LC-MS/MS Analysis of Acrylamide in Drinking Water Using Large Volume Injection

Published By: Restek Corporation

Year of Publication: 2020


Abstract: In this work, we share a method for the analysis of acrylamide in drinking water at low ppt levels using large volume injections directly into an LC-MS/MS.

Restek Offers First and Only Complete CRMs for EPA Method 525.3

525 3_PR_imageRestek has just released the only certified reference materials (CRMs) developed specifically for EPA Method 525.3. These standards include all the required analytes and no unnecessary compounds, and they are formulated to provide maximum stability in concentrations convenient for dilution. Restek® CRMs are manufactured and QC-tested in our ISO-accredited labs and are quantitatively tested to confirm composition and ensure quality. The new 525.3 standards join Restek’s existing 525.2 standards, so a complete, specially formulated standards set is now available for both versions of the method.

Learn more at


Misselwitz and Rattray to Speak at the EPA’s 22nd Annual Quality Assurance Conference

Chris Rattray

Chris Rattray

Michelle Misselwitz

Michelle Misselwitz

From October 15–19, 2012, the U.S. Environmental Protection Agency (EPA) will hold its 22nd Annual Quality Assurance Conference in Region 6, Dallas, TX. Two Restek chemists, Michelle Misselwitz and Chris Rattray, will be making the trip south to present some of their latest work, including GCxGC analysis of pesticides and pharmaceutical and personal care products (PPCPs) as well as lowering detection limits for drinking water methods using large volume splitless injection (LVSI). For more details on each presentation, see below.

This free conference has been organized for years by the incredibly dedicated Charles Ritchie and is a great way to network with a wide range of colleagues and get caught up to speed on recent developments in environmental analysis. You can learn more about the Quality Assurance Conference on the EPA’s website ( and can also re-read Michelle Misselwitz’s blog on last year’s event ( .

We hope to see you there!


Technical Presentations


9:30 a.m. / Session E
The QuEChERS Sample Preparation Approach and Comprehensive Two-Dimensional Gas Chromatography Time-of-Flight Mass Spectrometry for the Analysis of Pesticides in Tobacco

Michelle Misselwitz

Tobacco is a high-value production crop for the United States and ranks 6th among the amount of pesticides applied per acre in American agriculture. Even after the processing of tobacco, some pesticide residues remain on the final product. We used the Quick–Easy–Cheap–Effective–Rugged–Safe (QuEChERS) sample preparation approach to isolate pesticide residues from loose cigarette tobacco. Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) was used to determine pesticide residues in the resulting extracts.

3:00 p.m. / Session C
Analysis of Pharmaceutical and Personal Care Products and Other Emerging Environmental Contaminants in Water Using a Highly Efficient GCxGC-TOFMS System

Michelle Misselwitz

Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) is a powerful multidimensional approach to sample analysis that is unmatched by traditional one-dimensional chromatography. By operating the system to maximize efficiency in both the first and second dimension, GCxGC-TOFMS has the ability to detect, identify, and quantify or semi-quantify an unlimited number of target, non-target, and unknown compounds (including emerging compounds of concern) with full mass spectra and sub- to low-pg sensitivity. Using this technique, water samples were collected from the urban river in Las Vegas to analyze a large number of pharmaceutical and personal care products and other emerging environmental contaminants.

4:00 p.m. / Session D
Achieving Lower Detection Limits for Multiple Drinking Water Methods Using Large Volume Splitless Injections on an Unmodified Split/Splitless Injection Port

Chris Rattray
For more information, email Chris Rattray.

Utilizing a large volume splitless injection is advantageous for many reasons. Some of these include shipping and extracting significantly smaller sample sizes, reducing extract concentration, or decreasing limits of detection for trace-level analysis in drinking water. The drawback for many is that large volume injections typically require a specialized injection port. However, with concurrent solvent recondensation-large volume splitless injection (CSR-LVSI), a large volume injection can be achieved on an unmodified Agilent split/splitless injection port. Here we analyzed multiple drinking water methods using CSR-LVSI on an Agilent 7890/5975C GC-MSD and injected up to 10 µL to achieve lower detection limits.

Restek Chromatographers Lend Their Expertise to NEMC 2012

As in years past, Restek sent a contingent of environmental and air chromatography experts to the National Environmental Monitoring Conference (NEMC). This year’s event took place in Washington, DC, and featured talks from our own Michelle Misselwitz, Jason Herrington, and Chris Rattray. See below to review their abstracts and presentations.

Restek was also involved with NEMC from an organizational standpoint—Joe Konschnik supported Earl Hansen, NEMC’s Technical Program Chair, by serving as Co-Chair of the Air Methods & Monitoring Session. In this role, Joe helped plan, coordinate, and moderate oral presentations by some of the industry’s brightest minds. The session received such unprecedented interest that it was split into three sections!

We are also proud to announce that Joe has been invited to join the steering committee for NEMC 2013. We hope you consider making the trip to San Antonio, TX, on August 5–9 for what is sure to be an enlightening conference.

For more information on NEMC, visit their website at

Technical Presentations

Characterization of Crude Oils and Tar Balls Using Biomarkers and Comprehensive Two-Dimensional Gas Chromatography

Michelle Misselwitz (presenter), Jack Cochran, Chris English, Barry Burger

Abstract: The analysis of petroleum biomarkers is commonly used to determine the origin of crude oil samples. These biomarkers are “molecular fossils” that are complex hydrocarbon molecules from formerly living organisms in the source rock. Utilizing biomarkers to fingerprint crude oils is advantageous because they are resistant to weathering or degradation and provide a unique profile for oil-to-oil correlations. This information can be used by environmental forensic chemists to pinpoint source oil from spills, or in this case, tar balls washed along the shore of the Gulf of Mexico.

Gas chromatography mass spectrometry (GC-MS) is typically used to monitor the ratios of hopane and sterane isomers. This work will focus on characterizing crude oil samples, including from the broken riser pipe collected via an underwater robot during the Deepwater Horizon oil spill of 2010, by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS). GCxGC is a two-dimensional separation using two columns of different selectivity with thermal modulation. Utilizing a retention plane provides a structured chromatogram that aids in fingerprinting complex oil samples. The hopane/sterane profile of these oils will then be compared to extracts of tar balls that washed ashore on the Gulf of Mexico beaches months after the spill occurred. 

Concerns Regarding 24-Hour Sampling for Formaldehyde, Acetaldehyde, and Acrolein Using 2,4-Dinitrophenylhydrazine (DNPH)-Coated Solid Sorbents

Jason Herrington
For more information, email Jason Herrington.

Abstract: There is high demand for accurate and reliable airborne carbonyl measurement methods due to the human health and environmental impacts of carbonyls and their effects on atmospheric chemistry. Carbonyl sampling methodologies based on derivatization with 2,4-dinitrophenylhydrazine (DNPH)-coated solid sorbents are the current standard. However, these methods present multiple challenges that detract from an accurate understanding of carbonyl-related exposure, health effects, and atmospheric chemistry. Since their original development in the late 1970s, these methods have been extensively evaluated and developed. However, studies have demonstrated formaldehyde interferences from 2,4-dinitrophenylazide (DNPA) and 2,2-dinitrochlorobenze (DNCB); low acetaldehyde collection efficiencies for 24-hour sampling; and numerous acrolein sampling interferences. This presentation will discuss the sampling issues associated with DNPH-coated solid sorbents, the potential for remedies, and will provide recommendations and areas for future research. The presentation of this information is important because it seems clear that carbonyl data produced utilizing DNPH-based methods are being reported without acknowledgment of the method short-comings or how to best address them.

Click here to download a PDF of the full presentation.

Lowering Detection Limits for 1,4-Dioxane in Drinking Water using EPA 522 with Concurrent Solvent Recondensation – Large Volume Splitless Injection

Christopher Rattray (presenter), Jack Cochran, Scott Grossman, Chris English
For more information, email Christopher Rattray.

Abstract: The third Unregulated Contaminant Monitoring Regulation (UCMR 3) is scheduled to begin next year and includes a requirement for 1,4-dioxane analysis using EPA Method 522. EPA Method 522 was originally written to be performed using a standard gas chromatograph (GC) equipped with a single quadrupole mass spectrometer (MS). However, a recent reevaluation of 1,4-dioxane’s carcinogenic risk resulted in the EPA lowering the suggested minimum reporting limit from 0.3 to 0.07 µg/L, and even when operating in selected ion monitoring (SIM) mode, most GC-MS instruments would be hard pressed to meet this lower 0.07 µg/L limit. One way to lower detection limits is to inject more sample, but large volume splitless injection (LVSI) for gas chromatography typically requires a special injection port such as a programmable temperature vaporizer (PTV). The technique described here for the analysis of 1,4-dioxane in drinking water uses an unmodified split/splitless inlet with LVSI to lower reporting limits without concentrating extract. With an injection volume of 10 µL, we achieved a linear calibration range exceeding 3 orders of magnitude, with levels ranging from 5 to 10,000 pg on column. We saw 89% recovery when 1 L of bottled water fortified at 0.005 µg/L was extracted using coconut charcoal SPE tubes and analyzed according to EPA Method 522 with LVSI, matching the method performance data published by the EPA. This LVSI technique requires absolutely no changes to standard laboratory instrumentation.

Click here to download a PDF of the full presentation.

Air Methods/Monitoring Sessions

• Data Interpretation and Policy Development

• Developments in Analytical Methods

• Sorbent Based Sampling Methods

Session Chairs & Moderators: Joe Konschnik1, George Lucier2, Deb Gaynor3, Michael Flournoy4, Nicola Watson5
1. Restek Corporation, 2. Battelle Memorial Institute, 3. Phoenix Chemistry Services, 4. SGS-Analytical Perspectives, 5. Markes International

For more information, visit

Screen Drinking Water for EPA 539 Hormones Using a Calibration Standard Specially Formulated for UCMR3

The Unregulated Contaminant Monitoring Rule 3 (UCMR3) requires monitoring of all public drinking water systems with 10,000 or more customers. For hormone screening in finished drinking water, UCMR3 lists the same seven compounds as EPA Method 539; however, the concentrations differ between the two lists.

A new certified reference material (CRM) released by Restek contains the seven hormones listed in EPA Method 539 conveniently formulated to the concentrations outlined by UCMR3 to save analysts time and labor. For those following EPA 539 guidelines, Restek also offers the same mix of hormones with the appropriate concentrations.

Compound List for Restek's EPA Method 539 CRMs

Of course, like all Restek CRMs, these standards are both manufactured and QC-tested in an ISO-accredited lab to easily satisfy ISO requirements.

Analyze a Full EPA 524.3 List Using Just Three Ampuls With New Restek EPA 524.3 Certified Reference Materials!

In support of the U.S. Safe Drinking Water Act (SDWA), Restek has formulated a complete set of EPA 524.3 reference standards for the monitoring of purgeable organic compounds in drinking water—using as few as three ampuls! This collection of certified reference materials (CRMs) also covers the seven volatile organic compounds (VOCs) included in the Unregulated Contaminant Monitoring Rule 3 (UCMR3), which requires monitoring of all public drinking water systems with 10,000 or more customers. It is also ideal for surface water and groundwater testing inside or outside the U.S.

This new set of reference standards offers a full 82-component EPA 524.3 list using as few as three ampuls to reduce prep time and chances for error or contamination. The EPA 524.3 VOA MegaMix® ampul includes the required oxygenates group for convenient ordering, while the volatile gases are prepared separately to allow replacement of shorter-life components without wasting money on the full list. Internal and surrogate standards are available independently or as a combined mix, letting analysts choose the option that works best for them. Of course, like all Restek certified reference materials (CRMs), they are manufactured and QC-tested in an ISO-accredited lab to easily satisfy ISO requirements.

Simplify your EPA 524.3 analyses and start saving today with Restek’s new reference standards set.

Lowering Detection Limits for 1,4-Dioxane in Drinking Water Using Large Volume Injection in an Unmodified Splitless GC Inlet

Author(s): Chris Rattray, Jack Cochran, Chris English

Published By: LCGC North America

Issue: June 2012

Year of Publication: 2012

Abstract: Recent work analyzing 1,4-dioxane in drinking water using large volume splitless injection is summarized in this  LCGC North America application note. Concurrent solvent recondensation–large volume splitless injection (CSR-LVSI), an alternative to programmed temperature vaporization (PTV), typically requires a special GC inlet. The technique described here uses an unmodified split/splitless inlet with CSR-LVSI to lower detection limits for the analysis of 1,4-dioxane in drinking water. The complete version of this application is also available and can be found here:

Large Volume Splitless Injection Using an Unmodified Split/Splitless Inlet and GC-TOFMS for Pesticides and Brominated Flame Retardants

Author(s): Michelle Misselwitz, Jack Cochran

Published By: Restek Corporation

Year of Publication: 2011


Abstract: Concurrent solvent recondensation large volume splitless injection (CSR-LVSI) GC/MS is used here for analyzing pesticides and brominated flame retardants in drinking water based on EPA Method 527. CSR-LVSI allows a time-consuming sample extract concentration step to be eliminated, but can also be used with extract concentration for lower detection limits.