Kenneth R. Neubauer is with perkinElmer LAS, Shelton, Connecticut.

Kenneth Neubauer

Elemental analysis of food substances presents a challenge because of the wide variety of food types and range of concentrations that need to be analyzed. The complexity of food matrices requires digestion to both break down the matrix and to convert solids into liquids for analysis. ICP-MS has the ability to measure both trace and elevated analyte levels during the same analysis, while the use of cell-based ICP-MS systems can remove the effects of interferences, allowing lower levels to be determined. This article discusses the analysis of a variety of food matrices with a single digestion procedure and instrumental method. 

Food safety is an area of growing concern as a result of pollution, which can enter the food supply and be passed along to consumers, leading to health problems. Therefore, it is important that all food types are monitored for contaminants and toxic elements. It is also equally important to monitor levels of nutritionally significant elements, which are present at elevated levels. Much work has been done on the analysis of food substances with inductively coupled plasma–mass spectrometry (ICP-MS) (1–9). 

To establish analytical conditions for the determination of metals in a variety of food types, several food standard reference materials have been analyzed for both elevated and trace elemental content using ICP-MS. Emphasis was placed on finding a single set of sample preparation and analytical conditions that would be applicable to a number of different food matrices.  

Table I: Standard reference materials analyzed 

The samples analyzed in this study were all standard reference materials from NIST (Gaithersburg, Maryland) and represent a variety of food types. Table I shows the materials analyzed. Approximately 0.5 g of sample was digested in triplicate (along with a blank) with 4 mL of Optima-grade HNO

 (Fisher Scientific, Pittsburgh, Pennsylvania) and 2 mL of Optima-grade H

 (Fisher Scientific) in a Multiwave 3000 microwave digestion system (Anton Paar, Graz, Austria). Precleaned HF-100 vessels were used in a 16-position rotor. A pressure–temperature sensor was used to monitor the pressure and temperature of the sample in position 1 of the rotor. The external infrared sensor provided the temperatures for each individual sample in the rotor. The digestion program consisted of 30 min of heating and 15 min of cooling, as shown in Table II. The samples were dissolved completely, resulting in clear solutions that were diluted with 1% HNO

Mixed element calibration standards of appropriate concentrations were prepared from PerkinElmer Pure multielement and single element standards (PerkinElmer LAS, Shelton, Connecticut) in 1% HNO

. The following internal standard mix was spiked into each sample, blank, and standard: Sc, Ga, In, and Tm.  

All analyses were performed on an ELAN DRC II (PerkinElemerSciex, Concord, Ontario, Canada); instrumental parameters appear in Table III.  

Most elements were analyzed in standard mode (that is, no reaction gas in the cell). However, those elements that suffered from interferences were measured in dynamic reaction cell (DRC) mode using oxygen and ammonia as the reaction gases. Because no elements were certified in the sucrose sample, spike recoveries of common elements were measured.  

Table V: Analysis of NIST 8433: Corn Bran 

Sodium and potassium were measured in standard mode, but with a different Rpa (DC voltage) than other elements. Both of these elements were present at high concentrations in the final solution and are either monoisotopic (Na) or greater than 90% natural abundance at the primary isotope (

K). As a result, it could be difficult to measure these elements in the same sample along with elements present in the low microgram-per-liter range. If the sample is not diluted adequately, Na and K could saturate the detector. If the sample is diluted too much, the other trace elements cannot be measured.  

Table VI: Analysis of NIST 8436: Durum Wheat Flour 

To solve this problem, the signals from sodium and potassium were attenuated selectively without affecting the sensitivity of other elements (10). This was accomplished by increasing the RPa on the reaction cell quadrupole only for sodium and potassium. Varying the RPa value changes the amount of the attenuation, effectively extending the dynamic range. Table IV shows the reaction cell parameters for the analytes measured in DRC and extended dynamic range modes.  

Table VII: Analysis of NIST 8414: Bovine Muscle Powder 

All quantitative measurements were made against aqueous, external three- or five-point calibration curves.    

Table VIII: Analysis of NIST 2976: Mussel Tissue 

Tables V–X show results for the various food matrices analyzed. The majority of results are within the certified ranges, demonstrating the robustness and applicability of the methodology for various food types.  

Table IX: Analysis of NIST 1549: Nonfat Milk Powder 

This work has demonstrated the ability to analyze a variety of food samples accurately for elements present at both trace and nutritional levels. A single microwave digestion procedure and ICP-MS method were used for all samples, demonstrating their robustness and flexibility. The ability to attenuate the intensities of specific elements selectively without affecting other isotopes allows for the analysis of both trace and high-level analytes to be performed using a single dilution. The analytical results show that microwave digestion followed by ICP-MS analysis effectively measures both toxic and nutritional elements in a variety of food matrices.  

 are with PerkinElmer, Waltham, Massachusetts. 

(2)  M. Resano, E. Garcia-Ruiz, L. Moens, and F. Vanhaecke, 

(3)  R.B. Myors, R. Hearn, and L.G. Mackay, 

(4)  M. Shah, R.G. Wuilloud, S.S. Kannamkumarath, and J.A. Caruso, 

(5)  C. Fragniere, M. Haldimann, A. Eastgate, and U. Krahenbuhl, 

(6)  C.R. Quetel, J.P. Snell, Y. Aregbe, L. Abranko, Zs. Jokai, C. Brunori, R. Morabito, W. Hagan, S. Azemard, E. Wyse, V. Fajon, M. Horvat, M. Logar, O.F.X. Donard, E. Krupp, J. Entwisle, R. Hearn, M. Schantz, K. Inagaki, A. Takatsu,P. Grinberg, S. Willie, B. Dimock, H. Hintelmann, J. Zhu, E. Blanco Gonzalez, G. Centineo, J. Ignacio Garcia Alonso, A. Sanz-Medel, and E. Bjorn, 

(7)  D. Hammer, M. Nicolas, and D. Andrey, 

(8)  W. Dufalilly, L. Noel, and T. Guerin, 

(9)  M.A. Knopp, F. Chan, and K.R. Neubauer, Analysis of Food Substances with Dynamic Reaction Cell ICP-MS, PerkinElmer Field Application Report, 2004. 

(10) F. Abou-Shakra, "Extending the Dynamic Range of the ELAN DRC by Selective Attenuation of High Signal" PerkinElmer Field Application Report 007437_01 (2005). 

Articles

Elemental analysis of food substances presents a challenge because of the wide variety of food types and range of concentrations that need to be analyzed. This article discusses the analysis of a variety of food matrices with a single digestion procedure and instrumental method.

The Analysis of Food Substances by ICP-MS

Geochemists represent some of the most demanding users of inductively coupled plasma mass spectrometry (ICP-MS). Invariably they are looking for ultratrace levels in the presence of large concentrations of major elements in digested rock samples. This alone presents difficulties for the sample introduction and interface region because of the potential for signal drift caused by the geological material depositing on the cones and ion lens system (1). In addition, if there are large concentrations of high-mass elements present in the sample, they can cause severe matrix suppression on the analyte masses (2). Another potential problem is that major and trace components in the sample can combine with argon-, solvent-, and acid-based species to produce quite severe polyatomic, isobaric, doubly charged, and oxide-based spectral interferences (3). When this is combined with the extremely demanding sample preparation methods using highly corrosive materials like concentrated aqua regia (hydrochloric acid–nitric acid, HCl/HNO

), hydrofluoric acid (HF), and fusion mixtures to dissolve the samples, the result is that geological matrices are some of the most difficult to analyze by ICP-MS. 

The determination of low levels of precious metals was one of the very first applications that attracted geochemists to ICP-MS (4), mainly because of the lengthy sample preparation and analysis times involved with previously used techniques including atomic absorption (AA), ICP-optical emission spectrometry (OES) and neutron activation analysis (NAA) (5, 6). However, even though ICP-MS offered significant benefits over these techniques, it was not without its problems because of the potential for spectral interferences from matrix components in the sample. In addition, refractory and rare earth elements in rocks, minerals, and natural water samples have a tendency to readily form oxide species, which potentially could interfere with the precious metal analytes. For that reason, instrument parameters usually need to be optimized, depending upon the analyte levels being determined and the kinds of interferences present in the sample.  

 Figure 1. Optimized NH3 reaction gas flow rates for 101Ru, showing nickel-copper-chloride matrix (green), matrix plus 0.5 Âµ/L analyte (blue) and calculated background equivalent concentration (BEC) (red).						

For example, plasma power and nebulizer gas flows often need to be adjusted to minimize the formation of oxide species. This is necessary because an oxide or hydroxide species of one element can interfere spectrally with the analyte element. The problem can be alleviated by using a sample desolvation device, such as a chilled spray chamber, to reduce oxide formation but unfortunately cannot be eliminated completely. For that reason, to obtain the best detection capability for precious metals in geological matrices, instrument sensitivity often must be sacrificed in order to maximize the reduction of oxide and other spectral interferences and even then, mathematical correction equations often have to be applied (7).  

However, with the recent development of collision–reaction cell technology to reduce or avoid the formation of problematic polyatomic spectral interferences, geochemists have another powerful analytical tool at their disposal. Commercialized about five years ago, collision–reaction cells have proven themselves to be an extremely useful addition to quadrupole technology to reduce the effects of troublesome matrix and argon-derived polyatomic interferences (8).  			

Initially used to improve the detection capability of semiconductor-significant elements such as Fe, Ca, and K (9), collision–reaction cell technology has expanded its applicability to other elements and has gained wider acceptance in the environmental (10) and clinical application segments (11). As more and more applications move into the public domain, geochemists are beginning to take an interest in collision–reaction cells to reduce the formation of the myriad of spectral interferences associated with the determination of low analyte levels in rocks and mineral samples. 

One such development that is gaining a great deal of attention because of its interference reduction capabilities, is dynamic reaction cell (DRC) technology. The dynamic reaction cell, which previously has been described in the open literature (12), is a pressurized quadrupole positioned before the analyzer quadrupole. A highly reactive gas such as ammonia (NH

) is supplied to the cell, where ion-molecule chemistry takes place. Through various reaction mechanisms, the gaseous molecules react with the interfering ions to convert them either into species of different mass than the analyte or form an ionic complex–cluster with the analyte at a higher mass than the interfering ion. The analyte ion then emerges from the dynamic reaction cell free of its interference and enters the analyzer quadrupole for conventional mass separation. 

The advantages of using a quadrupole in the reaction cell for geological-type samples is that the ion stability regions are well defined compared with higher order multipoles used in simple collision cells. As a result, the quadrupole inside the reaction cell can be operated with a narrower mass transmission window, not as just an ion guide. Therefore, by optimization of the quadrupole electrical fields (known as dynamic bandpass tuning), unwanted reactions between the gas and the geological sample matrix and solvent, which can generate new interferences, are prevented, while transmission of the analyte ions is not affected. Every time an analyte and interfering ion enters the dynamic reaction cell, the dynamic bandpass of the quadrupole is optimized automatically for that specific analysis and then changed on-the-fly for the next analyte. The added benefit of this approach for multielement analysis is that the instrument can be operated in both DRC and normal modes. By incorporating stabilization times in the method, different gases (and gas flows) can be used for the DRC elements, while the normal (non-DRC) mode can be used for the other elements in the same multielement run. 

An ELAN DRC II (PerkinElmer SCIEX, Concord, ON, Canada) was used to carry out an investigation into the determination of the platinum group elements (PGE) in two notoriously difficult matrices, copper-bearing ores and precious metal-containing minerals. In the case of copper ores, which are digested in concentrated hydrochloric acid to remove the copper, high levels of chloride, copper and nickel ions together with argon ions from the plasma form polyatomic complexes, which interfere with the determination of rhodium, ruthenium, and palladium. This is emphasized in Table I, which shows some of the most common polyatomic spectral interferences in a copper–nickel chloride matrix and the PGE they potentially can interfere with.  

Table I. The major isotopes of ruthenium, rhodium, and palladium together with some of the most common polyatomic spectral interferences in a copper-nickel chloride matrix.						

In the analysis of digested minerals, the refractory metals hafnium, zirconium, and tantalum readily form oxides and interfere with the isotopes of palladium, gold, and platinum. This is shown in Table II.  

Table II. Isotopes of palladium, gold, and platinum with potential refractory metal oxide interferences.			

To test the capability of the dynamic reaction cell to reduce or avoid the interferences expected in a copper ore, a synthetic sample was prepared containing 0.5 µ/L of ruthenium, rhodium, and palladium dissolved in a matrix of 80 mg/L Ni and 40 mg/L Cu in 1% HCl, which represented typical analyte and matrix levels in solution. 							

To test the instrument's ability to reduce or avoid refractory oxide interferences in a digested rock, a synthetic sample was prepared containing approximately 0.5 µ/L of palladium, gold and platinum in 2 µ/L of Ta and Hf, together with 200 µ/L Zr in 0.5% HCl–0.33% HNO

, which represented typical analyte and matrix levels in solution.   

Table III. Sampling conditions for both the copper-nickel chloride and digested rock matrices.

The sample introduction components and conditions for both sample-types are shown in Table III. These instrumental conditions then were used to optimize the gas flows and quadrupole electrical fields in order to maximize the number of analyte ions and reduce the formation of interfering species in the dynamic reaction cell. 			

DRC Optimization of Copper-Nickel-Chloride Matrix

In a series of experiments, which are beyond the scope of this study, ammonia was chosen as the reaction gas to reduce the formation of the kinds of Cu-Ni-Cl polyatomic spectral interferences shown in Table I. In these experiments, 

Pd were selected as the best isotopes to continue the investigation. The optimized NH

 reaction gas flow rates for the nickel–copper–chloride matrix (green), matrix plus 0.5 µ/L analytes (blue) and calculated background equivalent concentration (BEC) (red) for all three masses, are shown in Figures 1–3 respectively.  

Figure 2. Optimized NH3 reaction gas flow rates for 103Rh, showing nickel-copper-chloride matrix (green), matrix plus 0.5 Âµ/L analyte (blue) and calculated BEC (red).						

It can be seen in all three plots that as the NH

 reaction gas flow rate increases, the sensitivity of the analyte in the matrix (blue plot) also increases (up to about 0.5–0.6 mL/min), while the background of the matrix (green plot) decreases gradually. At about 1 mL/min gas flow, the analyte signal compared with background appears to be at a maximum and as a result the calculated BEC (red plot) is at its lowest. It can be seen from the plots that both ruthenium and rhodium generated single-digit ppt BEC values, while palladium was slightly high at 10–20 ppt.  

Figure 3. Optimized NH3 reaction gas flow rates for 105Pd, showing nickel-copper-chloride matrix (green), matrix plus 0.5 Âµ/L analyte (blue), and calculated BEC (red).			

It should be noted that BEC is defined as the apparent concentration for the background signal based upon the sensitivity of the element at a specified mass. The lower the BEC value, the more easily a signal generated by an element can be discerned from the background. Many analysts believe that the BEC is a more accurate indicator of the performance of an ICP-MS system, particularly as a means of comparing background reduction techniques (13).  

Figure 4. Optimized CH3F reaction gas flow rates for 105Pd, showing the Ta-Hf-Zr acid matrix (green), matrix plus 0.5 Âµ/L analyte (blue), and calculated BEC (red).			

DRC Optimization of Digested Rock–Refractory Element Matrix

In another series of experiments, which also are beyond the scope of this study, methyl fluoride (CH

F) was chosen as the reaction gas to minimize the impact of the kinds of refractory oxide polyatomic spectral interferences described earlier. To overcome these interference problems, the CH

F reaction gas is utilized in two different ways. First, it is used to break up the 

 for quantitation. However, for the quantitation of gold and platinum, advantage is taken of the DRC's ability to measure gold and platinum cluster ions, 

 at 226 amu, respectively. This use of ion-molecule chemistry (14) avoids the hafnium and tantalum oxides, which interfere spectrally with monoisotopic gold and the major isotopes of platinum, as shown in Table II.  

Figure 5. Optimized CH3F reaction gas flow rates for  197 Au 12 CH319 F + , showing the Ta-Hf-Zr acid matrix (green), matrix plus 0.5 Âµ/L analyte (blue), and calculated BEC (red).						

F gas flow optimization plots for all three masses are shown in Figures 4–6. The background intensity of the matrix composed of 2 µ/L Ta, 2 µ/L Hf and 200 µ/L Zr in 0.5% HCl–0.33% HNO

 is shown by the green line. The intensity of the matrix spiked with 0.5 µ/L of the analyte is shown by the blue line, while the calculated BEC from these two signals is represented by the red line.  

Figure 6. Optimized CH3F reaction gas flow rates for 194Pt12CH19F+ showing the Ta-Hf-Zr acid matrix (green), matrix plus 0.5 Âµ/L analyte (blue), and calculated BEC (red).			

It can be seen in all three plots that as the CH

F reaction gas flow rate increases the sensitivity of the analyte in the matrix (blue plot) also increases, while the background of the matrix (green plot) gradually decreases. In the case of the optimization of palladium and gold, the best BEC value (red plot) is obtained at 1.4–1.5 mL/min. However, with platinum, the lowest BEC value (red plot) is reached at a much lower gas flow (approx 0.5 mL/min). At the optimum gas flows, palladium and platinum generated BEC's in the single-digit ppt range, while gold was slightly higher at 10–20 ppt. This means that in a multielement run, to achieve the best detection capability, Pd and Au would in all probability be measured at the same reaction gas flow of 1.5 mL/min, while Pt would be determined at a much lower rate of 0.5 mL/min. 

The potential for signal drift, matrix suppression, and spectral interference, in addition to demanding sample preparation, can make geological matrices some of the most difficult to analyze by conventional inductively coupled plasma-mass spectrometry.

Kenneth Neubauer

Articles

The Analysis of Food Substances by ICP-MS

Reducing the Impact of Spectral Interferences on the Determination of Precious Metals in Complex Geological Matrices Using DRC ICP-MS