPLC) with detection by photodiode array (LC-DAD), fluorescence (LC-F), and stable isotope dilution mass spectrometry (SID-MS). These methods were used in a collaboration with the National Institute of Standards and Technology to characterize standard reference materials (SRM 1849, Adult/Infant Formula; SRM 3233, fortified Cereal; and 3280, Multivitamin/Multielement Tablets). A validated method was developed for vitamin B6 in collaboration with AOAC International and the financial support of the Office of Dietary Supplements at NIH. This method was capable of analyzing a wide variety of samples from the relatively pure vitamin supplements to very messy foods such as gummy bears. In the field of lipid soluble vitamins, the main focus was vitamin D (vit D). To support the Nutrient Data Lab (BHNRC) and panel examining new Dietary Recommended Intakes of vit D at the National Academy of Science, a method for vit D was developed based on the combination of two validated methods from AOAC International. The resulting �wet� method was very long and tedious, requiring extraction, saponification, drying, and dissolution of the sample followed by a clean-up column, an analytical column, and detection with a photodiode array detector and mass spectrometry. This method was used to characterize 5 �control� materials (cereal, cheese, milk, orange juice, and salmon) that were used for quality assurance standards for the vit D project. A simplified method was developed for the analysis of vit D supplements in gelatin capsules by simply diluting the oil from the capsules in hexane and skipping the wet chemistry preparation step. This method dramatically increased the speed of analysis and also allowed the quantification of triacylglycerols (TAGs) in the excipient oils of the supplements and the determination of vitamins, A, E, and K. The �dilute and shoot� method was extended to of solid powdered dietary supplement capsules and NIST SRM 3280 compressed powder supplement tablets by extracting the vit D for direct analysis. This method was also applied to the determination of vitamin D2 in mushrooms. The success of the vit D methods is attributable to the use of multiple (3 and 4) mass spectrometers (MSs) for detection. The dilute and shoot and extract and shoot methods provide more complex matrices but accurate analyses are achieved by detection with multiple MSs using different ionization mechanisms and different ion monitoring. Thus, highly accurate and precise vit D results were achieved with nominal mass measurements, i.e. without an expensive high resolution MS. Progress in FY 2014 is presented under the new project 1235-52000-063- 00D.
Impacts
(N/A)
Publications
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Progress 10/01/12 to 09/30/13
Outputs
Progress Report Objectives (from AD-416): Objective 1: Evaluate existing measurement systems and determine the need for improved measurements for water and lipid soluble vitamins (e.g., vitamins D and E and selected B vitamins), for which significant public health concern and inadequate composition data exists in foods and dietary supplements. Sub-Objective 1.A: Systematically evaluate public health concerns and adequacy of food composition data for vitamins and matrices to prioritize improved measurement needs, including methods and available Reference Materials. Sub-Objective 1.B. Develop detailed evaluations of measurement systems for priority analytes and matrices. Sub-Objective 1.C. Develop specific purpose statements for development and/or updating of methods for measurements of single or multiple vitamins. Objective 2: Develop and validate new or updated analytical methods using current technology to determine the levels of water-soluble vitamins (WSV), lipid soluble vitamins (LSV) and/or other components for foods and dietary supplements. Sub-Objective 2.A: Develop/update and optimize measurement procedures to establish validated capability for simultaneous measurements of multiple WSV (SimWSV). Sub-Objective 2.B: Develop and validate analytical methods for the determination and quantification of LSV (A, D, E, and K) and lipids in food matrices and dietary supplements. Sub-Objective 2.C Develop/update and optimize measurement procedures to establish validated capability for measurements of vitamin B12 in dietary supplements and foods. Sub-Objective 2.D Develop multivariate calibration methods for simultaneous determination of multiple vitamins in extracts with no prior chromatographic separations. Objective 3: Develop and validate sample preparation procedures to optimize extraction, remove interferences, and/or to concentrate difficult to analyze vitamins in foods and dietary supplements. Objective 4: Catalyze cooperative activities to identify and provide improved measurement systems and essential Reference Materials for vitamins in foods and dietary supplements. Provide analytical data to characterize the vitamin content of selected Reference Materials. Sub-Objective 4.A: Generate information with developed and validated methods to assign value-added information on vitamin content to available Reference Materials. Sub-Objective 4.B: Catalyze development of overall measurement systems for vitamins in foods and dietary supplements. Approach (from AD-416): Objective 1: Evidence-based reviews will provide priorities for specific vitamins, define adequacy of existing data, and define quality of data required for future needs. The present state of the performance of individual labs and the adequacy of analysis of specific vitamin measurement systems will be evaluated from extensive data available from the USDA contract analyses conducted as part of NFNAP and DSID. Clearly defined purpose statements will be developed for specific applications. Objective 2: Improved procedures will be developed to simultaneously measure water soluble vitamins (SIMWSV) [thiamin, riboflavin, niacin, pyridoxine, folic acid, pantothenic acid, biotin, choline, and ascorbic acid] in foods and dietary supplements (DS). SIMWSV and LC-IDMS methods for DS will be extended to fortified foods. The additional challenges of natural levels of vitamins in unfortified foods require different approaches or compromise conditions to obtain acceptable analytical results. We will examine newer chromatographic separation modes such as hydrophilic interaction liquid chromatography (HILIC) and aqueous normal phase (ANP) chromatography to improve these separations. A defined protocol of intra-laboratory validation will be carried out following AOAC guidelines. The FCMDLVitamin D method is implemented for analysis of food samples, and additional foods, dietary supplements and reference materials will be analyzed. IDMS methods will be initiated for other lipid soluble vitamins A, E, and K. The FCMDL method to determine the low levels of B12 in vitamin supplements using dual column LC/UV will be extended to fortified foods using sensitive LC/MS techniques and collaboratively cross-validated to the microbiological method. The possibility to calibrate spectral fingerprints (information with no chromatographic separation) of extracts of various types of food and dietary supplement materials to obtain quantitative information about vitamin content will be explored. Calibration models will be developed and validated. Objective 3: Multiple extractions for WSV with different buffers, pHs, and multiple extraction approaches (including classical and modern methods such as pressurized liquid extraction [PLE], microwave-assisted extraction [MAE], ultrasonic irradiation, stirring, shaking, and Soxhlet) will be systematically explored to ensure complete extraction and compare extraction efficiencies of different procedures. The lipid soluble vitamins (LSV) (A, D, E, K) would be similarily extracted with a organic solvents of different polarities. Objective 4: FCMDL capability for high quality vitamin determinations will be applied to provide reference measurements to value to NIST SRMs such as the Adult/Infant Formula SRM and Fortified Cereal SRM. Through initiating and providing guidance for a number of nutrition metrology- related activities, FCMDL will catalyze improvement of the overall measurement system for vitamins. FCMDL will participate as collaborators in method validation studies as appropriate. FCMDL will continue to organize and advise the development and conduct of symposia, and other appropriate workshops. A �dilute and shoot� method developed at FCMDL for the determination of vitamin D as well as triacylglycerols (TAGs) in the excipient oil in dietary supplement gelatin capsules was improved and expanded (see Accomplishment). The method was used to survey the vitamin D content of various oil-filled dietary supplements. Data are being processed and prepared for publication. A new method for the quantification of TAGs was developed based on response factors obtained from the comparison of HPLC-MS results with those obtained by gas chromatography with flame ionization detection (GC- FID). AOCS method Ce-1b-89 was implemented for GC-FID analysis but required modification and improvement to allow the very long chain fatty acid methyl esters to elute. GC-FID data were obtained for all oils in the dietary supplements (olive oil, soybean oil, sunflower oil, safflower oil, rice bran oil, canola oil) for comparison to results by LC-MS. A manuscript describing this new development has been submitted and is undergoing the first stage of review. The �dilute and shoot� method was applied to the analysis of solid powdered dietary supplement capsules and NIST SRM 3280 compressed powder supplement tablets. The �dilute and shoot� method was also applied to the determination of vitamin D in irradiated mushroom powders. Preliminary data suggests that this approach is feasible for solid samples and further research will be included in the new project goals. Accomplishments 01 A quadruple parallel mass spectrometer. Scientists at USDA in Beltsville, MD, have developed a �quadruple parallel mass spectrometer� for the analysis of vitamin D and triacylglycerols (TAGs) in dietary supplements. The instrumental design employs high performance liquid chromatography with seven detectors, including four mass spectrometer, for the identification and quantification of vitamin D3 and the TAGs in the oil. The data from these experiments allow a much higher degree of confidence in quantitative results, because multiple instruments acquire qualitative information on the same samples at the same time, in parallel. This represents a new �high water mark� for mass spectrometry that demonstrates a unique capability here at FCMDL that no one else currently possesses.
Impacts
(N/A)
Publications
- Byrdwell, W.C., Horst, R.L., Phillips, K.M., Holden, J.M., Patterson, K.Y., Harnly, J.M., Exler, J. 2013. Vitamin D levels in fish and shellfish determined by liquid chromatography with ultraviolet detection and mass spectrometry. Journal of Food Composition and Analysis. 10:1016/j.jfca. 2013.01.005.
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Progress 10/01/11 to 09/30/12
Outputs
Progress Report Objectives (from AD-416): Objective 1: Evaluate existing measurement systems and determine the need for improved measurements for water and lipid soluble vitamins (e.g., vitamins D and E and selected B vitamins), for which significant public health concern and inadequate composition data exists in foods and dietary supplements. Sub-Objective 1.A: Systematically evaluate public health concerns and adequacy of food composition data for vitamins and matrices to prioritize improved measurement needs, including methods and available Reference Materials. Sub-Objective 1.B. Develop detailed evaluations of measurement systems for priority analytes and matrices. Sub-Objective 1.C. Develop specific purpose statements for development and/or updating of methods for measurements of single or multiple vitamins. Objective 2: Develop and validate new or updated analytical methods using current technology to determine the levels of water-soluble vitamins (WSV), lipid soluble vitamins (LSV) and/or other components for foods and dietary supplements. Sub-Objective 2.A: Develop/update and optimize measurement procedures to establish validated capability for simultaneous measurements of multiple WSV (SimWSV). Sub-Objective 2.B: Develop and validate analytical methods for the determination and quantification of LSV (A, D, E, and K) and lipids in food matrices and dietary supplements. Sub-Objective 2.C Develop/update and optimize measurement procedures to establish validated capability for measurements of vitamin B12 in dietary supplements and foods. Sub-Objective 2.D Develop multivariate calibration methods for simultaneous determination of multiple vitamins in extracts with no prior chromatographic separations. Objective 3: Develop and validate sample preparation procedures to optimize extraction, remove interferences, and/or to concentrate difficult to analyze vitamins in foods and dietary supplements. Objective 4: Catalyze cooperative activities to identify and provide improved measurement systems and essential Reference Materials for vitamins in foods and dietary supplements. Provide analytical data to characterize the vitamin content of selected Reference Materials. Sub-Objective 4.A: Generate information with developed and validated methods to assign value-added information on vitamin content to available Reference Materials. Sub-Objective 4.B: Catalyze development of overall measurement systems for vitamins in foods and dietary supplements. Approach (from AD-416): Objective 1: Evidence-based reviews will provide priorities for specific vitamins, define adequacy of existing data, and define quality of data required for future needs. The present state of the performance of individual labs and the adequacy of analysis of specific vitamin measurement systems will be evaluated from extensive data available from the USDA contract analyses conducted as part of NFNAP and DSID. Clearly defined purpose statements will be developed for specific applications. Objective 2: Improved procedures will be developed to simultaneously measure water soluble vitamins (SIMWSV) [thiamin, riboflavin, niacin, pyridoxine, folic acid, pantothenic acid, biotin, choline, and ascorbic acid] in foods and dietary supplements (DS). SIMWSV and LC-IDMS methods for DS will be extended to fortified foods. The additional challenges of natural levels of vitamins in unfortified foods require different approaches or compromise conditions to obtain acceptable analytical results. We will examine newer chromatographic separation modes such as hydrophilic interaction liquid chromatography (HILIC) and aqueous normal phase (ANP) chromatography to improve these separations. A defined protocol of intra-laboratory validation will be carried out following AOAC guidelines. The FCMDL Vitamin D method is implemented for analysis of food samples, and additional foods, dietary supplements and reference materials will be analyzed. IDMS methods will be initiated for other lipid soluble vitamins A, E, and K. The FCMDL method to determine low levels of B12 in vitamin supplements using dual column LC/UV will be extended to fortified foods using sensitive LC/MS techniques and collaboratively cross-validated to the microbiological method. The possibility to calibrate spectral fingerprints (information with no chromatographic separation) of extracts of various types of food and dietary supplement materials to obtain quantitative information about vitamin content will be explored. Calibration models will be developed and validated. Objective 3: Multiple extractions for WSV with different buffers, pHs, and multiple extraction approaches (including classical and modern methods such as pressurized liquid extraction [PLE], microwave-assisted extraction [MAE], ultrasonic irradiation, stirring, shaking, and Soxhlet) will be systematically explored to ensure complete extraction and compare extraction efficiencies of different procedures. The lipid soluble vitamins (LSV) (A, D, E, K) would be similarily extracted with a organic solvents of different polarities. Objective 4: FCMDL capability for high quality vitamin determinations will be applied to provide reference measurements to value to NIST SRMs such as the Adult/Infant Formula SRM and Fortified Cereal SRM. Through initiating and providing guidance for a number of nutrition metrology- related activities, FCMDL will catalyze improvement of the overall measurement system for vitamins. FCMDL will participate as collaborators in method validation studies as appropriate. FCMDL will continue to organize and advise the development and conduct of symposia, and other appropriate workshops. A method was validated for the determination of vitamin B6 in most vitamin and mineral supplements. A general extraction method was used that was modified slightly depending on whether the supplement was a tablet, soft gel, liquid, sustained release material, or a �gummy-bear� type of material. Chromatographic separation was based on both high performance liquid chromatography (HPLC) and ultra-HPLC (U-HPLC). The U- HPLC separation was accomplished in less than 20 minutes. The vitamin was detected using ultraviolet absorption, fluorescence, and mass spectrometry. Accuracy and precision of �5% were achieved for all supplement materials. Accomplishments 01 A �triple parallel mass spectrometry� experimental arrangement in which three mass spectrometers are used in parallel to provide both qualitativ and quantitative information using complementary ionization techniques f mass spectrometry was applied to the analysis of Vitamin D. The data fr these experiments allow a much higher degree of confidence in quantitati results, because multiple instruments acquire qualitative information on the same samples at the same time. We are now able to obtain quantitati results on one instrument plus qualitative analysis on three other instruments simultaneously, using different and complementary ionization sources, each producing different types of data. This unique instrument offers unprecedented accuracy and specificity.
Impacts
(N/A)
Publications
- Byrdwell, W.C. 2011. Multiple parallel mass spectrometry for lipid and vitamin D analysis. 8:225-299.
- Byrdwell, W.C. 2011. 'Dilute-and-shoot' triple parallel mass spectrometry method for analysis of vitamin D and triacylglycerols in dietary supplements. Analytical and Bioanalytical Chemistry. 401:3317-3334.
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Progress 10/01/10 to 09/30/11
Outputs
Progress Report Objectives (from AD-416) Objective 1: Evaluate existing measurement systems and determine the need for improved measurements for water and lipid soluble vitamins (e.g., vitamins D and E and selected B vitamins), for which significant public health concern and inadequate composition data exists in foods and dietary supplements. Sub-Objective 1.A: Systematically evaluate public health concerns and adequacy of food composition data for vitamins and matrices to prioritize improved measurement needs, including methods and available Reference Materials. Sub-Objective 1.B. Develop detailed evaluations of measurement systems for priority analytes and matrices. Sub-Objective 1.C. Develop specific purpose statements for development and/or updating of methods for measurements of single or multiple vitamins. Objective 2: Develop and validate new or updated analytical methods using current technology to determine the levels of water-soluble vitamins (WSV), lipid soluble vitamins (LSV) and/or other components for foods and dietary supplements. Sub-Objective 2.A: Develop/update and optimize measurement procedures to establish validated capability for simultaneous measurements of multiple WSV (SimWSV). Sub-Objective 2.B: Develop and validate analytical methods for the determination and quantification of LSV (A, D, E, and K) and lipids in food matrices and dietary supplements. Sub-Objective 2.C Develop/update and optimize measurement procedures to establish validated capability for measurements of vitamin B12 in dietary supplements and foods. Sub-Objective 2.D Develop multivariate calibration methods for simultaneous determination of multiple vitamins in extracts with no prior chromatographic separations. Objective 3: Develop and validate sample preparation procedures to optimize extraction, remove interferences, and/or to concentrate difficult to analyze vitamins in foods and dietary supplements. Objective 4: Catalyze cooperative activities to identify and provide improved measurement systems and essential Reference Materials for vitamins in foods and dietary supplements. Provide analytical data to characterize the vitamin content of selected Reference Materials. Sub-Objective 4.A: Generate information with developed and validated methods to assign value-added information on vitamin content to available Reference Materials. Sub-Objective 4.B: Catalyze development of overall measurement systems for vitamins in foods and dietary supplements. Approach (from AD-416) Objective 1: Evidence-based reviews will provide priorities for specific vitamins, define adequacy of existing data, and define quality of data required for future needs. The present state of the performance of individual labs and the adequacy of analysis of specific vitamin measurement systems will be evaluated from extensive data available from the USDA contract analyses conducted as part of NFNAP and DSID. Clearly defined purpose statements will be developed for specific applications. Objective 2: Improved procedures will be developed to simultaneously measure water soluble vitamins (SIMWSV) [thiamin, riboflavin, niacin, pyridoxine, folic acid, pantothenic acid, biotin, choline, and ascorbic acid] in foods and dietary supplements (DS). SIMWSV and LC-IDMS methods for DS will be extended to fortified foods. The additional challenges of natural levels of vitamins in unfortified foods require different approaches or compromise conditions to obtain acceptable analytical results. We will examine newer chromatographic separation modes such as hydrophilic interaction liquid chromatography (HILIC) and aqueous normal phase (ANP) chromatography to improve these separations. A defined protocol of intra-laboratory validation will be carried out following AOAC guidelines. The FCMDLVitamin D method is implemented for analysis of food samples, and additional foods, dietary supplements and reference materials will be analyzed. IDMS methods will be initiated for other lipid soluble vitamins A, E, and K. The FCMDL method to determine the low levels of B12 in vitamin supplements using dual column LC/UV will be extended to fortified foods using sensitive LC/MS techniques and collaboratively cross-validated to the microbiological method. The possibility to calibrate spectral fingerprints (information with no chromatographic separation) of extracts of various types of food and dietary supplement materials to obtain quantitative information about vitamin content will be explored. Calibration models will be developed and validated. Objective 3: Multiple extractions for WSV with different buffers, pHs, and multiple extraction approaches (including classical and modern methods such as pressurized liquid extraction [PLE], microwave-assisted extraction [MAE], ultrasonic irradiation, stirring, shaking, and Soxhlet) will be systematically explored to ensure complete extraction and compare extraction efficiencies of different procedures. The lipid soluble vitamins (LSV) (A, D, E, K) would be similarily extracted with a organic solvents of different polarities. Objective 4: FCMDL capability for high quality vitamin determinations will be applied to provide reference measurements to value to NIST SRMs such as the Adult/Infant Formula SRM and Fortified Cereal SRM. Through initiating and providing guidance for a number of nutrition metrology- related activities, FCMDL will catalyze improvement of the overall measurement system for vitamins. FCMDL will participate as collaborators in method validation studies as appropriate. FCMDL will continue to organize and advise the development and conduct of symposia, and other appropriate workshops. A method was developed for the determination of vitamin B6 in vitamin and mineral supplements. A general extraction method was used that was modified slightly depending on whether the supplement was a tablet, soft gel, liquid, sustained release material, or a �gummy-bear� material. Chromatographic separation was based on both high performance liquid chromatography (HPLC) and ultra-HPLC (U-HPLC). U-HPLC separation was accomplished in less than 20 minutes. Vitamin B6 was detected using ultraviolet absorption, fluorescence, and mass spectrometry. Accuracy and precision of �5% were achieved for all supplement materials. A method was developed for the determination of vitamin D, as well as the excipient oil in dietary supplement gelcaps. This "dilute and shoot" method eliminates the labor- and resource-intensive sample pretreatment typically required for vitamin D analysis. The method uses six types of detectors, including ultraviolet detection, and three types of mass spectrometry, which provide not only quantification of vitamin D3 but also characterization of the triacylglycerols (TAGs) in the oil, and identification of TAG oxidation products and glycerin polyglycerols. Accomplishments 01 Determination of Vitamin D in orange juice. Levels of vitamin D in natural and fortified foods have been questioned because of the inadequa of the analytical methods. Levels in orange juice are particularly suspect because the fat-soluble vitamin D is incorporated into a water matrix. In this work, samples of vitamin D-fortified orange juice obtained from retail food stores were analyzed for vitamin D3 content using a method developed by combining the best features of two AOAC methods. The method was applied to 40 samples of American orange juice brands collected using a statistically designed sampling plan as part of the National Food and Nutrient Analysis Program. Vitamin D3 values rang from 1.071 �g/100 g (43 IU/100 g) to 1.663 �g/100 g (67 IU/100 g), with average across 55 samples analyzed, including duplicates, of 1.4 � 0.1 �g/100 g (57 � 5 IU/100 g, indicating that a typical 8 oz. (240 mL = 240 cm3) glass of orange juice provided 3.4 � 0.3 �g (140 � 10 IU) vitamin D This work provided analytical values for vitamin D to the USDA National Nutrient Databank for Standard Reference, used in estimating intakes of vitamin D for the Institute of Medicine Dietary Reference Intakes Committee review of Vitamin D reference values.
Impacts
(N/A)
Publications
- Patterson, K.K., Exler, J., Byrdwell, W.C., Phillips, K.M., Horst, R., Lemar, L.E., Holden, J.M. 2010. Vitamin D content and variability in fluid milk from a USDA nationwide sampling to update values in the National Nutrient Database for Standard Reference. Journal of Dairy Science. 93(11) :5082-5090.
- Phillips, K.M., Ruggio, D.M., Horst, R.L., Minor, B., Simon, R., Feeney, M. , Byrdwell, W.C., Haytowitz, D.B. 2011. Vitamin D and sterol composition of ten types of mushrooms from retail suppliers in the United States. Journal of Agricultural and Food Chemistry. 59(14):7841-7853.
- Byrdwell, W.C., Exler, J., Gebhardt, S.E., Harnly, J.M., Holden, J.M., Horst, R., Patterson, K.K., Phillips, K., Wolf, W.R. 2010. Ultraviolet and mass spectrometric analysis of vitamin D in retail fortified orange juice. Journal of Food Composition and Analysis. 24:299-306.
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Progress 10/01/09 to 09/30/10
Outputs
Progress Report Objectives (from AD-416) Objective 1: Evaluate existing measurement systems and determine the need for improved measurements for water and lipid soluble vitamins (e.g., vitamins D and E and selected B vitamins), for which significant public health concern and inadequate composition data exists in foods and dietary supplements. Sub-Objective 1.A: Systematically evaluate public health concerns and adequacy of food composition data for vitamins and matrices to prioritize improved measurement needs, including methods and available Reference Materials. Sub-Objective 1.B. Develop detailed evaluations of measurement systems for priority analytes and matrices. Sub-Objective 1.C. Develop specific purpose statements for development and/or updating of methods for measurements of single or multiple vitamins. Objective 2: Develop and validate new or updated analytical methods using current technology to determine the levels of water-soluble vitamins (WSV), lipid soluble vitamins (LSV) and/or other components for foods and dietary supplements. Sub-Objective 2.A: Develop/update and optimize measurement procedures to establish validated capability for simultaneous measurements of multiple WSV (SimWSV). Sub-Objective 2.B: Develop and validate analytical methods for the determination and quantification of LSV (A, D, E, and K) and lipids in food matrices and dietary supplements. Sub-Objective 2.C Develop/update and optimize measurement procedures to establish validated capability for measurements of vitamin B12 in dietary supplements and foods. Sub-Objective 2.D Develop multivariate calibration methods for simultaneous determination of multiple vitamins in extracts with no prior chromatographic separations. Objective 3: Develop and validate sample preparation procedures to optimize extraction, remove interferences, and/or to concentrate difficult to analyze vitamins in foods and dietary supplements. Objective 4: Catalyze cooperative activities to identify and provide improved measurement systems and essential Reference Materials for vitamins in foods and dietary supplements. Provide analytical data to characterize the vitamin content of selected Reference Materials. Sub-Objective 4.A: Generate information with developed and validated methods to assign value-added information on vitamin content to available Reference Materials. Sub-Objective 4.B: Catalyze development of overall measurement systems for vitamins in foods and dietary supplements. Approach (from AD-416) Objective 1: Evidence-based reviews will provide priorities for specific vitamins, define adequacy of existing data, and define quality of data required for future needs. The present state of the performance of individual labs and the adequacy of analysis of specific vitamin measurement systems will be evaluated from extensive data available from the USDA contract analyses conducted as part of NFNAP and DSID. Clearly defined purpose statements will be developed for specific applications. Objective 2: Improved procedures will be developed to simultaneously measure water soluble vitamins (SIMWSV) [thiamin, riboflavin, niacin, pyridoxine, folic acid, pantothenic acid, biotin, choline, and ascorbic acid] in foods and dietary supplements (DS). SIMWSV and LC-IDMS methods for DS will be extended to fortified foods. The additional challenges of natural levels of vitamins in unfortified foods require different approaches or compromise conditions to obtain acceptable analytical results. We will examine newer chromatographic separation modes such as hydrophilic interaction liquid chromatography (HILIC) and aqueous normal phase (ANP) chromatography to improve these separations. A defined protocol of intra-laboratory validation will be carried out following AOAC guidelines. The FCMDLVitamin D method is implemented for analysis of food samples, and additional foods, dietary supplements and reference materials will be analyzed. IDMS methods will be initiated for other lipid soluble vitamins A, E, and K. The FCMDL method to determine the low levels of B12 in vitamin supplements using dual column LC/UV will be extended to fortified foods using sensitive LC/MS techniques and collaboratively cross-validated to the microbiological method. The possibility to calibrate spectral fingerprints (information with no chromatographic separation) of extracts of various types of food and dietary supplement materials to obtain quantitative information about vitamin content will be explored. Calibration models will be developed and validated. Objective 3: Multiple extractions for WSV with different buffers, pHs, and multiple extraction approaches (including classical and modern methods such as pressurized liquid extraction [PLE], microwave-assisted extraction [MAE], ultrasonic irradiation, stirring, shaking, and Soxhlet) will be systematically explored to ensure complete extraction and compare extraction efficiencies of different procedures. The lipid soluble vitamins (LSV) (A, D, E, K) would be similarily extracted with a organic solvents of different polarities. Objective 4: FCMDL capability for high quality vitamin determinations will be applied to provide reference measurements to value to NIST SRMs such as the Adult/Infant Formula SRM and Fortified Cereal SRM. Through initiating and providing guidance for a number of nutrition metrology- related activities, FCMDL will catalyze improvement of the overall measurement system for vitamins. FCMDL will participate as collaborators in method validation studies as appropriate. FCMDL will continue to organize and advise the development and conduct of symposia, and other appropriate workshops. Methods for water-soluble vitamins (WSVs) were developed based on LC with fluorescence and mass spectrometric detection (LC-F and LC-MS) and with stable isotope dilution with MS detection (IDMS). These methods were used to provide data for WSVs in Standard Reference Material (SRM) 1849 � Infant/Adult Nutritional Formula and SRM 3233 � Fortified Cereal. Multi- lab validation of the methods was achieved by comparing the results from FCMDL with those from NIST and other participating labs. Results from the LC-F method are being used in on-going research to develop a method to analyze the WSVs without LC separation. Methods for vitamin B12 and vitamin B6 were developed based on the WSV methods. The vitamin B6 method was selected by AOAC INTERNATIONAL for development as a Single Lab Validated Method (see 1235-52000-059-01R). FCMDL also compared a variety of extraction techniques for vitamins in dietary supplements and fortified cereals. Optimized extraction methods were used to analyze WSVs in series of vitamin-fortified cereal samples that were collected regionally. Initial results show that almost all cereals had vitamin levels significantly higher than label claim values, in line with the general manufacturing practice of over-fortifying to provide adequate shelf life. Development of methods and acquisition of data for vitamin D was extended to a second year. Improvements included: 1) a three-point calibration curve, 2) two columns in series, and 3) use of more potassium hydroxide in the initial step for a more thorough digestion of the sample. These improvements enhanced accuracy and eliminated interferences. This method was used to analyze seafood samples for the National Nutrient Database. The vitamin D method was further modified for the analysis of vitamin D2 in mushrooms. This method allowed both Vitamin D3 and D2 to be determined simultaneously. New efforts are underway to incorporate the analysis of 25-hydroxy vitamin D3, present in meats, to provide additional information on active forms of vitamin D in foods. A third modification to the vitamin D method, a �dilute-and-shoot� method, was developed for determination of vitamin D and triacylglycerols in gel cap dietary supplements. The saponification and extraction steps were completely eliminated, reducing sample preparation time and allowing quantification of intact triacylglycerols (normally be decomposed by saponification). The new method is being used to quantify vitamin D in numerous 1000 IU, 2000 IU, and 5000 IU gel cap dietary supplements. FCMDL scientists participated in advisory groups and expert committees on methods and metrology related to vitamins in foods, planned and participated in the ODS workshop on evaluation of vitamin methods for dietary supplements, were invited to the First International Vitamin Symposium and to the AOAC Stakeholder Panel on Infant Formula and Adult Nutritionals (SPIFAN), and one was elected to the USP Expert Committee on Dietary Supplements. Accomplishments 01 Development of a standard reference material for infant and adult nutritional formulas. The National Institute of Standards and Technolog was contracted to develop a standard reference material �Infant/Adult Nutritional Formula� (SRM� 1849) by the Office of Dietary Supplements of the National Institutes of Health. FCMDL was selected to submit results for the analysis of water soluble vitamins and vitamin D. These values were used to assign values for the Certificate of Analysis issued in Jul 2009. This SRM is available nationally and internationally, is used by laboratories to validate analytical measurements, and is an essential component to the international metric system.
Impacts
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Publications
- Chen, P., Wolf, W.R., Castanheira, I., Sanches-Silva, A. 2010. A LC/UV/Vis method for determination of cyanocobalamin in multivitamin dietary supplements with on-line sample clean-up. Analytical Methods. 2:1171-1175.
- Byrdwell, W.C. 2010. Dual parallel mass spectrometry for lipid and vitamin D analysis. Journal of Chromatography A. 1217(25):3992-4003.
- Goldschmidt, R.J., Wolf, W.R. 2010. Simultaneous determination of water- soluble vitamins in SRM 1849 Infant/Adult Nutritional Formula powder by liquid chromatography-isotope dilution mass spectrometry. Analytical and Bioanalytical Chemistry. 397(2):471-481.
- Wolf, W.R. 2010. History of reference materials for food and nutrition metrology: as represented in the series of BERM symposia. Analytical and Bioanalytical Chemistry. 397(2):413-421.
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