Determination of Sulfur Species in Acid Mine Drainage Studies Using X-ray Photoelectron Spectroscopy
Hylton G. McWhinney, Prairie View A&M University
Paul Behum, Office of Surface Mining Reclamation and Enforcement, US Department of Interior
Jon E. Brandt, Surface Mining and Reclamation Division, Railroad Commission of Texas
Tameka Harney, Prairie View A&M University
Tony Grady, Prairie View A&M University

Emerging Technology Key to Accurate and Rapid Analysis for Arsenic in Environmental Wastewater and Soil 
David K. Beck, B.S., Lancaster Laboratories, Inc.
Parker D. Lindstrom, B.S., Lancaster Laboratories, Inc.
Kevin T. Moran, B.S., M.B.A., Lancaster Laboratories, Inc.
Robert Strocko, B.S., Lancaster Laboratories, Inc.

Comparison of Naphthalene Ambient Air Sampling & Analysis Methods at a Former Manufactured Gas Plant Site
Alyson Fortune, Columbia Analytical Services Air Quality Laboratory
Leo Gendron, ENSR
Michael Tuday, Columbia Analytical Services Air Quality Laboratory

Adding Method 6800 to the Hexavalent Chromium Analysis Toolbox
Mark Bruce, PhD, TestAmerica, North Canton , OH
Albert Vicinie III, TestAmerica, Pittsburgh , PA
William Reinheimer, TestAmerica, Pittsburgh , PA

Determination of Sulfur Species in Acid Mine Drainage Studies Using X-ray Photoelectron Spectroscopy
Hylton G. McWhinney, Prairie View A&M University, P.O. Box 2502, Prairie View, TX 77446, Tel: 936-261-3112, Email: hgmcwhinney@pvamu.edu
Paul Behum, Office of Surface Mining Reclamation and Enforcement, US Department of Interior, Email: pbehum@osmre.gov 
Jon E. Brandt, Surface Mining and Reclamation Division, Railroad Commission of Texas Austin, TX  78701, Email: jon.brandt@rrc.state.tx.us 
Tameka Harney, Prairie View A&M University, P.O. Box 2502, Prairie View, TX 77446, Tel: 936-261-3102, Email: tharney@pvamu.edu 
Tony Grady, Prairie View A&M University, P.O. Box 2502, Prairie View, TX 77446, Tel: 936-261-3112, Email: tgrady2000@yahoo.com

This project addresses one of the most costly and longest lasting environment problems of the coal mining industry.  The problem of acid mind drainage (AMD) associated with coal mining or acid rock drainage (ARD) associated with mineral mining from tailing, open pits, and underground shafts, results from the mineralogy and mining activities at coal and mineral mining operations.  The loading of surface and subsurface waters with such metals as arsenic, cadmium, copper, zinc and silver (via leaching in acid media) increases the problem of AMD and exacerbates the potential for environmental damage.  In order to either prevent or mitigate environmental damage by AMD, regulators rely heavily on predictive tests, and models (tools) to assess the long-term potential for acid generation, at new mines, old mines and current mines.  Predictive tools take into account many factors of which static and kinetic chemical testing methods are good predictors of acid generation potential.  While several modifications have been made to these tests over the years, there are still some short comings.  These may include: (a) Over compensating for reactive sulfur content by including sulfate from gypsum and other non reactive sulfur in the total sulfur determination (b) In the determination of neutralization potential (NP), strong acids may cause the dissolution of stable minerals giving rise to erroneous results. (c) The presence of carbonates of manganese and iron in samples can be problematic in the determination of NP. (d) The formation of metal hydroxides in titrations involving NaOH can also lead to problems. X-ray Photoelectron Spectroscopy (XPS), a surface sensitive technique, shows strong potential as a non-destructive/non-invasive technique for the routine characterization of mine site materials for its elemental and mineral composition.  This study shows the potential to delineate information on the sulfate/sulfide ratio of representative samples in overburden matrices as low as 0.5% total bulk sulfur composition.

Emerging Technology Key to Accurate and Rapid Analysis for Arsenic in Environmental Wastewater and Soil
David K. Beck, B.S., Lancaster Laboratories, Inc., 2425 New Holland Pike, Lancaster, PA  17601, United States, Tel: 717-656-2300 ext. 1923, Fax: 717-656-2681, Email: DBeck@lancasterlabs.com
Parker D. Lindstrom, B.S., Lancaster Laboratories, Inc., 2425 New Holland Pike, Lancaster, PA  17601, United States, Tel: 717-656-2300 ext. 1503, Fax: 717-656-2681, Email: PLindstrom@lancasterlabs.com 
Kevin T. Moran, B.S., M.B.A., Lancaster Laboratories, Inc., 2425 New Holland Pike, Lancaster, PA  17601, United States, Tel: 717-656-2300 ext. 1339, Fax: 717-656-2681, Email: KMoran@lancasterlabs.com
Robert Strocko, B.S., Lancaster Laboratories, Inc., 2425 New Holland Pike, Lancaster, PA  17601, United States, Tel: 717-656-2300 ext. 1207, Fax: 717-656-2681, Email: Rstrocko@lancasterlabs.com

There are three key concerns that arise for any business that submits analytical samples for testing to a contract laboratory.  These are the technical accuracy of the results, complete regulatory compliance of the data, and rapid turnaround time.

Due to tighter regulatory limits for arsenic, and the variety of sample matrices being tested, achieving all three of these objectives can be a challenge.  It is key for users of today’s technology to possess a keen ability to recognize the limitations of the various technologies and select the most appropriate technique.  More robust techniques, like ICP-OES, are capable of rapid turnaround time, but are now unable to obtain detection limits low enough to meet today’s regulatory limits for Arsenic.  More sensitive techniques, like GFAA and quadrapole ICP-MS, possess the theoretical sensitivity to meet these limits, but often present a struggle due to matrix based interferences, that often lead to dilutions of the sample and delays in the analysis due to more frequent maintenance intervals.  Even worse, on some quadrapole ICP-MS systems, failure to recognize the occurrence of polyatomic interferences can lead to errors in the data that can be very costly both for the end user of the data and the laboratory conducting the testing.

One emerging technology that will play a key role in fortifying both the quality of analytical results and the speed in which the results can be obtained, is collision cell ICP-MS.  This process can also be equipped with a sample introduction system that is designed to handle many of the high matrix samples being analyzed.  This case study will demonstrate how an ICP-MS set up with both an HMI and a collision cell is a highly effective way of analyzing environmental samples at low detection limits.

 

Comparison of Naphthalene Ambient Air Sampling & Analysis Methods at a Former Manufactured Gas Plant Site
Alyson Fortune, Columbia Analytical Services Air Quality Laboratory, 2655 Park Center Drive, Simi Valley, CA 93065, Tel: 978-501-2735, Fax: 978-742-9897, Email: afortune@caslab.com
Leo Gendron, ENSR, 2 Technology Park Drive , Westford , MA 01886 , Tel: 978-589-3000, Fax: 978-589-3100, lgendron@ensr.aecom.com
Michael Tuday, Columbia Analytical Services Air Quality Laboratory, 2655 Park Center Drive, Simi Valley, CA 93065, Tel: 805-526-7161, Email: mtuday@caslab.com

Naphthalene is a contaminant of concern at former Manufactured Gas Plant (MGP) and other property redevelopment sites across the country. A major component of coal tar waste and a possible human carcinogen (EPA Group C), naphthalene is a chemical that may adversely affect human health at remediation sites. Due to its boiling point and vapor pressure, naphthalene can express both volatile and semi-volatile characteristics; therefore the question can arise of how to properly measure naphthalene in the vapor phase.  Two commonly applied methods of measuring vapor phase naphthalene include EPA Method TO-15, which utilizes whole air sampling in passivated stainless steel canisters; and EPA Method TO-13A, which utilizes high volume sorbent based sampling with polyurethane foam/XAD resin cartridges. Analytical differences between these two methods will be discussed, keeping reference to naphthalene’s unique chemical properties. This case study will present weekly data spanning a nine month period (December 2006-December 2007) from co-located EPA Method TO-15 and TO-13A ambient air samples at the perimeter of two MGP cleanup remediation sites. Distinct trends are noted and discussed in this paper when comparing the concentration results from the two methods.

 

Adding Method 6800 to the Hexavalent Chromium Analysis Toolbox
Mark Bruce PhD, TestAmerica, 4101 Shuffel St. NW, North Canton , OH , 44720 , USA ,  Tel: 330-966-7267, Email: Mark.Bruce@testamericainc.com
Albert Vicinie III, TestAmerica, 301 Alpha Dr. RIDC Park, Pittsburgh , PA , 15238 , USA ,  Tel: 412-963-7058, Email: Rusty.Vicinie@testamericainc.com
William Reinheimer, 301 Alpha Dr. RIDC Park, Pittsburgh , PA , 15238 , USA , Tel: 412-963-7058, Email: Bill.Reinheimer@testamericainc.com

Accurate site characterization of hexavalent chromium contamination is needed to assess risk and direct cleanup responses. Typically, an alkaline digestion (Method 3060A) is used to prepare solid samples for analysis. Colorimetric analysis (Method 7196A) and ion chromatographic analysis (Method 7199) are common, but can produce low biased results in reducing or highly absorptive matrices. Speciated isotope dilution analysis (Method 6800) monitors hexavalent chromium losses and transformations, and then mathematically compensates to produce more accurate results in difficult matrices.

We recommend a tiered approach to produce the most accurate data for the lowest cost. Start with the low cost 7196A analysis, if accuracy (matrix spike recovery) is unacceptable, analyze by 7199. If accuracy is still unacceptable, analyze by 6800.

Method 6800 is now available as an analytical option. It is designed to produce more accurate data in difficult matrices. Isotopically labeled Cr(VI) and Cr(III) species are added to each sample aliquot at the beginning of the sample preparation process. Method 3060A is used for solid sample preparation. Chromium species losses and transformations are monitored via chromium isotopes 50, 52 and 53 by ion chromatographic separation with ICP-Mass spec detection. The calculated Cr(VI) result uses the additional data from the isotopically labeled internal standards of Cr(VI) and Cr(III) to mathematically compensate for moderate species losses and transformations.

Adding Method 6800 to the analytical toolbox provides a means to improve data accuracy when Method 7196A and 7199 can’t meet measurement quality objectives for hexavalent chromium in difficult matrices.