Progress 02/22/04 to 02/21/09
Outputs
Progress Report Objectives (from AD-416) 1) Develop robust multi-element methods and quality control materials for trace and ultratrace elements important to human health, 2) develop method for total vitamin B12 in foods, 3) develop elemental speciation methods for vitamin B12 (cobalamin), 4) develop analytical methods for the determination of hemeprotein and heme Fe in meats, and 5) develop elemental fingerprinting method for food and botanical materials. Approach (from AD-416) Analytical methods for the trace and ultratrace elements will be based on graphite furnace atomic-absorption spectrometry (GF-AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and ICP-mass spectrometry (ICP-MS). Total vitamin B12 and heme Fe will be determined using selective extraction and ICP-AES. Speciation of vitamin B12 will be based on capillary electrophoresis ICP-MS. Elemental fingerprinting methods will use semi-quantitative ICP-MS. Significant Activities that Support Special Target Populations Over the five year period of this project, methods were developed and/or modified for the determination of trace elements in foods and biological materials using flame and graphite furnace atomic absorption spectrometry (FAAS and GF-AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), and ICP-mass spectrometry (ICP-MS). Instrumental modifications were developed for coupling liquid chromatography and capillary electrophoresis to the ICP-MS. These methods were important for the support of on-going research on trace element content in foods and their organic complexes. In 2004, the Food Composition and Methods Development Laboratory (FCMDL) collaborated with the National Food Processors (NFP) Analytical Chemistry Subcommittee to develop more robust trace element methods. In 2006, FCMDL collaborated with the National Institute of Standards and Technology (NIST) to determining the concentration of aluminum (Al) in a bovine serum Standard Reference Material using GF-AAS. Subsequent research demonstrated that calcium (Ca) in soy milk settled out with time and was difficult to re-dissolve. Additional collaboration with NIST scientists characterized trace elements in a multivitamin/multielement Standard Reference Material (SRM 3280). Development of a method for profiling the trace element content of plant materials using the full scan mode (90 elements) of the ICP-MS was undertaken. A method for the determination of iron in a porphoryn complex (heme Fe) based on the classic Hornsey extraction method using acidified acetone was developed. The concentration of heme Fe is of importance since it is absorbed by a different process than dietary inorganic Fe. A size exclusion chromatography-FAAS instrument for detection of Fe eluting as myoglobin, hemoglobin, ferritin, and transferrin was developed. Scientists collaborated with the Plant, Soil, and Nutrition Lab (USDA, Ithica, NY) on the evaluation of cooking on the bioavailability of Fe. The results indicated that 100% of the hemoglobin and myoglobin are denatured (and thus the protein and heme Fe separate) at 140 degrees F and that 30% of the heme form of Fe is destroyed during cooking.
Impacts
(N/A)
Publications
- Beecher, G., Stewart, K., Holden, J.M., Harnly, J.M., Wolf, W.R. 2009. Legacy of Wilbur O. Atwater: human nutrition research expansion at the USDA-interagency development of food composition research. Journal of Nutrition. 139:178-184.
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Progress 10/01/06 to 09/30/07
Outputs
Progress Report Objectives (from AD-416) 1) Develop robust multi-element methods and quality control materials for trace and ultratrace elements important to human health, 2) develop method for total vitamin B12 in foods, 3) develop elemental speciation methods for vitamin B12 (cobalamin), 4) develop analytical methods for the determination of hemeprotein and heme Fe in meats, and 5) develop elemental fingerprinting method for food and botanical materials. Approach (from AD-416) Analytical methods for the accurate determination of trace elements in foods will be developed using inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP- MS) and graphite furnace atomic absorption spectrometry (GFAAS). The appropriate method will depend on the metal concentration in the foods. Elements of interest include: Mn, Zn, Fe, Cu, Mg, Ca and P (ppm levels) as well as Co, Cr, Ni and V (ppb levels). Methods developed will be evaluated by commercial labs through collaborative studies. We will be involved in the preparation and characterization of a range of trace element control materials. Elemental speciation methods will be developed by combining microseparation methods with ICP-MS detection focusing on cobalamins (Vitamin B12 species). Species specific cobalamin data will be important for studying absorption and bioavailabilitly and the current official AOAC method is a time consuming, microbiological method which can measure only cyanocobalamin - not all the naturally occurring cobalamin species. Finally, iron species will be measured using size exclusion chromatography and UV/Vis and flame atomic absorption spectrometry. Total iron will be measured in meat samples as well as hemeprotein and heme iron. Appropriate speciation control materials will be developed and characterized to facilitate technology transfer. Preliminary elemental speciation food composition data speciation data tables will be prepared. Significant Activities that Support Special Target Populations Activities related to this project have been dramatically curtailed as a result of the early and unexpected retirement of the lead scientist. Most of the research to be conducted in the original proposal has been modified or delayed. The research that is continuing is described below under the direction of the Research Leader. Naturally occurring levels of Vitamin B12 are extremely low and difficult to detect even by mass spectrometry. A project was initiated to determine B12 based on detection of cobalt (Co) that is incorporated in the porphyrin ring of the vitamin, using inductively coupled plasma-mass spectrometry (ICP-MS). Direct analysis of a digested ready-to-eat dry cereal gave results approximately five-fold higher than the Nutrition Facts label value, indicating the possible presence of Co in a form other than B12. An acidified acetone extraction similar to that used for heme- iron, a metal also present in a porphyrin ring, initially gave results that were approximately 20% high compared to the label value. This research will continue using both Co detection and liquid chromatography- MS methods. The levels of calcium (Ca) in soy milk that are associated with the solids were investigated. It was demonstrated that after moderate centrifugation, 90% of the Ca was found in the solid cake. This suggested that there would be little Ca in the liquid phase of soy milk products that had sat on the shelf for some time. The level of Ca in the liquid phase would strongly depend on how vigorous the consumer shook the milk container prior to use. These results suggest that the next step is to determine the extent of settling in soy milk products and ability of users to re-mix the Ca with shaking. Trace metals (calcium, copper, iron, magnesium, manganese, phosphorous, potassium, and zinc) were analyzed in the multivitamin/multielement tablet Standard Reference Material (SRM) 3280 being developed by the National Institutes of Standards and Technology (NIST). These data were submitted to NIST for use in establishing the reference values. The Food Composition and Methods Laboratory (FCML) also participated in the National Marine Analytical Quality Assurance Program for the determination of trace metals in marine mammal tissue sponsored by NIST and the National Oceanic and Atmospheric Administration. Values for cadmium, copper, iron, manganese, and zinc were reported to NIST. Studies were initiated to develop a method for profiling the elemental content of samples using the full scan mode of the inductively coupled plasma-mass spectrometer (ICP-MS). This method determines semi- quantitative values for all elements from mass 6 to 238 based on internal standardization. The method was first used to determine the elemental profile of dry bean samples. The semi-quantitative values of the scanning method were compared to values determined using a routine analytical method based on ICP-atomic emission spectrometry for 15 elements. This research addresses National Program 107, Human Nutrition, Action Plan Component 1, Composition of Foods.
Impacts
(N/A)
Publications
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Progress 10/01/05 to 09/30/06
Outputs
Progress Report 1. What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? Why does it matter? The research to be undertaken falls under National Program 107 - Human Nutrition and addresses performance goal 3.1.2.B as described in the National Program Action Plan. Goal 3.1.2 is "Food Composition and Consumption: Develop techniques for determining food composition, maintain national food composition databases, monitor the food and nutrient consumption of the U.S. population, and develop and transfer effective nutrition intervention strategies." This project directly addresses Priority Objective B. Develop Analytical Methodology for Nutrients. There is an ever-increasing need for trace element food composition data. Much of the trace element data in the latest National Nutrient Database for Standard Reference was generated many years ago and needs to be updated because foods have
changed. Review of the data suggests that in some cases, unsophisticated analytical methodology produced less than accurate results due to problems with contamination, matrix interference effects, or instrumental background correction strategies. Graphite furnace-atomic absorption spectrometry (GF-AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) are newer instrumental techniques that are readily available to commercial labs. All provide better detection limits for many elements as compared to flame atomic absorption spectrometry and GF-AAS and ICP-AES offer the advantage of multielement determinations, allowing for the generation of accurate data for as many as 15-20 elements simultaneously. This project is organized into four objectives: 1) development of robust multielement methods suitable to industry; 2) development of sensitive, ultratrace methods for cobalt (Co), chromium (Cr), nickel (Ni), and
Vanadium (V); 3) development of a method for cobalamin species; and 4) development of methods for the determination of iron (Fe) species. The field of nutrition and public health will benefit, in general, from an improved nutrient database for trace elements and increased knowledge regarding the concentrations and species of trace elements in foods. The field of analytical chemistry will benefit from improved methods for: 1) the simultaneous determination of manganes (Mn), zinc (Zn), Fe, copper (Cu), magnesium (Mg), calcium (Ca), and phosphorus (P); 2) the determination of Co, Cr, Ni, and V; 3) the determination of individual cobalamin species; and 4) the determination of Fe in a porphyrin complex (heme Fe). In addition, the field of analytical chemistry will benefit from improved reference materials. 2. List by year the currently approved milestones (indicators of research progress) Year 1 (FY 2004) 1. Robust Multielement Methods *Develop and circulate a questionnaire to food
industry analytical labs on methods for low levels of Mn, Zn, and Cu in foods. *Evaluate responses to questionnaire. 2. Ultratrace Methods *Develop GF-AAS and ICP methods for Co and Cr. 3. Cobalamin Speciation *Develop method for cobalamin species using capillary electrophoresis and ICP-MS. *Start development of sample preparation method for cobalamins focusing on solid phase extraction. 4. Fe Speciation *Acquire standards for Fe species. *Initiate development of an High Performance Liquid Chromatography (HPLC) separation method for Fe species extracted from meat. Year 2 (FY 2005) 1. Robust Multielement Methods *Complete evaluation of questionnaire. *Develop in-house food control materials for evaluation by food industry labs. 2. Ultratrace Methods *Complete development of GF-AAS and ICP methods for Co and Cr. *Initiate development of GF-AAS and ICP methods for Ni, and V. 3. Cobalamin Speciation *Complete development of sample preparation method for cobalamins. 4. Fe Speciation
*Continue development of HPLC method for Fe species extracted from meat. *Determine effect of cooking and acidification on heme Fe. *Set up in vitro digestion system to study heme Fe. *Initiate study of bioavailability of heme Fe. Year 3 (FY 2006) 1. Robust Multielement Methods *Initiate development of ICP methods for food materials. 2. Ultratrace Methods *Complete development of methods for Ni, and V. *Initiate development of in-house control materials for Co, Cr, Ni, and V. 3. Cobalamin Speciation *Initiate determination of cobalamins in foods and supplements. *Develop fresh-frozen quality control materials. 4. Fe Speciation *Continue study with in vitro digestion system for heme Fe. *Continue study of bioavailability of heme Fe. *Initiate quantification of total Fe and heme Fe in foods for database. Year 4 (FY 2007) 1. Robust Multielement Methods *Develop Association of Analytical Chemists (AOAC) method(s) for determination of multi-elements in food materials using ICP. 2.
Ultratrace Methods *Complete in-house control materials for Co, Cr, Ni, and V. *Initiate determination of Co, Cr, Ni, and V in food materials. 3. Cobalamin Speciation *Initiate development of a dietary supplement quality control material for cobalamins. 4. Fe Speciation *Finish study with in vitro digestion system for heme Fe. *Finish study of bioavailability of heme Fe. *Determine total Fe and heme Fe in foods for database. Year 5 (FY 2008) 1. Robust Multielement Methods *Complete AOAC method(s) for determination of multi-elements in food materials using ICP. 2. Ultratrace Methods *Complete determination of Co, Cr, Ni, and V in food materials 3. Cobalamin Speciation *Complete development of dietary supplement quality control material for cobalamins. 4. Fe Speciation *Determine total Fe and heme Fe in foods for database. 4a List the single most significant research accomplishment during FY 2006. This research was conducted in support of National Program 107 - Human Nutrition and
addresses performance goal 3.1.2.B "Food Composition and Consumption: Develop techniques for determining food composition, maintain national food composition databases, monitor the food and nutrient consumption of the U.S. population, and develop and transfer effective nutrition intervention strategies." Completed development of a method for the determination of heme Fe in meats, using an acidified acetone extraction with inductively coupled plasma-atomic emission spectrometridc (ICP-AES) detection. This allows Heme Fe, which is more accessible in foods, to be accurately analyzed. FCL demonstrated that only heme Fe was extracted by the acidified acetone and that Fe was accurately determined by ICP-AES after finding consistent errors with atomic absorption spectrometry. This method can be used routinely for the determination of heme Fe in meats. 4b List other significant research accomplishment(s), if any. This research was conducted in support of National Program 107 - Human
Nutrition and addresses performance goal 3.1.2.B "Food Composition and Consumption: Develop techniques for determining food composition, maintain national food composition databases, monitor the food and nutrient consumption of the U.S. population, and develop and transfer effective nutrition intervention strategies." Supported development of a new Bovine Serum Standard Reference Material in collaboration with scientist at the National Institutes of Standards and Technology. Helped analyze aluminum (Al), a particularly troublesome element because of its susceptibility to contamination. Showed that the Al concentration was 2.8 ng/mL in the new bovine material and was 2.5 ng/mL in the old material. This was significant, since the previously accepted level for the old standard was 4.0 ng/mL. This new standard will allow standardization of biological analyses. 5. Describe the major accomplishments to date and their predicted or actual impact. Participated in the characterization of two
new international food quality control (QC) materials providing trace element data to colleagues in Poland for a corn flower and a soya bean flour reference material. The materials both were fairly homogeneous and quality control data all confirm the accuracy of the determinations. The only element which led to some problems was Potassium (K) at unusually low levels (in corn starch). Developed and circulated a questionnaire to colleagues from the National Food Processor's Analytical Chemists Subcommittee regarding low level trace element methods. Information gathered includes: methods used for trace element determinations, quality control strategies, interest in fresh food QC materials, and interest in participation in a study to improve low level trace element determinations for Mn, Zn, Fe and Cu. All of the laboratories contacted are commercial analytical labs. Many are associated with food producing companies and some are contract labs but all of them generate food composition
data. The expected outcome of the study is development and technology transfer of robust methods suitable for industrial labs for the production of multielement food composition data. Another product is the production of much needed in- house food QC materials. Participated in an inter-laboratory collaborative study determining nine trace elements (Ca, Cu, Fe, Na, K, P, Mg, Zn, and Mn) in a nutritional liquid (similar to Ensure) and a cereal (similar to Cheerios). FCL are 1 of 22 laboratories that participated and FCL data were in good agreement with the mean values from the study. Developed method for heme Fe in meats that employed the classic Hornsey extraction (acidified acetone) and determined the extracted Fe using atomic absorption spectrometry. Demonstrated that the use of spectrophotometry for the determination of Fe in the Hornsey extract gave results that are biased high by 15% to 40%. Initiated development of HPLC method to separate components extracted by the Hornsey
method to verify that all the Fe was heme Fe.
Impacts
(N/A)
Publications
- Yanes Santos, E.G., Miller-Ihli, N.J. 2005. Parallel path nebulizer: critical parameters for use with microseparation techniques combined with inductively coupled plasma mass spectrometry. Spectrochimica Acta. 60:555- 561.
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Progress 10/01/04 to 09/30/05
Outputs
1. What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? What does it matter? There is an ever-increasing need for trace element food composition data. Much of the trace element data in the latest National Nutrient Database for Standard Reference was generated many years ago and needs to be updated because foods have changed. Review of the data suggests that in some cases, unsophisticated analytical methodology produced less than accurate results due to problems with contamination, matrix interference, effects or instrumental background correction strategies. Graphite furnace-atomic absorption spectrometry (GF-AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) are newer instrumental techniques that are readily available to commercial labs. All provide better detection limits for many elements as
compared to flame atomic absorption spectrometry and the latter two offer the advantage of multielement determinations, allowing for the generation of accurate data for as many as 15-20 elements simultaneously. This project is organized into four objectives: 1) development of robust multielement methods suitable of industry; 2) development of sensitive, ultratrace methods for Co, Cr, Ni, and V; 3) developement of a method for cobalamin species; and 4) development of methods for the determination of Fe species. The research to be undertaken falls under National Program 107 - Human Nutrition and addresses performance goal 3.1.2.B as described in the National Program Action Plan. Goal 3.1.2 is "Food Composition and Consumption: Develop techniques for determining food composition, maintain national food composition databases, monitor the food and nutrient consumption of the U.S. population, and develop and transfer effective nutrition intervention strategies." This project directly
addresses Priority Objective B. Develop Analytical Methodology for Nutrients. The field of nutrition and public health will benefit, in general, from an improved nutrition database for trace metals and increased knowledge regarding the concentrations and species of trace metals in foods. The field of analytical chemistry will benefit from improved methods for 1) the simultaneous determination of Mn, Zn, Fe, Cu, Mg, Ca, and P; 2) the determination of Co, Cr, Ni, and V; 3) the determination of individual cobalamin species; and 4) the determination of Fe as a porphyrin complex (heme Fe). In addition, the field of analytical chemistry will benefit from improved reference materials. 2. List the milestones (indicators of progress) from your Project Plan. Year 1 (FY 2004) Robust Multielement Methods *Develop and circulate a questionnaire for food industry analytical labs on methods for low levels of Mn, Zn, and Cu in foods. *Evaluate responses to questionnaire. Ultratrace Methods *Develop
GF-AAS and ICP methods for Co and Cr. Cobalamin Speciation *Develop method for cobalamin species using capillary electrophoresis and ICP-MS. *Start development of sample preparation method for cobalamins focusing on solid phase extraction. Fe Speciation *Acquire standards for Fe species. *Initiate development of an High Performance Liquid Chromatography (HPLC) separation method for Fe species extracted from meat. Year 2 (FY 2005) Robust Multielement Methods *Complete evaluation of questionnaire. *Develop in-house food control materials for evaluation by food industry labs. Ultratrace Methods *Complete development of GF-AAS and ICP methods for Co and Cr. *Initiate development of GF-AAS and ICP methods for Ni, and V. Cobalamin Speciation *Complete development of sample preparation method for cobalamins. Fe Speciation *Continue development of HPLC method for Fe species extracted from meat. *Determine effect of cooking and acidification on heme Fe. *Set up in vitro digestion system to
study heme Fe. *Initiate study of bioavailability of heme Fe. Year 3 (FY 2006) Robust Multielement Methods *Initiate development of ICP methods for food materials. Ultratrace Methods *Complete development of methods for Ni, and V. *Initiate development of in-house control materials for Co, Cr, Ni, and V. Cobalamin Speciation *Initiate determination of cobalamins in foods and supplements. *Develop a fresh frozen quality control materials. Fe Speciation *Continue study with in vitro digestion system for heme Fe. *Continue study of bioavailability of heme Fe. *Initiate quantification of total Fe and heme Fe in foods for database. Year 4 (FY 2007) Robust Multielement Methods *Develop Association Of Analytical Chemists (AOAC) method(s) for determination of food materials using ICP. Ultratrace Methods *Complete in-house control materials for Co, Cr, Ni, and V. *Initiate determination of Co, Cr, Ni, and V in food materials. Cobalamin Speciation *Initiate development of a dietary supplement
quality control material for cobalamins. Fe Speciation *Finish study with in vitro digestion system for heme Fe. *Finish study of bioavailability of heme Fe. *Determine total Fe and heme Fe in foods for database. Year 5 (FY 2008) Robust Multielement Methods *Complete AOAC method(s) for determination of food materials using ICP. Ultratrace Methods *Complete determination of Co, Cr, Ni, and V in food materials Cobalamin Speciation *Complete development of dietary supplement quality control material for cobalamins. Fe Speciation *Determine total Fe and heme Fe in foods for database. 3a List the milestones that were scheduled to be addressed in FY 2005. For each milestone, indicate the status: fully met, substantially met, or not met. If not met, why. 1. Robust Multielement Methods *Evaluation of questionnaire. *Develop in-house food control materials for evaluation by food industry labs. Milestone Not Met Critical SY Vacancy 2. Ultratrace Methods *Develop of GF-AAS and ICP methods for
Co and Cr. *Develop of GF-AAS and ICP methods for Ni, and V. Milestone Not Met Critical SY Vacancy 3. Cobalamin Speciation *Develop of sample preparation method for cobalamins. Milestone Not Met Critical SY Vacancy 4. Fe Speciation *Continue development of HPLC method for Fe species extracted from meat. *Determine effect of cooking and acidification on heme Fe. *Set up in vitro digestion system to study heme Fe. *Initiate study of bioavailability of heme Fe. Milestone Fully Met 3b List the milestones that you expect to address over the next 3 years (FY 2006, 2007, and 2008). What do you expect to accomplish, year by year, over the next 3 years under each milestone? FY 2006 Robust Multielement Methods - no plans for completion, Principle Investigator (PI) took medical retirement Ultratrace Methods - no plans for completion, PI took medical retirement Cobalamin Speciation *Initiate determination of cobalamins using heme Fe extraction method and AAS and HPLC determination. Fe Speciation
*Continue study with in vitro digestion system for heme Fe. *Continue study of bioavailability of heme Fe. *Initiate quantification of total Fe and heme Fe in foods for database. FY 2007 Robust Multielement Methods - no plans for completion, PI took medical retirement Ultratrace Methods - no plans for completion, PI took medical retirement Cobalamin Speciation *Initiate development of a dietary supplement quality control material for cobalamins. Fe Speciation *Finish study with in vitro digestion system for heme Fe. *Finish study of bioavailability of heme Fe. *Determine total Fe and heme Fe in foods for database. FY 2008 Robust Multielement Methods - no plans for completion, PI took medical retirement Ultratrace Methods - no plans for completion, PI took medical retirement Cobalamin Speciation *Continue development for cobalamins in foods. Fe Speciation *Determine total Fe and heme Fe in foods for database. Due to the unexpected retirement of the PI in 2004, some goals of this
project will be abandoned. We plan to rework the team projects of the Lab in the next year to make maximum use of new personnel and changes in program priorities. 4a What was the single most significant accomplishment this past year? Developed a method for the determination of heme Fe in meats using an acidified acetone extraction with HPLC-diode array detection. Heme Fe is more accessible in foods but a definitive method is lacking and there is no database for heme Fe. This method allows for the conclusive identification of heme Fe using the HPLC retention time and the molecular spectra and mass balance is achieved by comparing the Fe in the sample with the sum of the Fe in the extract and the remaining solids. This method will allow us to establishe a heme Fe database based on a nation wide sampling program implemented by the Nutrient Data Lab. 4d Progress report. Determined the effect of cooking on the integrity of myogolbin Fe and heme Fe in meats. This research addresses the
question of what form of Fe reaches the small intestine. Initial results suggest that 100% of the myoglobine Fe is denatured and 30% of the heme Fe is destroyed. Collaborated with the Plant, Soil, and Nutrition Lab in Ithaca, NY, on evaluation of cooking on the bioavailability. Bile juices are critical to solubilizing heme Fe after denaturation of the myoglobin after cooking. 5. Describe the major accomplishments over the life of the project, including their predicted or actual impact. Participated in the characterization of two new international food quality control materials providing trace element data to colleagues in Poland for a corn flower and a soya bean flour reference material. The materials both were fairly homogeneous and QC data all confirm the accuracy of the determinations. The only element which led to some problems was K at unusually low levels (in corn starch). Developed and circulated a questionnaire to colleagues from the National Food Processor's Analytical
Chemists Subcommittee regarding low level trace element methods. Information gathered includes: methods used for trace element determinations, quality control strategies, interest in fresh food QC materials, and interest in participation in a study to improve low level trace element determinations for Mn, Zn, Fe and Cu. All of the laboratories contacted are commercial analytical labs. Many are associated with food producing companies and some are contract labs but all of them generate food composition data. The expected outcome of the study is development and technology transfer of robust methods suitable for industrial labs for the production of multielement food composition data. Another product is the production of much needed in- house food QC materials. Participated in an interlaboratory collaborative study determining nine trace elements (Ca. Cu, Fe, Na, K, P, Mg, Zn, and Mn) in a nutritional liquid (similar to Ensure) and a cereal (similar to Cheerios). We were 1 of 22
laboratories who participated and our data were in good agreement with the mean values from the study. Developed method for heme Fe in meats that employed the classic Hornsey extraction (acidified acetone) and determined the extracted Fe using atomic absorption spectrometry. Demonstrated that the use of spectrophotometry for the determination of Fe in the Hornsey extract gave results that are biased high by 15% to 40%. Initiated development of HPLC method to separate components extracted by the Hornsey method to verify that all the Fe was heme FE.
Impacts
(N/A)
Publications
- Yanes Santos, E.G., Miller-Ihli, N.J. 2005. Parallel path nebulizer: critical parameters for use with microseparation techniques combined with inductively coupled plasma mass spectrometry. Spectrochimica Acta. 60:555- 561.
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Progress 10/01/03 to 09/30/04
Outputs
1. What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? What does it matter? There is an ever-increasing need for trace element food composition data. Much of the trace element data in the latest National Nutrient Database for Standard Reference was generated many years ago and needs to be updated because foods have changed. Review of the data suggests that in some cases, unsophisticated analytical methodology produced less than accurate results due to problems with contamination, matrix interference, effects or instrumental background correction strategies. Graphite furnace-atomic absorption spectrometry (GF-AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) are newer instrumental techniques that are readily available to commercial labs. All provide better detection limits for many elements as
compared to flame atomic absorption spectrometry and the latter two offer the advantage of multielement determinations, allowing for the generation of accurate data for as many as 15-20 elements simultaneously. This project is organized into four objectives: 1) development of robust multielement methods suitable of industry; 2) development of sensitive, ultratrace methods for Co, Cr, Ni; and V, 3) developement of a method for cobalamin species; and 4) development of methods for the determination of Fe species. The research to be undertaken falls under National Program 107 - Human Nutrition and addresses performance goal 3.1.2.B, as described in the National Program Action Plan. Goal 3.1.2 is "Food Composition and Consumption: Develop techniques for determining food composition, maintain national food composition databases, monitor the food and nutrient consumption of the U.S. population, and develop and transfer effective nutrition intervention strategies." This project directly
addresses Priority Objective B. Develop Analytical Methodology for Nutrients. The field of nutrition and public health will benefit, in general, from an improved nutrition database for trace metals and increased knowledge regarding the concentrations and species of trace metals in foods. The field of analytical chemistry will benefit from improved methods for 1) the simultaneous determination of Mn, Zn, Fe, Cu, Mg, Ca, and P; 2) the determination of Co, Cr, Ni, and V; 3) the determination of individual cobalamin species; and 4) the determination of Fe s a porphyrin complex (heme Fe). In addition, the field of analytical chemistry will benefit from improved reference materials. 2. List the milestones (indicators of progress) from your Project Plan. Year 1 (FY 2004) Robust Multielement Methods: * Develop and circulate a questionnaire for food industry analytical labs on methods for low levels of Mn, Zn, and Cu in foods. * Evaluate responses to questionnaire. Ultratrace Methods: *
Develop GF-AAS and ICP methods for Co and Cr. Cobalamin Speciation: * Develop method for cobalamin species using capillary electrophoresis and ICP-MS. * Start development of sample preparation method for cobalamins focusing on solid phase extraction. Fe Speciation: * Acquire standards for Fe species. * Initiate development of an HPLC separation method for Fe species extracted from meat. Year 2 (FY 2005) Robust Multielement Methods: * Complete evaluation of questionnaire. * Develop in-house food control materials for evaluation by food industry labs. Ultratrace Methods: * Complete development of GF-AAS and ICP methods for Co and Cr. * Initiate development of GF-AAS and ICP methods for Ni, and V. Cobalamin Speciation: * Complete development of sample preparation method for cobalamins. Fe Speciation: * Continue development of HPLC method for Fe species extracted from meat. * Determine effect of cooking and acidification on heme Fe. * Set up in vitro digestion system to study
heme Fe. * Initiate study of bioavailability of heme Fe. Year 3 (FY 2006) Robust Multielement Methods: * Initiate development of ICP methods for food materials. Ultratrace Methods: * Complete development of methods for Ni, and V. * Initiate development of in-house control materials for Co, Cr, Ni, and V. Cobalamin Speciation: * Initiate determination of cobalamins in foods and supplements. * Develop a fresh frozen quality control materials. Fe Speciation: * Continue study with in vitro digestion system for heme Fe. * Continue study of bioavailability of heme Fe. * Initiate quantification of total Fe and heme Fe in foods for database. Year 4 (FY 2007) Robust Multielement Methods: * Develop AOAC method(s) for determination of food materials using ICP. Ultratrace Methods: * Complete in-house control materials for Co, Cr, Ni, and V. * Initiate determination of Co, Cr, Ni, and V in food materials. Cobalamin Speciation: * Initiate development of a dietary supplement quality
control material for cobalamins. Fe Speciation: * Finish study with in vitro digestion system for heme Fe. * Finish study of bioavailability of heme Fe. * Determine total Fe and heme Fe in foods for database. Year 5 (FY 2008) Robust Multielement Methods: * Complete AOAC method(s) for determination of food materials using ICP Ultratrace Methods: * Complete determination of Co, Cr, Ni, and V in food materials Cobalamin Speciation: * Complete development of dietary supplement quality control material for cobalamins. Fe Speciation: * Determine total Fe and heme Fe in foods for database. 3. Milestones: A. List the milestones (from the list in Question #2) that were scheduled to be addressed in FY 2004. How many milestones did you fully or substantially meet in FY 2004 and indicate which ones were not fully or substantially met, briefly explain why not, and your plans to do so. Year 1 (FY 2004) Robust Multielement Methods: * Develop and circulate a questionnaire for food industry
analytical labs on methods for low levels of Mn, Zn, and Cu in foods. * Evaluate responses to questionnaire. Ultratrace Methods: * Develop GF-AAS and ICP methods for Co and Cr. Cobalamin Speciation: * Develop method for cobalamin species using capillary electrophoresis and ICP-MS. * Start development of sample preparation method for cobalamins focusing on solid phase extraction. Fe Speciation: * Acquire standards for Fe species. * Initiate development of an HPLC separation method for Fe species extracted from meat. The milestones for the first three objectives were not completed due to extended illness of the principle investigator. All milestones for Fe Speciation were completed. B. List the milestones (from the list in Question #2) that you expect to address over the next 3 years (FY 2005, 2006, & 2007). What do you expect to accomplish, year by year, over the next 3 years under each milestone? Year 2 (FY 2005) Robust Multielement Methods: * Complete evaluation of
questionnaire. * Develop in-house food control materials for evaluation by food industry labs. Ultratrace Methods: * Complete development of GF-AAS and ICP methods for Co and Cr. * Initiate development of GF-AAS and ICP methods for Ni, and V. Cobalamin Speciation: * Complete development of sample preparation method for cobalamins. Fe Speciation: * Continue development of HPLC method for Fe species extracted from meat. * Determine effect of cooking and acidification on heme Fe. * Set up in vitro digestion system to study heme Fe. * Initiate study of bioavailability of heme Fe. Year 3 (FY 2006) Robust Multielement Methods: * Initiate development of ICP methods for food materials. Ultratrace Methods: * Complete development of methods for Ni, and V. * Initiate development of in-house control materials for Co, Cr, Ni, and V. Cobalamin Speciation: * Initiate determination of cobalamins in foods and supplements. * Develop a fresh frozen quality control materials. Fe Speciation:
* Continue study with in vitro digestion system for heme Fe. * Continue study of bioavailability of heme Fe. * Initiate quantification of total Fe and heme Fe in foods for database. Year 4 (FY 2007) Robust Multielement Methods: * Develop AOAC method(s) for determination of food materials using ICP. Ultratrace Methods: * Complete in-house control materials for Co, Cr, Ni, and V. * Initiate determination of Co, Cr, Ni, and V in food materials. Cobalamin Speciation: * Initiate development of a dietary supplement quality control material for cobalamins. Fe Speciation: * Finish study with in vitro digestion system for heme Fe. * Finish study of bioavailability of heme Fe. * Determine total Fe and heme Fe in foods for database. Completion of the first three goals is now in question because of the health problems of the principle investigator. The investigator has applied for a disability retirement. When possible, the investigator will be replaced. While the goals are still valid,
they will undoubtedly be altered when a new scientist is recruited. The goals for Fe speciation are being pursued and are of considerable interest to the nutritional community. 4. What were the most significant accomplishments this past year? A. Single most significant accomplishment during FY 2004: The wide disparity of results coming from different labs and different analytical methods jeopardizes the reliability of low level trace element results in the USDA nutrient database. A questionnaire was developed and circulated to analytical laboratories that are members of the National Food Processor's Analytical Chemists Subcommittee regarding their choice of methods. This information will be used to develop appropriate, robust analytical methods and quality control materials suitable for industrial labs for the production of multielement food composition data. The result will be more accurate and reliable data for foods. B. Other significant accomplishments: None. C. Significant
accomplishments/activities that support special target population: None. D. Progress Report: Participated in an inter-laboratory collaborative study determining nine trace elements (Ca, Cu, Fe, Na, K, P, Mg, Zn, and Mn) in a nutritional liquid (similar to Ensure) and a cereal (similar to Cheerios). We were 1 of 22 laboratories who participated and our data were in good agreement with the mean values from the study. Participated in the characterization of two new international food quality control materials providing trace element data to colleagues in Poland for a corn flower and a soya bean flour reference material. The materials both were fairly homogeneous and QC data all confirm the accuracy of the determinations. The only element which led to some problems was K at unusually low levels (in corn starch). Developed method for heme Fe in meats that employed the classic Hornsey extraction (acidified acetone) and determined the extracted Fe using atomic absorption spectrometry.
Demonstrated that the use of spectrophotometry for the determination of Fe in the Hornsey extract gave results that are biased high by 15% to 40%. Initiated development of HPLC method to separate components extracted by the Hornsey method to verify that all the Fe was heme FE. 5. Describe the major accomplishments over the life of the project, including their predicted or actual impact. Same response as to question 4A. This is the first year of a new CRIS project. 7. List your most important publications in the popular press and presentations to organizations and articles written about your work. A better measure for B12. 2004. Agricultural Research, Feb., p.23.
Impacts
(N/A)
Publications
- Yanes Santos, E.G., Miller-Ihli, N.J. 2004. Use of a parallel path nebulizer for capillary-based microseparation techniques coupled with an inductively coupled plasma mass spectrometer for speciation measurements. Spectrochimica Acta. 59:883-890
- Yanes Santos, E.G., Miller-Ihli, N.J. 2004. Cobalamin speciation using reversed phase micro high-performance liquid chromatography interfaced to inductively coupled plasma mass spectrometry. Spectrochimica Acta. 59:891- 899.
- Miller-Ihli, N.J., Pehrsson, P.R., Cutrufelli, R.L., Holden, J.M. 2004. Fluoride content of municipal water in the united state: What percentage is fluoridated?. Journal of Food Composition and Analysis. 16:621-628
- Yanes Santos, E.G., Miller-Ihli, N.J. 2004. Characterization of microconcentric nebulizer uptake rates for capillary electrophoresis inductively coupled plasma mass spectrometry. Spectrochimica Acta. 58:949- 955
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