1 Annual Report 1994 RESEARCH AND DEVELOPMENT 1 Analytical Laboratory Services Ontario Ministry of Environment Energy & 1 March, 1995 I-:ND Copyright Provisions and Restrictions on Copying: This Ontario Ministry of the Environment work is protected by Crown copyright (unless otherwise indicated), which is held by the Queen's Printer for Ontario. It may be reproduced for non-commercial purposes if credit is given and Crown copyright is acknowledged. It may not be reproduced, in all or in part, for any commercial purpose except under a licence from the Queen's Printer for Ontario. For information on reproducing Government of Ontario works, please contact ServiceOntario Publications at copyright aontario.ca 1 ISSN 1203-0104 1 1 1994 ANNUAL REPORT RESEARCH AND DEVELOPMENT ANALYTICAL LABORATORY SERVICES MARCH, 1995 JUNE 1995 Cette publication technique nest disponibie qu'en anglais. Copyright: Queen's Printer for Ontario, 1995 This publication may be reproduced for non-commercial purposes with appropriate attribution. PIBS 2511-02 1 1 MOEE Analytical Laboratory Services - 1994 R&D Antiual Report OVERVIEW Research and Development is an important component of the Ontario Ministry of Environment and Energy (MOEE) analytical laboratory services mandate to provide expert consultation and reference capabilities for environmental analysis. This year's R&D Report represents a further evolution in the reporting of the ministry's analytical research activities. The nature of the individual reports of analytical research studies has changed little from the format used last year. However, the collaborative studies with external groups are reported here for the first time in a separate section. Also, the report includes research performed by Regional laboratory staff, in addition to work done at the Laboratory Services Branch. Thus, this year's R&D report reflects the work performed in the MOEE laboratory system, and not just from one centre. The amount of collaborative work performed by MOEE analytical laboratory staff is increasing. This reflects the need to conserve resources, and to involve expertise from external organizations where collaboration is mutually beneficial. As such cooperation permits a much greater range of expertise to tackle difficult problems, these collaborations ultimately result in significant benefits to the research itself. More rapid solution of problems, higher quality, and broader scope of application of results are some of the benefits received by university, industry, and government partners. For further information on any of the projects described in this report, readers are directed to the Author: Dr. Ray Clement 1 Chair, Analytical Laboratory Services R&D Committee Ontario Ministry of Environment & Energy Laboratory Services Branch 125 Resources Road Etobicoke, Ontario M9P 3V6 phone: 416-235-5906 fax: 416-235-5744 - i - MOEE.Analytical Laboratory Services - 1994 R&D Annual Report Table of Contents pale ........................................................i Overview ................................ New Applications of Technology 1 .............. I. Microwave Digestion Technique for Trace Metals Analysis 2 of Vegetation, Soil, and Sediment ................. I II. Negative Ion Chemical Ionization (NICI) Confirmation 3 of Halogenated Organics ......................... III. LC/MS Analysis of Environmental Samples 3 ................... IV. Evaluation of Ion Trap Mass Spectrometry Detector 5 (ITD) for Organics in Drinking Water .......................................... Methods Development 9 ............. 1. Development of Analysis Protocols for Compost Materials 10 ....................... II. GC/MS Analysis of PAH in Drinking Waters 11 .................. III. Expansion of Drinking Water Analysis Capabilities 12 ....................................... IV. Disinfection By-Products 15 .......... V. The Determination of Geosmin (GEO) and 2-Methylisoborneol 16 (2-MIB) by Isotope Dilution High Resolution Mass Spectrometry ....................... VI. Hexane Micro-Extraction Roller Methodology 18 ................... VII. Methods for Regulation 347 - Waste Derived Fuel 20 1 MOEE Analytical Laboratory Services - 1994 R&D Annual Report Partnerships ................................................... 23 ................ I. Determination of Chromium Species in Environmental 24 Samples Using HPLC-DIN-ICP-MS ........ II. Supercritical Fluid Extraction of Soil Samples for PCDDs/PCDFs 25 ............ III. Field Evaluation of a Membrane Filter/ Dissolution Method 26 for the Recovery of Cryptosporidium Oocysts and Giardia Cysts from Potable Water .............. IV. Improved Presence-Absence Medium for the Analysis of 28 Treated Drinking Water .... V. PLS/IR Analysis of Oils and Greases in Water and Sediment Samples 29 External Research .............................................. 31 I. ERP 701G: The Application of Quadrupole Ion Trap Mass Spectrometry 32 to the Development of New Analytical Protocols for Dioxins/Furans ...... II. ERP 707G: Analysis of Sulfur-Containing PAH in Ambient Air and 34 in Selected Sources ................ III. ERP 72OG: Automated Counting of Bacterial Colonies 34 ........ IV. ERP 7290: Development of an Efficient Extraction and Clean-Up 35 Procedure Based on Commercially Available Solid-Phase Cartridges for the Determination of Chlorinated Dioxins and Furans in Biological Tissues ........................... Publications and Presentations - 1994 37 Analytical Laboratory Services - iv - MOEE Analytical Laboratory Services - 1994 R&D Annum Report 1 New Applications of Technology Introduction 1 The evaluation, application, and adoption of technologies for improved I environmental analysis is an ongoing activity. In 1994, the Analytical Laboratory Community of the Ontario Ministry of the Environment and Energy (MOEE) was involved with several projects in which the principal focus was to evaluate novel applications of technologies. Sample preparation technologies such as microwave digestion and solid-phase extraction were examined. A variety of mass spectrometer- based (MS) technologies were also developed, including liquid chromatography-MS (LC-MS), LC-Inductively Coupled Plasma/MS (LC-ICP/MS), negative ion chemical ionization MS (NICIMS), and Ion Trap MS (ITD). The general thrust in the above development is to provide our customers with improved analytical services, such as lower detection limits, greater specificity, faster turnaround and reduced cost. An additional important in-house concern is to adopt "greener" methods, i.e. - ones that require reduced dependence on toxic organic solvents and mineral acids for extractions and digestions. The projects described here are not fundamental investigations into the nature of instrumentation systems, nor are they designed to develop new hardware for application to environmental analysis in the remote future. These projects are ones for which the basic technology used is available commercially, but where the specific application development depends more on the technology used than other aspects of the methodology. 1 1 2 MOEE Analytical Laboratory Services - 1994 R&D Annual Report 1 I. Microwave Digestion Technique for Trace Metals Analysis of Vegetation, Soil, and Sediment 1 Study Leader: Liz Pastorek Study Team: Jane Thrush Customer: Objectives Primary objectives were to: perform metals preparation of soil and vegetation matrices to produce results to within +/- 20 % of initial agreement of present method results; ensure no carryover or contamination of samples; preserve the present detection limits; improve throughput time at the preparation stage; Backgrou nd Historically, the MOEE lab has carried out its vegetation, soil, and sediment metals sample preparation using a strong mixed acid heated digestion. This tends to be labour intensive, time consuming and potentially unsafe.. The latest developments in the sample preparation area have included various microwave techniques. One of these, the high pressure vessel microwave system, while relatively fast is still labour intensive. Flow-through systems are being developed that could save staff time while matching the present methods in extraction capability. As an initial step a flow-through system, from CEM, was brought in for evaluation. I Results A second study, this time of the Questron System, was carried out. In addition to the basic advantages as shown in the study of the CEM System, the Questron has the advantage of an automatic predigestion of samples if needed. Results using the Questron system matched those obtained by using the present MOEE method very well. MOEE Analytical Laboratory Services - 1994 R&D Annual Report 3 Current Status A system, CEM or Questron will be purchased, based on the evaluations conducted. At that time detailed optimization studies will be performed, followed by method validation by parallel testing with the present method. This will start once the system is installed, expectedly in May or June, 1995. II. Negative Ion Chemical Ionization (NICI) Confirmation of Halogenated Organics 1 Study Leader: Don Robinson Study Team: Vince Taguchi, Kim Ngo, Bob Kleins I Customer: Mass Spectrometry Laboratory Objective 1 To improve Branch capability to identify unknown organic compounds. Background Analytical techniques based on the use of gas chromatography/ mass spectrometry (GC/MS) instrumentation are considered to be state-of-the-art for the determination of trace organic compounds in environmental samples. These systems work by converting organic molecules into a series of ions, based on the structure of the molecule. The pattern and relative abundances of the ions formed are characteristic of the specific molecule, like a fingerprint. Negative ions can also be formed, but for various reasons their use has been somewhat limited. One of the major drawbacks of using negative ions is that standard patterns (mass spectra) of these ions are not available for many compounds. To create a library of negative ion mass spectra would help identify unknown organic compounds by providing supplemental information to that obtained by examining positive ion mass spectra. 1 Results Negative Ion Chemical Ionization (NICI) was set up on the Finnigan 4500 GC/MS systems and an NICI library of 90 compounds was created. Confirmation of toxaphenes and PCBs have been done in fish extracts. 1