Insights into analytical instrumentation of the future

Series: MOMENTUM

Forecasts of dramatic increases in the world’s population have triggered efforts worldwide to find new sources of energy and more effective ways of exploiting conventional energy sources.

The focus on energy has also prompted concerns over associated environmental issues and the impact of energy consumption and generation processes on water, air, and soil. Fossil fuels are a prime example, where continued reliance on coal could lead to greater amounts of carbon dioxide being released into the atmosphere, escalating a number of environmental problems. Needless to say, it is necessary to devise alternative energy solutions that have a low impact on the environment.

At Shimadzu Corporation we want to use our internationally renowned analytical instruments to solve energy-related environmental problems. For example, the Gas Chromatograph Mass Spectrometer (GC-MS) enables the qualitative and quantitative analysis of the chemical composition of samples. This analytical instrument can help towards evaluating and improving the efficiency of energy generation techniques—for both conventional and new approaches.

Another example is the Total Organic Carbon Analyzer (TOC). The analysis of samples of water from energy extraction sites allows environmental evaluation and identification of different sources of pollution. In particular, the carbon content of water is a useful indicator of water pollution. Our TOC is used extensively for these kinds of environmental applications. In this way analytical instruments manufactured by Shimadzu Corporation can be used for ongoing monitoring of environmental health, as well as one-off evaluations thus contributing to society through science and technology 

Shimadzu Center for Advanced Analytical Chemistry

In this issue of Momentum, we meet Kevin Schug, The University of Texas at Arlington (UT Arlington) Associate Professor of Chemistry and Biochemistry, Shimadzu Distinguished Professor of Analytical Chemistry and Shimadzu Science Advisor to the Vice President for Research. He tells us about his challenging research on the environmental effects of extracting shale gas in northern Texas and how Shimadzu instruments contribute to his work.

“We have one of almost every analytical instrument produced by Shimadzu,” explains Schug. “Collaboration and partnerships with Shimadzu have been extremely productive in helping us meet our analytical goals.” The suite of instruments at the Shimadzu Center for Advanced Analytical Chemistry (SCAAC) include a TOC, a headspace gas chromatograph (headspace-GC), multiple GC-MS, multiple liquid chromatograph mass spectrometers (LC-MS), and an inductively coupled plasma optical emission spectrometer (ICP-OES). 

The SCAAC was opened on 9 April 2012 with Dr Kozo Miseki representing Shimadzu Corporation. The Center houses chromatography, spectroscopy, and mass spectrometry equipment worth US$6 million. Its mission is to provide support for science and engineering research to academia, government, and industry, either per sample or on a contract basis. 

It is part of UT Arlington's Shimadzu Institute for Research Technologies. The Institute is a $25.2 million (US) endeavor fueled by Shimadzu Scientific Instruments' $7.5 million corporate gift to the University and their previous in-kind gift of nearly $3 million in instrumentation. 

“I have used analytical equipment made by Shimadzu since my graduate school days”, says Schug. “I am able to act as a conduit for new research avenues for the Center and local researchers in academia and industry. I also coordinate partnerships between UT Arlington, Shimadzu Scientific Instruments, Inc., and Shimadzu Corporation.” 

The roots of Schug’s research are in chromatography but he is extending his work towards studies aimed at a better molecular level understanding of separation systems. An example is the improved methods under development for metabolite analysis based on hydrophilic interaction liquid chromatography.

Electrospray ionization is another area of expertise for the Schug group. Here the goal is to develop increased throughput methods for measurement by mass spectrometry of non-covalent binding for high-efficiency drug discovery protocols.

The applications of Schug’s research stem from his fundamental understanding of the advantages of combining high-efficiency separations with high-sensitivity mass spectrometry detection.

Furthermore, Schug is optimizing on-line sample preparation using restricted access media, specifically the CoSense instrumentation set-up and MAYI semi-permeable surface phases, in conjunction with LC-MS workflows.

“This approach is under-exploited in the United States,” says Schug. “We have first-hand experience of the significant benefits of direct injection of biological fluids for the determination of traces of small bioactive molecules.” Experiments on the determination of steroid hormones and endocrine disruptors from matrices, such as plasma, cerebrospinal fluid, urine, and saliva, show higher recoveries and improved detection limits using CoSense compared with off-line sample preparation techniques.
The instrumentation at SCAAC has played a pivotal role in Schug’s research on the potential impact of industrial processes on the environment. These include ‘fracking’ and its effect on the quality of water in private wells in Texas. The studies have made full use of Shimadzu instruments, such as GC-MS and ICP-OES for chemical and metal speciation in water samples. “We are quite excited about our most recent acquisition of GCMS-TQ8030 technology,” says Schug. “This will be used to determine the byproducts of disinfection and other environmental contaminants in water.” 

The Shimadzu Center is also a hub for student education. Schug explains how his students are highly trained users on many of the instruments in the Center. “Their experience of working on research projects enables them to train other researchers,” he adds. 

Schug is also participating in the development of new inquiry-based laboratory experiments for introductory chemistry courses at UT Arlington. Notably, of the US$18.5M allocated for acquisition of instrumentation for the Shimadzu Institute for Research Technologies, which was formally established in February 2013 and includes the SCAAC, approximately US$3M was earmarked for instrumentation for undergraduate teaching. The accessibility of instrumentation at SCAAC within a research environment provides an unprecedented opportunity for students at UT Arlington to contribute to research and development. 

As Schug stresses, there are few other places in the world where first-year undergraduate students are exposed to state-of-the-art GC-MS, LC-MS, and other spectroscopy instrumentation as part of their science laboratory coursework.

“The collaboration between Shimadzu and UT Arlington is a truly unique partnership, and it is exciting to play a central role in directing much of this activity.” 

Research on the environmental impact of ‘fracking’

Hydraulic fracturing or ‘fracking’ is a procedure used to recover gas and oil from layers of shale rock lying several kilometers below the Earth’s surface. More precisely, in the process of fracking, a hole is drilled into the Earth after which a high-pressure liquid mixture of water, chemicals, and sand is injected into the rock with the goal of forcing the gas to flow to the well head. Often, the well is drilled horizontally into the rock to create cracks that release gas.

Schug is working with colleagues to clarify whether fracking has any negative effects on private well water quality. But why look at private wells? Schug explains that in spite of fracking being ‘big business in Texas’, with extraction sites near highly populated areas, organizations such as the Environmental Protection Agency only regularly monitor municipal water quality. Private well water is not regularly tested.

In a recent publication Schug and his colleagues reported finding higher levels of arsenic in groundwater near North Texas shale gas wells [1]. “We analyzed water from 100 wells in this, the largest study of its kind ever conducted,” says Schug. They used a variety of analytical techniques including Shimadzu GC-MS, Shimadzu headspace-GC, and an ICP-MS.

The findings generated considerable interest within the media and the scientific community. The researchers at UT Arlington are keen to document their findings for use as ‘best practices’ for minimizing potential contamination related to fracking.

Schug and his team have started further studies in other parts of Texas where new fracking is starting. “In west Texas, we were able to initiate a time course study to include a baseline of water quality parameters prior to the start of hydraulic fracturing activities,” says Schug. 

Recent research highlights from the Kevin Schug Group

Antibacterial drug discovery 

One of Kevin Schug’s projects is on the development of new materials for antibacterial drug discovery based on an ambient ionization mass spectrometry workflow [2]. This is research that is being conducted with two other UT Arlington chemists: physical materials chemist, Professor Richard Timmons and synthetic organic chemist, Professor Frank Foss.

The initial proof-of-principle results of this project demonstrate what may potentially be a promising method for identifying unknown bioactive compounds in complex mixtures. Their approach further develops functionalized polymeric mesh screens for selective compound extraction and direct analysis by transmission-mode desorption electrospray ionization (TM-DESI) mass spectrometry. The researchers envision this tool offering a new approach for natural-product drug discovery from less well-known natural sources that are only present in limited quantities.

Bulk derivatization for high-sensitivity detection of target molecules

In conjunction with his research on CoSense and on-line sample preparation, Schug is also working on bulk derivatization [3]. Here, a derivatization reagent, which acts as a probe to target small molecules of interest, is added directly to a biological fluid sample prior to any other pre-treatment, except perhaps pH adjustment.

The role of the derivatization reagent is to facilitate increased ionization efficiency in electrospray ionization mass spectroscopy. This improves the lower limits of detection for the target compound.

“Although derivatization in general is often considered to be a hassle, it is our experience that as much as two to three orders of magnitude in sensitivity can be gained with molecules such as estrogens by appending a group that increases the surface activity and a propensity for charge acquisition,” says Schug.

The researchers are preparing manuscripts for publication that fully describe automated protocols so that a biological fluid sample need only be placed in the auto sampler for the necessary pre-treatment. Schug adds that such methods would be especially useful for the analysts at the SCAAC at UT Arlington.

The future of analytical instrumentation

Schug has his own vision of how analytical instrumentation will evolve by “getting smaller and more sensitive”. He also expects a revolution in the next few years with increased use of cloud computing to handle big data.

He adds that massive data mining will allow researchers to address many questions in parallel and get answers back fast. The challenges include devising effective training methods, namely, interfacing computer science and informatics with analytical chemistry.

Shimadzu Corporation has an excellent pedigree to lead the advance of this new analytical technology with its wide-ranging instrumentation. Indeed, UT Arlington is working with Shimadzu to develop new streamlined solutions for data analysis by using cloud computing resources at UT Arlington.

“We are extremely excited about our future plans for collaborating with Shimadzu to develop multivariate data correlations in research areas as diverse as environmental contamination and disease biomarker discovery.”

* Affiliates and titles of the persons mentioned in this article reflect their status at the time of the interview.

Further information

1. Brian E. Fontenot †, Laura R. Hunt †, Zacariah L. Hildenbrand †, Doug D. Carlton Jr †, Hyppolite Oka †, Jayme L. Walton †, Dan Hopkins ‡, Alexandra Osorio §, Bryan Bjorndal §, Qinhong H. Hu †, and Kevin A. Schug *†

   An Evaluation of Water Quality in Private Drinking Water Wells Near Natural Gas Extraction Sites in the Barnett Shale Formation

   † Department of Biology, Department of Chemistry and Biochemistry, and Department of Earth and Environmental Sciences, University of Texas at Arlington, Arlington, Texas 76019, United States
   ‡ Geotech Environmental Equipment Inc., Carrollton, Texas 75006, United States
   § Assure Controls Inc., Vista, California 92081, United States

   Environ. Sci. Technol., 2013
   DOI: 10.1021/es4011724
   Published online: July 25, 2013

2. Samuel H. Yang, Evelyn H. Wang, John A. Gurak, Sumit Bhawal, Rajendrasing Deshmukh, Aruna B. Wijeratne, Brian L. Edwards, Frank W. Foss, Jr, Richard B. Timmons, and Kevin A. Schug

   Affinity Mesh Screen Materials for Selective Extraction and Analysis of Antibiotics Using Transmission Mode Desorption Electrospray Ionization Mass Spectrometry.

   Langmuir, 2013, 29, 8046–8053

3. S. H. Yang, A. A. Morgan, H. P. Nguyen, H. Moore, B. J. Figard, and K. A. Schug *

   Quantitative Determination of Bisphenol A from Human Saliva using Bulk Derivatization and Trap-and-Elute HPLC-Electrospray Ionization – Mass Spectrometry.

   Environ. Toxicol. Chem. 2011, 30, 1243–1251