The Commercialization of Method 6800- Speciated Isotope Dilution Mass Spectrometry for the Determination of Hexavalent Chromium

Albert F. Vicinie III,* Mark Bruce, PhD. ** William Reinheimer* *Severn Trent Laboratories, Inc., Pittsburgh, PA; **Severn Trent Laboratories, Inc., North Canton, OH

ABSTRACT
Method 6800 has recently been approved for the determination of the various species of metals such as Chromium III and Chromium VI. It is a hyphenated technique that couples ion chromatography (IC) with Inductively Coupled Plasma/Mass Spectrometry (ICP/MS). To date use of this method has been primarily in academia and limited project support. The method offers two primary challenges. It utilizes a mathematical approach to deconvolute the species that is unique to other traditional methods utilized in commercial environmental methods. Also the method does not specify in detail quality control practices and deliverables to be performed and provided to allow the data user to effectively evaluate the data set. This paper identifies the primary differences in this method from traditional as well as proposed QA/QC practices along with a deliverable to allow effective data validation and assessment.

INTRODUCTION
Method 6800 may be utilized to determine the total metal content for various elements using isotope dilution mass spectrometry (IDMS) and determining the elemental species for numerous metals using speciated isotope dilution mass spectrometry (SIDMS). We are focusing our discussions on the analysis of soils, leachates and waters for hexavalent chromium (Cr VI) using the SIDMS approach of 6800. This method is providing investigators much new and valuable additional information to allow the assessment of hexavalent chromium in soil matrices that are not suitable to provide data of known and acceptable quality with other analysis methods in order to support environmental decisions. Method 6800 provides solutions to the analytical challenges and refers to the base technology methods and Chapters One and Two of SW-846 as well as individual project plans for the development and incorporation of appropriate quality control procedures. We discuss in the following paragraphs suggested practices and procedures that will provide additional information to the investigators and regulating community to assist in assessing the data generated by this method.

Specified Quality Control Measures

Method 6800 SIDMS specifies the following quality control measures explicitly. Dead Time Determination- This determines the interval during which the detector and its associated counting electronics are unable to resolve successive pulses. The measured counts are lower than the true counts if no correction occurs. Current instrument operating software allows this to be set and controlled for each instrument. Alternatively method 6800 provides guidance on determining the dead time. This should be performed/evaluated daily.

Mass Bias- This is the deviation of the measured isotope ratio from the true value caused by the differential sensitivity of the instrument to mass. This effect may occur in the ionization process or from differential transition/detection by the mass spectrometer. The resultant mass bias factor is the number used to correct for the mass bias of the measured isotope ratios and is determined by performing 4 replicate measurements of an isotopically certified standard. We are proposing that this be performed at the beginning of each analytical sequence and at the end of each analytical sequence or every 4 hours whichever is more frequent. Background Blank- This is the background associated the solutions used for sample dilution (eluent) and with the chromatographic baseline. Preparation (Reagent) Blank- This is blank laboratory grade water that is carried through the complete preparation procedure and contains the same volumes of reagents as the sample solutions. We propose that this be performed at a minimum of 1 per sample batch with batch size not to exceed 20 samples that is consistent with normal quality control practices. These are QC measures that are not routinely included in the base ICP/MS methods such as SW846 6020 but are inherent to the performance of this method. There are no existing criteria to assess their performance, nor any precedent in presenting them as part of a deliverable. The dead time determination ensures that the measurements are made within the appropriate range and the mass bias factor becomes part of the solution to solving the equation to determine the actual isotope ratios used for the calculation.

Non-Specified Quality Control Measures

These measures are not directly specified as part of method 6800 for Cr VI or other elements. We are proposing the following measures that are either normally included in laboratory/project quality plans, part of the base methods such as method 6020 for the use of ICP/MS in the determination of metals in waters and soils or other related hexavalent chromium methods. 1. Holding Times a. For soils we default to existing published guidance in method 3060A of 30 days for soils stored cool at 4 deg C. Once extracted the alkaline digestion has been demonstrated to be stable for 7 days by this same method. Method 3060A is the alkaline digestion sample preparation method used to prepare soil/sediment samples for analysis using method 6800 for Cr VI. b. For waters being analyzed by the routine method of 7196A these are typically collected unpreserved and submitted for analysis within a 24 hour holding time. Due to the more complex nature of method 6800 this may be impractical in routine use. USEPA method 1636 provides that aqueous samples preserved by pH adjustment to > 9 may be stored for up to 30 days at 4 deg. C. We recommend this preservation technique for any project associated field QC samples such as equipment blanks to be analyzed by method 6800 for Cr VI.

2. Instrument Performance a. Cross Calibration of Mass Spectrometer Detector- this determines levels at which the detector switches from pulse to analog measurements and is related to the dead time of the instrument. We are proposing that this be performed each day of instrument operation for this method. There are no performance limits associated with this action. b. Tune Check- (Performance Report) this tunes the mass spectrometer to a known material. We are proposing that the tuning criteria for the mass spectrometer be the same as that published in USEPA method 6020. c. Dynamic Range Determination- for screening samples using the Time Resolved Analysis (TRA) mode we propose analyzing 4 aqueous standards of Cr VI at concentration of 10, 50, 100 and 200 ug/L to provide quantitation of the screened samples that have not been spiked with the enriched isotopes. Data will be acquired using the 50, 52 and 53 amu masses with quantitative analysis performed using the 52 amu mass. There are no criteria set to evaluate this calibration and as it is only used to provide screening level data to allow appropriate spiking of enriched isotopes no criteria is proposed. We are however proposing to bracket the analytical sequence with a 50 ug/L solution that will be analyzed and quantitated against the instrument calibration and evaluated using method 6020 criteria. Samples should be diluted if necessary and analyzed within the range identified. d. Instrument Sensitivity- While not specified we recommend that instrument sensitivity be evaluated using aqueous standards of either Cr III or Cr VI by performing 7 replicate analyses and evaluating the data for the mean and standard deviation. No criteria is provided but we recommend utilizing the same criteria as provided for evaluating MDL studies in 40 CFR 136 to ensure the analysis is able to reliably be differentiated versus a blank. We recommend this be performed on a quarterly basis. Example data is provided in Table 1. 3. Method Performance a. Accuracy- We are proposing the analysis of a soil sample of known concentration such as an NIST SRM or a material provided by a NELAC approved PE vendor such as ERA or equivalent. These samples should be analyzed at a minimum of 1 for every batch of samples prepared through the alkaline digestion with batch size not to exceed 20 samples. Manufacturer provided criteria should be used to evaluate performance. b. Detection Limits- Due to the unique nature of this method as it applies mathematics to the direct measurement of the isotopic ratios which are spiked into each sample at known quantity the traditional method detection study as described in 40 CFR 136 does not directly apply to this method as there will by the nature of the method always be detectable levels of isotope. However we conducted and are proposing that a traditional MDL study be conducted through the alkaline digestion of a Cr VI spiked sample that is not spiked with the enriched isotope to provide an idea of the level at which the naturally occurring chromium isotopic abundance can be expected to be detected. We have provided an example of this data in Table 2.

c. Matrix Effect- As each sample is spiked with both a Cr III and Cr VI species the matrix of each sample is able to be evaluated and addressed by the method. As such there is no reason to include additional MS/MSD samples that are typically included in analytical batches. d. Interference Checks- ICSA/ ICSB interference checks that are commonly included in the ICP-AES and ICP/MS are not included in this method and not required as there is chromatographic separation, confirmation of retention time and mass spectral evaluation of isotope ratios at 50, 52 and 53.

CONCLUSIONS
Method 6800 is a much needed and useful tool in providing a more definitive evaluation of hexavalent chromium in soil samples that due to their matrix may not be able to be accurately characterized by other traditional methods. As this method provides a novel solution to these challenges it also presents challenges to the analytical community as well. These challenges are primarily involve the training and understanding of the analysts and data users to ensure the highest quality of data is generated and that the data can be assessed appropriately. We have proposed appropriate measures to allow for the evaluation of data using this method and that will allow it to be reproduced and evaluated.

ACKNOWLEGEMENTS
The authors would like to acknowledge Dr. H.M. Skip Kingston and Dr. G. M. Mizanur Rahman of Duquesne University, Department of Chemistry and Biochemistry, Pittsburgh, PA 15282 for all of their training and assistance in transitioning this analytical method into a commercial environmental laboratory.

Table 1: Cr VI Instrument Detection Limit Concentration ug/L actual measured 5 6.80 5 4.78 5 5.00 5 5.60 5 5.63 5 6.45 5 5.55 avg 5.69 %RSD 13% IDL 2.28

Table 2: Cr VI Method Detection Limit Concentration ug/L spike measured 10 7.79 10 8.63 10 7.05 10 7.00 10 5.46 10 8.37 10 6.39 avg 7.24 %RSD 15% MDL 3.52

REFERENCES
1 U.S. Environmental Protection Agency, Jan. 1998. Method 6800, Elemental and Speciated Isotope Dilution Mass Spectrometry. Office of Solid Waste. U.S. Environmental Protection Agency, 1992. SW-846 Chapters One & Two. Office of Solid Waste. U.S. Environmental Protection Agency, Dec. 1996. Method 3060A, Alkaline Digestion for Hexavalent Chromium, Office of Solid Waste. U.S. Environmental Protection Agency, Jul. 1992. Method 7196A, Chromium, Hexavalent (Colorimetric), Office of Solid Waste. U.S. Environmental Protection Agency, Jan. 1996. Method 1636, Determination of Hexavalent Chromium by Ion Chromatography, Office of Water.