SPOTLIGHT           ON APPLICATIONS.           FOR A BETTER           TOMORROW.VOLUME 1
INTRODUCTIONPerkinElmer Spotlight on Applications e-Zine – Volume 1PerkinElmer knows that the right training, methods, app...
CONTENTSChildren’s Product Safety• Determination of Formaldehyde Content in Toys using UV/Vis Spectrometry• Determination ...
a p p l i c at i o n n o t e                                                                                    Children’s...
Experimental                                                                The concentration of formaldehyde was found to...
Absorbance measurements were done between 35 minutesand 60 minutes from the time when the conical flasks wereplaced in a w...
Sample analysis: Three different toy samples, as shown in                                                                 ...
a p p l i c at i o n n o t e                                                                                  Children’s P...
Experimental                                                                         Absorbance measurement of calibration...
Method detection limit: 10 replicate reagent blank solutions  Table 3. Replicate spike recoveries.                        ...
ConclusionThe LAMBDA XLS+ UV/Vis spectrometer can be used tomeasure Cr(VI) contents in toys. The detection limit is suffic...
A P P L I C AT I O N                N O T e                                                                               ...
As a result of the health concerns over human exposure to BPA                  Results    this molecule is now monitored i...
Figure 4: Analysis of toy dwarf for BPA using water.The extraction procedure which heated the toy for 24 hours inwater at ...
applIcatIon note                                                                     Childrens Products                   ...
A variety of techniques can be used to meet the regula-                                 of children’s products, including ...
Samples were prepared for ICP-OES analysis by scraping                      elements over a wide dynamic concentration ran...
Table 5. Estimated Detection Limits.       Element                     Detection Limit         Detection Limit            ...
conclusion                                                                                                                ...
a p p l i c at i o n n o t e                                                                         ICP-OES              ...
Introduction                                                                  The analytical test methods found in SW-846 ...
Summary of Method 6010CTable I. Wavelengths Monitored and Viewing Modes Used forSW-846 6010C.                             ...
Batch Quality Control Samples                                    Initial Performance Demonstration    1. Analyze the Metho...
Linear RangeTable III. Instrument Detection Limit (IDL) Data and Linear Dynamic Ranges (LDR).Analyte       Wavelength   ID...
Figure 2. Above figures show the rinse out time using the ESI FAST system. Al, Ca, Mg, and Na were run at 500 mg/L. Fe was...
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Spotlight on Analytical Applications Complete e-Zine Vol. 1
Upcoming SlideShare
Loading in …5
×

Spotlight on Analytical Applications Complete e-Zine Vol. 1

3,078 views

Published on

This document provides key analytical applications to help laboratories address the pressing concerns of the changing global landscape. Specifically, Volume 1 includes applications for Children's Product Safety, Environmental, Food & Beverage and Semiconductor.

Published in: Technology, Health & Medicine
0 Comments
1 Like
Statistics
Notes
  • Be the first to comment

No Downloads
Views
Total views
3,078
On SlideShare
0
From Embeds
0
Number of Embeds
2
Actions
Shares
0
Downloads
20
Comments
0
Likes
1
Embeds 0
No embeds

No notes for slide

Spotlight on Analytical Applications Complete e-Zine Vol. 1

  1. 1. SPOTLIGHT ON APPLICATIONS. FOR A BETTER TOMORROW.VOLUME 1
  2. 2. INTRODUCTIONPerkinElmer Spotlight on Applications e-Zine – Volume 1PerkinElmer knows that the right training, methods, applications, reporting andsupport are as integral to getting answers as the instrumentation. That’s whyPerkinElmer has developed a novel approach to meet the challenges that today’slabs face – that approach is called EcoAnalytix™, delivering you complete solutionsfor your applications challenges.In this effort, we are pleased to introduce to you our new Spotlight on Applicationse-Zine, delivering a variety of topics which address the pressing issues and analysischallenges you may face in your application areas today.Our Spotlight on Applications e-Zine consists of a broad range of applicationsyou’ll be able to access at your convenience. Each application in the table of contentsincludes an embedded link which will take you directly to the appropriate pagewithin the e-Zine.PerkinElmer
  3. 3. CONTENTSChildren’s Product Safety• Determination of Formaldehyde Content in Toys using UV/Vis Spectrometry• Determination of Hexavalent Chromium in Toys using UV/Vis Spectrometry• UHPLC Separation and Detection of Bisphenol A in Plastics• Lead & Other Toxic Metals in Toys Using XRF Screening and ICP-OES Quantitative AnalysisEnvironmental• Increased Laboratory Productivity for ICP-OES Applied to U.S. EPA Method 6010C• Increased Sample Throughput for ICP-OES Applied to U.S. EPA Method 200.7• Determination of Total Mercury in Soils and River Sediments using Thermal Decomposition and Amalgamation Coupled with Atomic Absorption• Determination of Total Mercury in Whole Blood using Thermal Decomposition and Amalgamation Coupled with Atomic AbsorptionFood & Beverage• Determination of Arsenic in Baby Foods and Fruit Juices by GFAAS• Determination of Total Mercury in Fish and Agricultural Plant Materials using Thermal Decomposition and Amalgamation Coupled with Atomic Absorption• Increased Throughput and Reduced Solvent Consumption for the Determination of Isoflavones by UHPLC• Extraction and Quantification of Limonene from Citrus Rinds using GC/MSSemiconductor• Analysis of Impurities in Semiconductor Grade Hydrochloric Acid by Dynamic Reaction Cell ICP-MS• Analysis of Impurities in Ultrapure Water by Dynamic Reaction Cell ICP-MS• Analysis of Semiconductor Grade TMAH by Dynamic Reaction Cell ICP-MS• Analysis of Impurities in Nitric Acid by Dynamic Reaction Cell ICP-MS PerkinElmer
  4. 4. a p p l i c at i o n n o t e Children’s Products Author Aniruddha Pisal PerkinElmer, Inc. Shelton, CT 06484 USADetermination of Figure 1. LAMBDA XLS+ UV/Vis spectrometer. Wavelength: 410 nm; Measurement Mode:Formaldehyde Content Absorbance; Cell 10 mm.in Toys using UV/VisSpectrometryIntroductionAs product safety regulations for industry are becoming stricter, more testing at lower levels is required for toxicelements or hazardous organic chemicals such as formaldehyde in children’s toys/clothing. Formaldehyde resinsare used in fabrics to bind pigments to the cloth, as a fire retardant and to provide stiffness. In cotton and cotton-blend fabrics they are used to enhance wrinkle resistance and water repellency. They can often be noted by theodor of treated fabric. The types of resins used include urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde. Resins without formaldehyde are typically much costlier. Increases in temperature (hot days) andincreased humidity both increase the release of formaldehyde from coated textiles.Long term chronic exposure or short-term exposure to high concentrations of formaldehyde can lead to cancer.In animal studies, rats exposed to high level of formaldehyde in air developed nose cancer. The European standardEN 71 specifies safety requirements for toys. EN 71, Part 9 contains requirements for organic chemical compoundsin toys and specifies the limit for accessible textile components of toys intended for children under 3 years of age.The limit specified for formaldehyde content is not more than 30 mg/kg or 2.5 mg/L in the aqueous migrate pre-pared following EN 71, Part 10. EN 71, Part 11, section 5.5.3 specifies a method of analysis.
  5. 5. Experimental The concentration of formaldehyde was found to be 1.99 mg/L. The analysis was carried out using a PerkinElmer LAMBDA ® ™ Formaldehyde dilute standard solution (0.001 mg/mL): XLS+ UV/Vis Spectrometer. 2.5 mL of formaldehyde stock solution was transferred to 50-mL volumetric flask; mixed well and diluted up to the Apparatus and reagents mark with water. 1 mL of this solution was further diluted to 100 mL with water and mixed well. Table 1. List of apparatus and reagents used.* Volumetric flasks, volume 50 mL A series of reference solutions were prepared by pipetting Volumetric flasks, volume 100 mL suitable volumes of above formaldehyde dilute standard Hot plate for distillation solution into a 50-mL conical flask as follows Boiling chips Erlenmeyer flasks, volume 100 mL Table 2. Calibration solutions. Eppendorf® micropipettes Concentration Ammonium acetate, anhydrous Amounts (mL) (mg/L) of Acetic acid, glacial Formaldehyde Formaldehyde dilute standard Amount of after making Pentane-2,4-dione solution in 50-mL pentane-2,4-dione volume to 30 mL conical flask reagent (mL) with water Hydrochloric acid, 1 mol/L Sodium Hydroxide solution 1 mol/L Blank – 5.0 0.0 Starch solution freshly prepared, 2 g/L Reference 1 5.0 5.0 0.167 Formaldehyde solution, 370 g/L to 400 g/L Standard iodine solution, 0.05 mol/L Reference 2 10.0 5.0 0.333 Standard sodium thiosulfate solution, 0.1 mol/L Reference 3 15.0 5.0 0.499 Water, deionized Stainless steel tweezers Reference 4 20.0 5.0 0.667 250 mL glass bottle with flat base, screw neck and PTFE lined rubber Reference 5 25.0 5.0 0.833 septum (Make: Schott Duran) Magnetic stirrer *The reagents, chemicals, standards used were of ACS grade. Absorbance measurement of calibration solutions: Absorbance measurements of calibration reference solutions Pentane-2,4-dione reagent: Dissolved 15 gm of anhydrous and blank were done by using water as reference. The calibra- ammonium acetate, 0.3 mL glacial acetic acid and 0.2 mL tion curve was constructed by subtracting absorbance value of pentane-2,4-dione reagent in 25 mL water and diluted up the blank solution (A2) from each of absorbances obtained to the mark in 100-mL volumetric flask with water. from the calibration solutions. Figure 2 shows calibration graph. Reagent without pentane-2,4-dione: Dissolve 15 gm of Sample preparation: Three different toy samples made up anhydrous ammonium acetate and 0.3 mL glacial acetic acid with fabrics were selected for analysis. Sample with surface in 25 mL water and diluted up to the mark in 100-mL volumetric area of 10 cm2 was taken and transferred to 250 mL extrac- flask with water. tion bottle with the help of tweezers. 100 mL of simulant (water, deionized) was added to the sample at 20 ˚C ±2 ˚C Formaldehyde stock solution: Transferred 5.0 mL of and the extraction bottle closed. The extraction bottle was formaldehyde solution into a 1000-mL volumetric flask kept on a magnetic stirrer for uniform stirring of the solu- and made up to the mark with water. tion over the period of 60 minutes. Aqueous migrate was then filtered through a plug of glass wool. 5.0 mL of aque- Standardization of formaldehyde stock solution: ous migrate was transferred into a 50-mL conical flask fol- 10.0 mL of freshly prepared formaldehyde stock solution lowed by addition of 5.0 mL of pentane-2,4-dione reagent was transferred into a conical flask, added 25.0 mL of a and 20.0 mL of water. standard iodine solution and 10.0 mL of sodium hydroxide solution. The solution was allowed to stand for 5 minutes. Sample reference solution: 5.0 mL of aqueous migrate Then the solution was acidified with 11.0 mL of hydrochloric was transferred into a 50-mL conical flask followed by acid and titrated for excess iodine by standard sodium thio- addition of 5.0 mL of reagent without pentane-2,4-dione sulfate solution. 0.1 mL of starch solution was added when and 20.0 mL of water. color of the solution became pale straw. After addition of starch solution, immediately the color was changed to These solutions were shaken for about 15 seconds and deep blue-black. The titration was continued until the color immersed in a thermostatic water bath at 60 ˚C ±2 ˚C for changes from deep blue-black to colorless. Similarly, the 10 minutes followed by cooling for about 2 minutes in a blank titration was performed. The difference between titration bath of iced water. values of blank and sample was used for calculation of formaldehyde contents in stock solution.2
  6. 6. Absorbance measurements were done between 35 minutesand 60 minutes from the time when the conical flasks wereplaced in a water-bath at 60 ˚C.Absorbance measurements of sample solutions were doneby using the reference solution as reference (A1).Calculation of analyte concentration: Calibration curvewas prepared manually by taking the absorbance valuesobtained for calibration reference solutions. To determinethe analyte concentration, absorbance value of blank solution Figure 3. Spectrum of color formed for the determination of ‘Formaldehyde’(A2) was subtracted from absorbance value of sample solution contents.(A1). The subtracted absorbance value was then read offfrom the manual calibration curve. The formaldehyde content in aqueous migrate was calculated by using following equation, Cs(mg/L) = C X 5 where, Cs = concentration of formaldehyde in the sample solution (mg/L) 5 = dilution factor of the sample solution. Results and discussion Calibration – linearity The six different levels of calibration standards were prepared in the range from 0.167 mg/L to 0.833 mg/L with the reagent blank as first level. Results showed linearity with a good correlation co-efficient of 0.9994. The calibration curve is shown in Figure 2. Figure 3 shows the spectrum of the developed color, confirming the peak maximum at 410 nm. Method detection limit: 10 replicate reagent blank solutions were prepared to make an estimate of method detection limit. To determine method detection limit, seven replicate aliquots of fortified reagent water (0.1 mg/L) were prepared and processed through entire analytical method. The method detection limit was calculated as follows, MDL = (t) X (s) where, t = student’s t value for a 99% confidence level and a standard deviation estimate with n-1 degrees of freedom. [t = 3.143 for seven replicates]. s = standard deviation of replicate analyses. The method detection limit was found to be 0.0178 mg/L.Figure 2. Calibration graph. 3
  7. 7. Sample analysis: Three different toy samples, as shown in ConclusionFigure 4, made up of polyester, rayon and synthetic fibers The LAMBDA XLS+ UV/Vis spectrometer can be used to mea-were analyzed as per the procedure given under ‘Experimental’. sure formaldehyde contents in fabric toys. The detection limitResults obtained in duplicate were averaged and are shown is sufficient to determine formaldehyde at the level of 30 mg/in Table 3. These measurements are below the action level kg in the original material or 2.5 mg/L in the aqueous migrateof 2.5 mg/L in the aqueous migrate. solution as specified in the current version of EN-71. Linearity and spike recoveries further validate the performance of this Table 3. Sample analysis results. methodology. Sample Concentration (mg/L) References Toy 1 (polyester fiber) 0.18 1. EN 71 Safety of Toys – Part 9, 10, 11 – organic chemical com- Toy 2 (rayon fiber) 0.25 pounds in toys – requirements, limits and sample extraction Toy 3 (synthetic fiber) Not Detected procedure. 2. 40 CFR, Part 136 Appendix B – Definition and Procedure forSpike recovery studies: A recovery study was performed by the Determination of the Method Detection Limit.spiking 0.5 mg/L concentration in three replicates of the syn-thetic fiber sample aqueous migrate. The results are summarizedin Table 4. As seen in Table 4 the recoveries are good, fallingwithin the usual acceptance range of 80-120% recovery. Table 4. Replicate spike recoveries. Sample % Recovery POLYESTER RAYON SYNTHETIC FIBER Sample 1 113 Figure 4. Toy samples. Sample 2 107 Sample 3 105PerkinElmer, Inc.940 Winter StreetWaltham, MA 02451 USAP: (800) 762-4000 or(+1) 203-925-4602www.perkinelmer.comFor a complete listing of our global offices, visit www.perkinelmer.com/ContactUsCopyright ©2009, PerkinElmer, Inc. All rights reserved. PerkinElmer® is a registered trademark of PerkinElmer, Inc. All other trademarks are the property of their respective owners.008765_01
  8. 8. a p p l i c at i o n n o t e Children’s Products Author Aniruddha Pisal PerkinElmer, Inc. Shelton, CT 06484 USADetermination of Introduction Toy safety is a joint responsibility among governments, the toy industries,Hexavalent Chromium regulatory bodies and parents. The toy safety regulations are intended to reduce potential risks children could be exposed to when playingin Toys by using with toys. Enforcement of the regulations aims to identify those toys that do not comply with the legislation and remove them from theUV/Vis Spectrometry market. The toxic elements that may be present in toys are heavy metals such as antimony, arsenic, chromium, lead, mercury, etc., which can accumulate in the body and may cause adverse effects. Therefore, analysis of such elements is important to ensure safety. The European standard EN 71 specifies safety requirements for toys. EN 71, Part 3 contains one section entitled “Migration of certain elements”. In this section it defines the limits for element migration from toy materials including hexavalent chromium. In EN 71, Part 3, the limit specified for migration of chromium is not more than 60 mg/kg. In the environment, chromium is found in several different forms including two oxidation states as trivalent i.e., Cr(III) and hexavalent i.e., Cr(VI). Cr(III) is considered to be an essential nutrient for the body. In contrast Cr(VI) is relatively mobile in the environment and is acutely toxic and carcinogenic. It is widely used in electroplating, stainless steel production, leather tanning, paint, and textile manufacturing. During the analysis, sample preparation was carried out using European method EN 71, Part 3, specifying extraction of sample by hydrochloric acid for 2 hours at 37 ˚C in darkness followed by colorimetric determination of hexavalent chromium by 1,5-diphenylcarbazide reagent. Figure 1. LAMBDA XLS+ UV/Vis spectrometer. Wavelength: 540 nm; Measurement Mode: Absorbance; Cell 10 mm.
  9. 9. Experimental Absorbance measurement of calibration solutions: The analysis was carried out using PerkinElmer LAMBDA ® ™ Background correction was performed with blank solution XLS+ UV/Vis spectrometer as shown in Figure 1. and absorbance of calibration reference solutions were measured at 540 nm using 10 mm cell. Figure 2 shows the calibration graph. Apparatus and reagents Sample analysis: Different toy samples selected for analysis Table 1. List of apparatus and reagents used. were, ‘yellow plastic’; ‘green fabric’ and ‘toy coated with pH meter paint’. 100 mg of test portion of sample was taken and cut Volumetric flasks, volume 100 mL into small pieces. For toy sample with paint coating, the Erlenmeyer flasks, volume 250 mL coating layer was scraped off for analysis. The test portion Water bath Boiling chips so prepared was mixed for about 1 minute with 5 mL of Eppendorf ® micropipettes 0.1 mol/L hydrochloric acid at 37 ˚C ±2 ˚C. pH of the solution Sodium hydroxide, 1N was adjusted to between 1 and 1.5 with 2 mol/L hydrochloric Potassium dichromate, dried acid. The mixture was protected from light, kept at 37 ˚C Nitric acid, concentrated ±2 ˚C and agitated for 1 hour continuously and then allowed Sulfuric acid, concentrated to stand for 1 hour at 37 ˚C ±2 ˚C. Then the solution was Sulfuric acid, 0.2 N filtered immediately through a membrane filter and diluted Phosphoric acid, concentrated to about 90 mL with distilled water. The pH of the solution Hydrochloric acid, 0.1 M was adjusted to 2.0 ±0.5 using phosphoric acid and 0.2 N 1,5 Diphenylcarbazide sulfuric acid. The solution was transferred to a 100-mL volu- Acetone metric flask and diluted up to the mark with distilled water. *The reagents, chemicals, standards used were of ACS grade. 2 mL of diphenylcarbazide solution was added to the solution and allowed to stand 10 minutes for full color Chromium stock solution (500 mg/L): Dissolved 141.4 mg development. An appropriate portion was transferred to a 1 cm of potassium dichromate in water and diluted to 100 mL. absorption cell and measured the absorbance at 540 nm with the blank as a reference. Chromium standard solution (5 mg/L): Diluted 1.0 mL of above chromium stock solution to 100 mL. Results and discussion Diphenylcarbazide solution: Dissolved 250 mg of Calibration – linearity 1,5-diphenylcarbazide in 50 mL acetone and stored in The seven different levels of calibration standards were brown bottle. prepared in the range from 0.1 mg/L to 1.0 mg/L with reagent blank as first level. Results showed linearity with Series of reference solutions were prepared by pipetting a good correlation co-efficient of 0.9997. The calibration suitable volumes of above chromium standard solution, curve is shown in Figure 2. as shown in Table 2, into 100-mL volumetric flasks. Spike recovery studies: Table 2. Calibration solutions. A recovery study was performed at 0.5 mg/L concentration in three replicates. The results are summarized in Table 3. Amount of chromium standard solution Concentration As seen in table, the recoveries are good, approximately (5 mg/L) in 100 mL (mg/L) 105 percent. This demonstrates that the extraction is not Blank – 0 causing transformation of the Cr(VI) spike to Cr(III). Reference 1 2 mL 0.10 Reference 2 4 mL 0.20 Reference 3 6 mL 0.40 Reference 4 8 mL 0.60 Reference 5 10 mL 0.80 Reference 6 20 mL 1.002
  10. 10. Method detection limit: 10 replicate reagent blank solutions Table 3. Replicate spike recoveries. were prepared to make an estimate of method detection Sample % Recovery limit. To determine method detection limit, seven replicate Sample 1 104.8 aliquots of fortified reagent water (0.01 mg/L) were pre- pared and processed through entire analytical method. Sample 2 104.6 The method detection limit was calculated as follows, Sample 3 104.6 MDL = (t) X (s) where, t = student’s t value for a 99% confidence level and a standard deviation estimate with n-1 degrees of freedom. [t = 3.143 for seven replicates]. s = standard deviation of replicate analyses. The method detection limit found to be 0.003 mg/L. Sample analysis: Results obtained for different toy samples are presented in Table 4. The yellow paint exceeds the limit specified in the current standard for total chromium (60 mg/Kg). The anticipated revision to the EU standard recommends a limit of 0.02 mg/Kg hexavalent chromium in a dry, brittle or pliable toy, much lower than the current standard and based on the species. The detection limit measured here is sufficient for the new regulatory level if a larger sample is taken for extraction or a smaller dilution is used. Table 4. Sample analysis results (calculations are based on total amount extracted and dilution factor). Sample Cr +6 – Total Chromium – UV result (mg/Kg) ICP result (mg/Kg) Yellow Plastic 5.4 29.9 Green Fabric ND 2.6 Blue Paint-1 7.2 89.5 Blue Paint-2 11 66.9 Yellow Paint-1 430 1790 Yellow Paint-2 360 1870 Red Paint-1 ND 58.4 Red Paint-2 ND 47.4 *ND: not detected The total amount of chromium in the extracts was measured using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) with resulting values in Table 4. Since the totalFigure 2. Calibration graph. chromium value is made up of both Cr(III) and Cr(VI) this is a good indication of the maximum amount of Cr(VI) that might be present. This provides an order-of-magnitude confirmation of the analysis. PaiNt-coateD toY GReeN FaBRic Yellow PlasticFigure 3. Toy samples. 3
  11. 11. ConclusionThe LAMBDA XLS+ UV/Vis spectrometer can be used tomeasure Cr(VI) contents in toys. The detection limit is sufficientto determine Cr(VI) at low levels and can be improved bytaking a larger sample for extraction and reducing the dilutionfactor if the new revisions to EN 71 require it. Linearity andspike recoveries further validate the performance of thismethodology.The sample extraction used here may not be representativeof the extraction that may be recommended in the final revisionof EN 71 specifically for Cr(VI), but represents a reasonableapproach to demonstrate the resulting analysis.Overall, the capability to measure Cr(VI) using the UV/Visprocedure with the LAMBDA XLS+ has been successfullydemonstrated.References1. Standard Methods for the Examination of Water and Wastewater”, Method 3500-Cr, American Public Health Association.2. EN 71-3:1995 Safety of Toys – Part 3 Migration of certain elements.3. 40 CFR, Part-136 Appendix B – Definition and Procedure for the Determination of the Method Detection Limit.PerkinElmer, Inc.940 Winter StreetWaltham, MA 02451 USAP: (800) 762-4000 or(+1) 203-925-4602www.perkinelmer.comFor a complete listing of our global offices, visit www.perkinelmer.com/ContactUsCopyright ©2009, PerkinElmer, Inc. All rights reserved. PerkinElmer® is a registered trademark of PerkinElmer, Inc. All other trademarks are the property of their respective owners.008766_01
  12. 12. A P P L I C AT I O N N O T e Liquid Chromatography Author Roberto Troiano, PerkinElmer William Goodman, PerkinElmerUHPLC seParationand deteCtion of IntroductionBisPHenoL a (BPa) The BPA or bisphenol A (Figure 1) has become well know over the past year as concerns for its effect on human healthin PLastiCs and well being have been raised. The concerns over BPA began with baby bottles and spread to include other types of bottles. BPA is used in the production of two very common polymers PVC and Polycarbonate. PVC, Polyvinyl chloride, is used in many different products including building materials, medical devices and children’s toys. BPA is used in PVC production as a polymerization inhibitor, residual BPA may remain after the polymerization is complete. Polycarbonate is another very commonly used plastic. It has very desirable properties for both optical clarity and heat resistance. BPA is an important monomer in the production of polycarbonate polymer, not all of the BPA is consumed in the pro- duction and may leach out of the polymer. Recently, many applications of polycarbonate have been replaced with new copolymers, such as co-polyester, to eliminate BPA. Figure 1: Structure of Bisphenol A (BPA).
  13. 13. As a result of the health concerns over human exposure to BPA Results this molecule is now monitored in specific products, including The BPA analyzed with the given LC conditions eluted at 5.43 baby bottles and other children’s products. Simple and robust mins (Figure 3). The UHPLC system was calibrated across a test methods are needed to determine the presence and amount range of 1 – 50 ppb (µg/L) BPA (Table 2). of BPA in plastic materials. This paper will present the extraction and HPLC analysis of children’s products for BPA. Figure 2: Childrens toy samples analyzed for BPA in this application note. Experimental The study presented here includes extraction of BPA from a toy matrix and analysis with UHPLC. The extraction procedure Figure 3: BPA calibration standard at 1 ppb. used here is intended to simulate the contact routes through which children are likely to encounter BPA. Two different extrac- tion techniques were used to analyze BPA in samples (30 g sam- Table 2: Table for the analysis of BPA across the range of 1 – 50 ppb (µg/L). ple used for each extraction). The first extraction method Concentration Response immersed the sample in 1 L of water, at 40 ˚C for 24 hours (EN 14372). The second immersed the sample with 1 L HCl (0.07 1 ppb 54163 M) at 10 ppb 378051 37 ˚C for 2 hours. Following extraction the samples were ana- 20 ppb 820335 lyzed with a PerkinElmer Flexar™ FX-10 UHPLC system includ- ing a PerkinElmer Series 200a Fluorescence detector. The sepa- 40 ppb 1548750 ration was performed on a Brownlee Validated C8 Column (see 50 ppb 1957851 Table 1). r2 0.9993 Table 1: HPLC Conditions for the Analysis of BPA HPLC System PerkinElmer Flexar FX-10 UHPLC The limit of quantitation (LOQ) for BPA with the method pre- Injection Volume 50 μL sented here is 1 ppb. The signal to noise at the LOQ is approxi- mately 10:1. The response across the calibration range fit a linear Column PerkinElmer C8 (150 mm x 4.6 mm, 5 μm) calibration with an r2 value of 0.9993. Blanks analyzed between Mobil Phase Methanol/Water (65/35) standards and samples showed the system was free from any BPA Flow Rate 1 mL/min contamination or carryover. Detector Wavelength Excitation – 275 nm / Emission – 313 nm BPA in the extracts of the toy samples were quantified using the calibration curve generated during standard analysis (Table 3). Detector Response Time 0.1 sec Figure 4 shows the chromatogram of the water extract of the toy PMT, Em BDW Super High, Wide dwarf sample. Run Time 15 min Table 3: Results from toy sample analysis. Sample Extraction Type µg/L µg/g Cube water 2.04 0.068 Cube HCl ND ND Die water 3.35 0.111 Die HCl 1.56 0.052 Dwarf water 4.32 0.144 Dwarf HCl 1.78 0.0592
  14. 14. Figure 4: Analysis of toy dwarf for BPA using water.The extraction procedure which heated the toy for 24 hours inwater at 40 ˚C extracted a significantly higher amount of BPAfrom the matrix than the extraction in acid. BPA was found in allthree water extractions within the calibration range of the stan-dard curve.ConclusionAs health concerns over exposure to BPA are raised, its analysisin plastics is becoming very important. The PerkinElmer FlexarFX-10 UHPLC system provides a sensitive and robust platformfor this analysis. Demonstrated here was a calibration of BPAacross a range of 1 – 50 ppb with a chromatographic run time ofless than 10 minutes. This analysis was applied to 3 toy samplesand BPA was identified in each sample.PerkinElmer, Inc.940 Winter streetWaltham, Ma 02451 UsaP: (800) 762-4000 or(+1) 203-925-4602www.perkinelmer.comFor a complete listing of our global offices, visit www.perkinelmer.com/ContactUsCopyright ©2009, Perkinelmer, inc. all rights reserved. Perkinelmer® is a registered trademark of Perkinelmer, inc. all other trademarks are the property of their respective owners.008731_01 Printed in Usa
  15. 15. applIcatIon note Childrens Products authors Zoe Grosser, ph.D. laura thompson lee Davidowski, ph.D. PerkinElmer Inc. Shelton, CT Suzanne Moller Innov-X Systems Woburn, MALead and Other Toxic Introduction From 2007 to 2008, the number of recalls for toys exceed-Metals in Toys Using ing the U.S. limits set for lead dropped 43%. This represents however, more than 300,000 individual products posingXRF Screening and potential hazardous exposure for children. The Consumer Product Safety Improvement Act of 2008 (CPSIA 2008)ICP-OES Quantitative defines a children’s product as a product primarily used byAnalysis a child under the age of 12 and defines new levels of lead allowed in those products1. Allowable lead in painted surfaces will be reduced from 600 mg/kg to 90 mg/kg one year from enactment of the legislation (enactment date: August 14, 2008). Allowable total lead content (surface and substrate) is reduced from 600 mg/kg to 100 mg/kg, incrementally over the course of three years. The American Academy of Pediatrics suggests that a level close to the background level in soil of 40 mg/kg would be most protective of children’s health2. Currently, EN-71, Part 3 and ASTM 963 specify evaluation of the toy by soaking in a mild hydrochloric acid solution at body temperature and measuring the accessible metal extracted into the solution. If a coating can be separated, a total analysis of the coating to comply with lead content requirements can be done. CPSIA 2008 provides no exemption for electroplated substrates, so that a total analysis on both coating and substrate must be done, though little other measurement guidance is currently available. EN-71 may also be revised in the near future to add other hazard- ous elements, such as aluminum, cobalt, copper, nickel, and others. The evolving need to measure lead and other metals at increasingly lower levels makes information on analysis technologies and performance valuable in making knowledgeable decisions.
  16. 16. A variety of techniques can be used to meet the regula- of children’s products, including toys that may require tions, including atomic absorption (both flame FLAA analysis? This question is addressed in this work using and graphite furnace GFAA), inductively coupled plasma ICP-OES and hand-held XRF to examine a variety of toy optical emission spectroscopy (ICP-OES) and inductively materials. Ease of use and agreement between techniques coupled plasma mass spectrometry (ICP-MS). Hand-held at the current level for lead were evaluated. energy dispersive XRF, requiring minimal or no sample preparation can provide a way to screen products on-site experimental as to determine whether further quantitative analysis is A variety of children’s toys were obtained randomly from required. a church nursery room and other sources. One known recalled item, Boy Scout totem badges of differing ages The techniques are compared for several parameters in were also obtained. Figure 1 shows the variety of toys, Table 1. including fabric, soft and hard toys and some with painted Since the techniques in Table 1 have different character- surfaces. istics, which would be the most suitable for the variety Table 1. Comparison of Several Analysis Techniques for Lead Determination (mg/kg). GFAA ICP-OES ICP-MS Hand-held XRF Estimated detection limit for lead* 0.025 0.5 0.025 NA** Sample prep required Yes Yes Yes No Simultaneous multielement No Yes Yes Yes * Includes a 500x dilution to account for sample preparation for GFAA, ICP-OES, and ICP-MS. Detection limits can be further improved if a smaller dilution is used. **NA: screening tool, detection limits matrix driven. Table 2. Microwave Digestion Program. Power (W) Ramp (min) Hold (min) Fan 500 5:00 15:00 1 900 10:00 15:00 1 0 20:00 2 Table 3. ICP-OES Instrumental Conditions. Instrument Optima 7300 DV ICP-OES RF Power 1450 W Figure 1. Variety of toys measured. Nebulizer Flow 0.55 L/min Auxiliary Flow 0.2 L/min Plasma Flow 15.0 L/min Sample Pump Flow 1.2 mL/min Plasma Viewing Axial Processing Mode Area Auto Integration 5 sec min-20 sec max Read Delay 30 sec Rinse 30 sec Replicates 3 Background Correction one or two points Spray Chamber Cyclonic Nebulizer SeaSpray (Glass Expansion®, Pocasset, MA) Figure 2. XRF result screen.2
  17. 17. Samples were prepared for ICP-OES analysis by scraping elements over a wide dynamic concentration range, fromoff the paint or cutting the substrate into small pieces. ppm levels up to virtually 100% by weight. An exampleApproximately 0.01-0.1 g was weighed into a Teflon® of the result obtained on the screen is shown in Figure 2.microwave digestion vessel and 6 mL of concentratednitric acid (GFS Chemical®, Columbus, Ohio) and 1 mL Results and Discussionof concentrated hydrochloric acid (GFS Chemical®, The analysis of the toys by hand-held XRF and ICP-OESColumbus, Ohio) were added. The samples were placed are shown in Table 4. The check mark in the XRF columnin the Multiwave™ 3000 microwave digestion system indicates the XRF analysis displayed a lead value higher(PerkinElmer, Shelton, Connecticut) and digested than the limit of 600 mg/kg in the screened toy indicatingaccording to the program shown in Table 2. further quantitative analysis is recommended. The value determined by ICP-OES confirms that the value wasThe Optima™ 7300 DV was used for analysis of the full higher than the regulatory limit in the coating or for asuite of elements currently regulated in EN-71, Part 33 total analysis of the substrate material. In this case, theand referenced in ASTM D9634, and CPSIA, including value measured with XRF is not reported although thelead. The conditions are as shown in Table 3. value would give further refinement of the concentrationThe Innov-X® Import Guard model was used for all hand- for the elements measured.held XRF measurements, and a general calibration was Detection limits for the ICP-OES are shown in Table 5 forperformed. For analysis of the same samples with XRF,no sample preparation was required. The system uses both the digested solution and the amount in the origi-energy dispersive X-ray fluorescence and easily identifies nal material. Since the amount taken for digestion may vary and the dilution can be changed, a 500x dilution was assumed for the calculation. This represents a typical 0.1 g of material diluted to a final volume of 50 mL. Duplicate sample preparation and analysis of several samples can indicate the reproducibility of the method, provided the samples are homogeneous. Table 6 shows the results for duplicate sample preparation and analysis of three different types of samples. The fabric and the uniformly-colored plastic show good agreement between the duplicate analyses (less than 20% relative percent difference). The puzzle board required scraping paint from the surface for analysis and it was difficult to uni- formly remove only the paint without taking some of the substrate, as shown in Figure 3. This may contribute toFigure 3. Puzzle board and scrapings. the very different values obtained for the duplicate analysis. Table 4. Results for Toys Measured with XRF and ICP-OES (mg/kg). XRF Antimony Arsenic Barium Cadmium Chromium Lead Mercury Selenium Toy Stove Knob √ 32 <DL 2 4 773 3950 <DL 13 Yellow Mega Block √ 12 <DL 56 3 774 3690 <DL 27 Badge-1 New (Yellow Paint) √ <DL <DL 16900 14 7340 34500 <DL 85 Badge-2 Older (Yellow Paint) √ <DL <DL 21200 2 8870 42100 <DL 20 Yellow Baby Rattle √ <DL <DL 70 <DL 544 2970 <DL 8 Yellow Crib Toy Holder Strap √ 15 <DL 146 <DL 377 1900 <DL <DL Green Cup <DL <DL 3220 2260 4 17 <DL 6 Red Ring <DL <DL 91 4 3 15 <DL 8 3
  18. 18. Table 5. Estimated Detection Limits. Element Detection Limit Detection Limit in Solution (mg/L) in Solid (mg/kg) Antimony (271 nm) 0.008 3.8 Arsenic (189 nm) 0.002 1.2 Barium (233 nm) 0.004 1.9 Cadmium (228 nm) 0.002 1.1 Chromium (267 nm) 0.003 1.6 Lead (220 nm) 0.010 6.4 Mercury (254 nm) 0.005 2.2 Selenium (196 nm) 0.011 5.7 Figure 4. Yellow ball measured in replicate. Table 6. Duplicate Sample Preparation and Analysis (mg/kg). Antimony Arsenic Barium Cadmium Chromium Lead Mercury Selenium Green Fabric 15 <DL 302 <DL 332 1780 <DL <DL Green Fabric -Duplicate 13 <DL 329 <DL 362 1940 <DL <DL Puzzle Board 919 <DL 14 4 21,200 121,000 <DL 49 Puzzle Board - Duplicate 2187 <DL 5 5 14,600 82,600 <DL 15 Yellow Handle <DL <DL 360 <DL 1310 4990 <DL <DL Yellow Handle - Duplicate <DL <DL 336 <DL 1200 4620 <DL 12 A more extensive analysis of reproducibility is shown in Table 8 shows an example for a hydrochloric acid extract Table 7. The standard deviation of five separate digestions from a toy, extracted and measured using procedures and analyses for a yellow ball (Figure 4) show excellent specified in EN-71, Part 3. Both the original set of ele- precision. ments reported and the elements determined later (in blue) by reprocessing the data to examine the informa- It is interesting to note the lead level is high, in agreement tion previously stored for those elements are listed. This with the XRF analysis. Several other elements, such as can be useful in assessing samples that may have been dis- chromium, are also high. The XRF value reported for posed or in better understanding the scope of samples in lead in the ball was 3940 mg/kg. preparing for future analyses. Regulations are continually changing and may require different elements to be monitored in the future, at dif- ferent concentration levels. One way to help in preparing for that eventuality is the use of the universal data acqui- Table 7. Analysis of Five Replicate Samples of a Yellow Ball. sition (UDA) feature, exclusive to the Optima ICP-OES software. In this case the Optima ICP-OES collects data Element Average (mg/kg) SD for all of the wavelengths all of the time. If a standard Antimony (271 nm) 10.6 0.49 is run at the time of the original data acquisition that Arsenic (189 nm) 12.4 1.8 includes more elements than the elements of interest Barium (233 nm) 707 3.1 at that moment, other elements can be measured with Cadmium (228 nm) 78.3 0.73 good quantitative accuracy by reprocessing at a later Chromium (267 nm) 414 2.3 date. If an elemental concentration is of interest for an Lead (220 nm) 1980 9.7 element that was not included in any of the usual multi- Selenium (196 nm) 16.3 1.3 element standards, reprocessing can provide a semiquan- Mercury (254 nm) <DL – titative result, usually within ±30% of the true value.4
  19. 19. conclusion ICP-OES and XRF are complementary techniques that workThe regulatory landscape of toy measurements for hazard- well together at the current regulatory level of 600 mg/kg.ous metals is changing and will continue to change as ele- XRF provides rapid screening with a high degree of confi-ments, concentrations, and sample preparation procedures dence when the sample is contaminated with lead. Highlyare refined and harmonized between the U.S. and Europe. accurate ICP analyses can be efficiently directed to theIndeed, the lowest limits of 90 and 100 ppm are designated samples most likely contaminated using hand-held XRF’sas what the CPSC deems to be feasible at the time and quick screening and no-sample prep characteristics.lower limits may be regulated in the future. Samples identified as contaminated can be prepared and analyzed by ICP with less wasted time on uncontaminatedICP-OES is the accepted certifying tool in determining a samples, because of the positive screening result. As thewide variety of metals that may contaminate toys, either in limits are lowered, XRF will continue to perform as athe substrate or a paint coating. Lead can be determined screening technique, with ICP-OES providing confirmationat the current 600 mg/kg concentration level permitted with regulatory requirements.and the ICP-OES has sufficient detection capability thatthe new limits of 90 mg/kg can be reliably detected. References 1. Consumer Product Safety Improvement Act, Table 8. Universal Data Acquisition for Additional http://www.cpsc.gov/ABOUT/Cpsia/legislation.html Elemental Data. 2. Testimony of Dana Best, MD, MPH, FAAP on Element mg/kg extracted from solid behalf of the American Academy of Pediatrics, Antimony (271 nm) 6.7 http://www.aap.org/visit/coeh/COEH Ltr Arsenic (189 nm) 1.5 2007-09-20 Lead Testimony.pdf Barium (233 nm) 1850 3. EN-71, Part 3 The Safety of Toys, Migration Cadmium (228 nm) < DL of Certain Elements, may be purchased from Chromium (267 nm) 655 http://www.standardsuk.com/shop/products_view. Lead (220 nm) 2900 php?prod=26164 Selenium (196 nm) < DL 4. ASTM D-963-07, Standard Consumer Safety Aluminum (396 nm) 438 Specification for Toy Safety, may be purchased Cobalt (228 nm) < DL from http://www.astm.org Copper (327 nm) < DL Manganese (257 nm) < DL Nickel (231 nm) < DL Tin (189 nm) < DL Zinc (206 nm) 1230perkinelmer, Inc.940 Winter StreetWaltham, MA 02451 USAP: (800) 762-4000 or(+1) 203-925-4602www.perkinelmer.comFor a complete listing of our global offices, visit www.perkinelmer.com/contactUsCopyright ©2009, PerkinElmer, Inc. All rights reserved. PerkinElmer® is a registered trademark of PerkinElmer, Inc. All other trademarks are the property of their respective owners.008598_01
  20. 20. a p p l i c at i o n n o t e ICP-OES Authors Paul Krampitz Stan Smith PerkinElmer, Inc. Shelton, CT 06484 USAIncreased Laboratory Abstract The use of an ESI SC FAST autosamplerProductivity for ICP- coupled to a Perkin Elmer Optima 7300 DV ICP can dramatically improve produc-OES Applied to U.S. tivity for the analysis of environmentalEPA Method 6010C samples using EPA SW-846 Method 6010C. Sample throughput, as determined by sample-to-sample run time can be improved by as much as 100% as compared to traditional sample introduction systems and autosampler configurations. Both sample analysis time and rinse out time are significantly reduced, allowing for a doubling of overall productivity. In addition, stability of the plasma and instrument is very robust allowing for long, unattended run times while meeting calibration and method QC requirements. Valuable man hours spent on instrument maintenance and recalibration are reduced. This paper will demonstrate that these productivity enhancement claims can be accomplished for implementation SW-846 Method 6010C.
  21. 21. Introduction The analytical test methods found in SW-846 are commonly Since 1980, the EPA has maintained a publication entitled used by laboratories for the analysis of a wide range of sample SW-846 Test Methods for Evaluating Solid Waste, Physical/ matrices including, but not limited to: groundwater, surface Chemical Methods, more commonly referred to simply water, leachates, soils, and a whole host of other solid and as SW-846. Currently, SW-846 is in its third edition and liquid wastes, both organic and aqueous. The RCRA regulatory includes several updates. Since the third edition was programs for which SW-846 is most commonly used can be released in 1986, there have been 9 updates (Updates I, II, found in the U.S. Code of Federal Regulations (CFR), specifically IIA, IIB, III, IIIA, IIIB, IVA, and IVB), the most recent of which Title 40 CFR Parts 122-270. One of the methods found in was dated February, 2007. Included in SW-846 are over 200 SW-846 that is commonly used by most environmental labora- documents related to quality control practices, analytical tories for the analyses of elements in environmental samples test methods, sampling methods, and other topics related is 6010C Inductively Coupled Plasma-Atomic Emission to the United States Environmental Protection Agency (EPA) Spectrometry (ICP-AES). Resource Conservation and Recovery Act (RCRA). Essentially, Method 6010C is the fourth version of this method and was SW-846 is the official compendium of analytical and sam- released as part of SW-846 Update IV in February, 2007. As pling methods that have been evaluated and approved by indicated in the method, all samples other than filtered, pre- the EPA for use in complying with RCRA regulations. served groundwaters require acid digestion prior to analysis. As indicated by the EPA, the analytical methods in SW-846 There are more than 8 acid digestion methods applicable to are intended to be guidance documents and are not intended ICP-AES found in SW-846 and some of those that are commonly to be overly prescriptive except in the cases where a particular used for the preparation of environmental samples include: analyte or parameter is considered method defined. Such • 3005A Acid Digestion of Waters for Total Recoverable or method-defined parameters are where the analytical result is Dissolved Metals for Analysis by FLAA or ICP Spectroscopy wholly dependent on the process and conditions of the test or preparation method such as the Toxicity Characteristic Leaching • 3010A Acid Digestion of Aqueous Samples and Extracts Procedure (TCLP), Method 1311, where the conditions specified for Total Metals for Analysis by FLAA or ICP Spectroscopy in the method directly affect the concentration of analytes extracted into the leaching solution. However, despite this clear • 3015A Microwave Assisted Acid Digestion of Aqueous indication from the EPA that SW-846 methods are intended as Samples and Extracts guidance documents, many regulatory agencies invoke these • 3050B Acid Digestion of Sediments, Sludges, and Soils methods with no permissible changes or modifications. • 3051A Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils Summary of Method Method 6010C is a general analytical method that is applicable to a wide variety of liquid and solid samples and that provides specific procedures and references for sample collection, preservation, and preparation (i.e., acid digestion), in addition to recommended instrument procedures for calibration, detection limits, and interference correction. In addition, SW-846 6010C also contains procedures for the preparation, analysis, and acceptance limits for quality control samples needed for each batch of samples to be analyzed. While the method is intended only as a guidance document and is subject to interpretation and modification, implementation of the QC criteria as stated in the method was followed for Figure 1. Schematic of FAST sample introduction system coupled to an Optima the work performed and summarized in this paper. The EPA 7300 DV ICP spectrometer. has approved this method for the analysis of 31 elements and Table I includes all the elements analyzed and their associated wavelengths. Following is a summary of the procedure from SW-846 6010C as performed in this work.2
  22. 22. Summary of Method 6010CTable I. Wavelengths Monitored and Viewing Modes Used forSW-846 6010C. Establish Initial Demonstration of Performance Wavelength 1. Perform Instrument Detection Limits (IDL)Analyte Symbol Monitored (nm) View 2. Determine Linear Dynamic Range (LDR)Aluminum Al 308.215 Radial a. Recovery of elements must be ±10% of the knownAntimony Sb 206.836 Axial values for each elementArsenic As 188.979 Axial 3. Determine whether interelement corrections are needed byBarium Ba 233.527 Axial analysis of an Interference Check Solution (ICS)Beryllium Be 234.861 Radial Routine AnalysisBoron B 249.677 Radial 1. Light plasma and warm up instrument, allowCadmium Cd 226.502 Axial 15-30 minutesCalcium Ca 315.887 Radial 2. Optimize instrument and plasma conditions per instrumentChromium Cr 267.716 Axial manufacturer 3. Calibrate ICP using blank and minimum of one standardCobalt Co 228.616 Axial a. Rinse with blank between each standardCopper Cu 327.393 Axial b. Use the average of multiple readings (3 replicates inIron Fe 238.204 Radial this study) for all standards and samplesLead Pb 220.353 Axial 4. Verify calibration by analyzing the Initial Calibration VerificationLithium Li 670.784 Radial (ICV) standardMagnesium Mg 285.213 Radial a. ICV standard must be from a separate source as used forManganese Mn 257.610 Axial calibration standardsMolybdenum Mo 202.035 Axial b. Recovery of elements must be ±10% of the known values for each elementNickel Ni 231.604 Axial 5. Verify the lowest quantification limit by analyzing the Lower Phosphorus P 213.617 Axial Limit of Quantitation Check Sample (LLQC)Potassium K 766.490 Radial a. LLQC standard should be from the same source as theSelenium Se 196.026 Axial calibration standardsSilicon Si 251.611 Radial b. Recovery of elements must be ±30% of the knownSilver Ag 328.068 Axial values for each element 6. Analyze the Initial Calibration Blank (ICB)Sodium Na 589.592 Radial a. Target elements should not be detected at or above theStrontium Sr 407.771 Radial Lower Limit of QuantitationThallium Tl 190.801 Axial 7. Analyze test samples along with appropriate batch qualityTin Sn 189.927 Axial control samplesTitanium Ti 334.940 Axial 8. After every 10 samples, verify calibration by analyzing theVanadium V 292.402 Axial Continuing Calibration Verification (CCV) standardZinc Zn 206.200 Axial a. CCV standard should be from the same source as the calibration standardsInternal Standards b. Recovery of elements must be ±10% of the known valuesYttrium Y 371.029 Radial/Axial for each elementTellurium Te 214.281 Radial/Axial 9. Immediately following the analysis of each CCV, analyze the Continuing Calibration Blank (CCB) a. Target elements should not be detected at or above the Lower Limit of Quantitation 10. The LLCCV must be analyzed at the end of each analytical batch but is also recommended to be analyzed after every 10 samples a. Recovery of elements must be ±30% of the known values for each element 11. At the end of the run, analyze the CCV and CCB a. Acceptance limits are the same as in steps 8 and 9 3
  23. 23. Batch Quality Control Samples Initial Performance Demonstration 1. Analyze the Method Blank Instrument Detection Limits a. Target elements should not be detected at or above The Instrument Detection Limits (IDL) for all elements were 10% of the Lower Limit of Quantitation determined using a reagent blank solution according the 2. Analyze the Laboratory Control Sample (LCS) procedures in Section 9.3 of SW-846 6010C. Specifically, a a. Recovery of elements must be ±20% of the spiked reagent blank was analyzed seven consecutive times, with values for each element routine rinsing procedures between each analysis, for all ele- ments three times on non-consecutive days. The IDLs were 3. Analyze the Matrix Spike then estimated by calculating the average of each element’s a. Recovery of elements must be ±25% of the spiked standard deviation. The obtained IDLs are presented in Table III. values for each element Evaluation of Interferences 4. Analyze the Sample Duplicate or Matrix Spike Duplicate Interferences were evaluated according to Section 4.2.10 of a. The precision criterion for duplicates is a relative Method 6010C. An interference check solution containing percent difference of no greater than 20% 500 mg/L of Al, Ca, Mg, Na, 200 mg/L of Fe and 50 mg/L of K was used for evaluation. Experimental Instrument Table II. FAST-Optima 7300 DV Instrumental Conditions and An Optima 7300 DV (PerkinElmer, Shelton, CT) was used Experimental Parameters. in conjunction with an SC-FAST (Elemental Scientific Inc., Optima 7300 DV Parameters Omaha, NE) for the analysis of all samples described in this work. The FAST sample introduction system is controlled RF Power 1450 watts through the Optima WinLab32™ software and a schematic Plasma Gas Flow 15 L/min of the FAST is shown in Figure 1. The elements, wavelengths, Auxiliary Gas Flow 0.2 L/min and plasma viewing modes used are listed in Table I. The Nebulizer Gas Flow 0.6 L/min instrument conditions for both the Optima ICP-OES and the Peristaltic Pump Speed 0.85 mL/min SC-FAST as well as the experimental parameters used are Nebulizer/Spray Chamber Sea Spray/Glass cyclonic provided in Table II. Torch Cassette Position -3 Standards Purge Normal Resolution Normal All calibration standards and non-sample solutions were prepared with ASTM Type I (i.e., >18MΩ-cm) deionized Integration Time 2 s min/5 s max water and trace metals grade or better nitric acid. Read Delay 14 s Wash Time 1s Internal Standards Number of Replicates 3 All samples were spiked with 1.5 mg/L of yttrium and 2.5 mg/L FAST Parameters of tellurium. The spiking solution was made from 1000 mg/L Sample Loop Volume 2 mL single element stock solutions. Sample Loop Fill Rate 27 mL/min Calibration Carrier Pump Tubing Black/Black (0.76 mm i.d.) Sample Load Time 7s The calibration blank and standards were prepared in 1% Rinse 1s nitric acid. Calibration was performed using a calibration blank and a single standard containing all elements at 1 mg/L. Analysis Time (total) 75 s (sample-to-sample) The calibration standard was prepared from a combination Experimental Parameters of single element and multi-element stock solutions, all Carrier Solution 1% HNO3 plus 0.05% surfactant containing elements at 1000 mg/L. Rinse Solution 1% HNO3 Acidity of Stds/Samples 1% HNO3 Monitored Wavelengths As previously mentioned, the monitored elements, wavelengths, and plasma viewing modes used are listed in Table I.4
  24. 24. Linear RangeTable III. Instrument Detection Limit (IDL) Data and Linear Dynamic Ranges (LDR).Analyte Wavelength IDL IDL IDL 6010C, LDR, The Linear Dynamic Range (LDR) was RUN 1 RUN 2 RUN 3 IDL, ug/L mg/L determined for each element and met the criterion in Section 10.4 of SW-846Ag 328.068 0.159 0.103 0.172 0.14 100 6010C as found in Table III. That is, theAl 308.215 1.732 0.630 1.898 1.42 2000 upper linear range was established byAs 188.979 0.349 0.415 0.774 0.51 100 analyzing standards against the sameB 249.677 4.504 1.400 1.109 2.34 2000 calibration used for analyzing samples andBa 233.527 0.056 0.016 0.034 0.04 25 obtaining recoveries within ±10% of theBe 234.861 0.034 0.018 0.075 0.04 50 known concentration value. The LowerCa 317.933 0.544 0.550 0.783 0.63 900 Limit of Quantitation was confirmedCd 226.502 0.041 0.037 0.073 0.05 100 through the analysis of the Lower LevelCo 228.616 0.076 0.092 0.078 0.08 250 Check Standard (LLICV and LLCCV) and obtaining recoveries within ±30% of theCr 267.716 0.086 0.099 0.071 0.09 100 known concentration value. The LLICVCu 327.393 0.062 0.047 0.158 0.09 300 and LLCCV were run at a concentrationFe 259.939 0.256 0.230 0.168 0.22 400 of 500 ug/L for this study.K 766.49 7.269 5.270 5.499 6.01(0.24) 2000Mg 279.077 1.763 2.030 3.108 2.30 700 Memory EffectsMn 257.61 0.005 0.009 0.018 0.01 40 Memory effect studies were performedMo 202.031 0.132 0.097 0.180 0.14 125 to obtain the rinse time needed betweenNa 589.592 1.147 2.364 1.609 1.71(0.2) 900 sample measurements using the ESI FASTNi 231.604 0.178 0.188 0.161 0.18 125 system. The elements studied were the most likely elements to be high for envi-Pb 220.353 0.427 0.229 0.368 0.34 100 ronmental samples run under SW 846:P 213.617 1.543 1.091 1.249 1.29 3000 Al, Ca, Fe, K, Mg, and Na. All of the data Li 670.784 0.214 0.176 0.364 0.25(0.03) 200 can be found in Figure 2. Five blanks wereSb 206.836 0.662 0.586 0.226 0.49 100 run, then five standards, then five blanksSe 196.026 0.875 0.953 0.485 0.77 100 again to obtain the rinse out profiles.Si 251.611 2.546 0.569 1.080 1.40 2500 Al, Ca, Mg, and Na were run at 500 mg/L. Sr 421.552 0.025 0.029 1.139 0.40(0.01) 50 Fe was run at 200 mg/L and K was run atSn 189.927 1.928 1.218 0.095 1.08(0.35) 2000 50 mg/L. The FAST parameters used were Ti 334.94 0.017 0.018 1.863 0.63 50 the same as listed in Table II above.Tl 190.801 0.574 0.568 0.114 0.42 100V 292.402 0.070 0.059 0.781 0.30 50Zn 206.2 0.051 0.039 0.086 0.06 100( ) = Axial 5
  25. 25. Figure 2. Above figures show the rinse out time using the ESI FAST system. Al, Ca, Mg, and Na were run at 500 mg/L. Fe was run at 200 mg/L and K was run at 50 mg/L. Samples were rinsed out to near baseline in 7 seconds. Quality Control and Sample Analysis samples analyzed were synthetic or natural water samples The accuracy and precision of the implementation of with no detectable turbidity or suspended solids, no acid Method 6010C was demonstrated through the analysis digestion procedures were performed. The batch QC consisted of several reference materials and a local filtered, treated of a method blank, a sample duplicate (DUP), a Laboratory surface water sample (Lake Michigan). The quality control Control Sample (LCS), a Matrix Spike (MS), and a Matrix procedures specified in SW-846 were followed throughout Spike Duplicate (MSD). A natural surface water sample was the work performed. Immediately following calibration, used to prepare the DUP, MS, and MSD. Results of all batch the ICV (second source), LLICV, and ICB were analyzed and QC samples were found to be within method-specified criteria. all results were determined to be within method-specified That is, no elements were detected within 10% of the criteria, ±10%, ±30%, and <LLQC respectively. Following LLQC, all elements detected in the sample and the sample the analysis of each sequence of ten samples, the CCV, DUP above the LLQC had relative percent differences of less LLCCV, and CCB were analyzed and found to be within the than 20, all elements in the LCS were recovered within 20% method-specified criteria (same as for ICV, LLICV, and ICB). of the known spike concentration, all elements in both the In additional to the sequential run QC (10% frequency), MS and MSD recovered within 25% of the known spike batch QC samples were also prepared and analyzed. As all concentration, and all spiked elements in the MS and MSD had relative percent differences of less than 20.6

×