Name: chemical analysis of water-accommodated fractions of crude oil spills using tims-ft-icr ms
Uploaded: 2017-03-03T14:00:00
Description: Watch this Scientific Journal Video about Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS at JoVE.com

This work was supported by the National Institute of Health (Grant No. R00GM106414 to FFL). We would like to acknowledge the Advanced Mass Spectrometry Facility of Florida International University for their support.

1. Preparation of the Low-energy Water-accommodated Fractions (LEWAF)
<ol>
	<li>Clean 2-L aspirator bottles by rinsing the bottles with methylene chloride in order to remove any potential contaminants.</li>
	<li>Fill bottles with 50&#160;mL of methylene chloride, close them, and agitate for 30 s. Drain them into the appropriate waste container. Repeat for a total of three washes.</li>
	<li>Use one aspirator bottle for the irradiation exposure and the other bottle as a control sample (perform duplicate sets of each if p...

<ol>
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M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Expansion+of+the+analytical+window+for+oil+spill+characterization+by+ultrahigh+resolution+mass+spectrometry:+beyond+gas+chromatography.">Expansion of the analytical window for oil spill characterization by ultrahigh resolution mass spectrometry: beyond gas chromatography.</a> Environ Sci Technol. 47 (13), 7530-7539 (2013).</li><li>Fernandez-Lima, F. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Petroleum+crude+oil+characterization+by+IMS-MS+and+FTICR+MS.">Petroleum crude oil characterization by IMS-MS and FTICR MS.</a> Anal Chem. 81 (24), 9941-9947 (2009).</li><li>Benigni, P., Marin, R., Fernandez-Lima, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Towards+unsupervised+polyaromatic+hydrocarbons+structural+assignment+from+SA-TIMS-FTMS+data.">Towards unsupervised polyaromatic hydrocarbons structural assignment from SA-TIMS-FTMS data.</a> Int J Ion Mobil Spectrom. 18 (3), 151-157 (2015).</li><li>Benigni, P., Thompson, C. J., Ridgeway, M. E., Park, M. A., Fernandez-Lima, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Targeted+high-resolution+ion+mobility+separation+coupled+to+ultrahigh-resolution+mass+spectrometry+of+endocrine+disruptors+in+complex+mixtures.">Targeted high-resolution ion mobility separation coupled to ultrahigh-resolution mass spectrometry of endocrine disruptors in complex mixtures.</a> Anal Chem. 87 (8), 4321-4325 (2015).</li><li>Benigni, P., Fernandez-Lima, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Oversampling+Selective+Accumulation+Trapped+Ion+Mobility+Spectrometry+coupled+to+FT-ICR+MS:+Fundamentals+and+Applications.">Oversampling Selective Accumulation Trapped Ion Mobility Spectrometry coupled to FT-ICR MS: Fundamentals and Applications.</a> Analytical Chemistry. , (2016).</li><li>Castellanos, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fast+Screening+of+Polycyclic+Aromatic+Hydrocarbons+using+Trapped+Ion+Mobility+Spectrometry+Mass+Spectrometry.">Fast Screening of Polycyclic Aromatic Hydrocarbons using Trapped Ion Mobility Spectrometry Mass Spectrometry.</a> Anal Methods. 6 (23), 9328-9332 (2014).</li><li>Benigni, P., DeBord, J. 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Critical Steps within the Protocol
The chemical complexity of LEWAFs requires accurate preparation in order for the laboratory experiments to accurately reflect what occurs naturally. A valid assessment of the data hinges on three criteria: minimizing the introduction of artifacts throughout sample handling (e.g., preparation of the LEWAF, sampling, extractions, and preparation of the sample for analysis), validating the experimental protocol (i.e., using dark controls for the p...

There are numerous sources of environmental exposure to crude oil, both from natural causes and from anthropogenic exposure. Upon release to the environment, particularly in the ocean, the crude oil can undergo partitioning, with the formation of an oil slick on the surface, a loss of volatile components to the atmosphere, and sedimentation. However, low-energy mixing of the poorly soluble oil and the water does occur, and this mixture, which is not classically solubilized, forms what is referred to as the low-energy water-accommodated fraction (LEWAF). The solubilization of the oil components in the water is typically enhanced during exposure of the oil-water interface to solar radiation. This photo-solubilization of the crude oil in the ocean can undergo significant chemical changes due to this exposure to solar radiation and/or due to enzymatic degradation1,2. Understanding these chemical changes and how they occur in the presence of the bulk matrix (i.e., the crude oil) is fundamental to mitigating the effects this exposure has on the environment.
Previous studies have shown that crude oil undergoes oxygenation, particularly the polycyclic aromatic hydrocarbons (PAHs), which represent a highly toxic source of contamination that harms organisms, undergoes bio-accumulation, and is bioactive3,5,6. Understanding the products of the different oxygenation processes is challenging because they occur only in the presence of the bulk matrix. Therefore, a single, standard analysis may not be representative of the changes occurring in nature. The preparation of the LEWAF must replicate the natural processes that take place in an environmental setting. Of particular interest is the oxygenation of PAHs, which occurs due to solar radiation.
The second challenge in the study of the water-accommodated fraction is the molecular identification of the different chemical constituents in the sample. Due to the complexity of the sample, caused by its high mass and degree of oxygen, the oxygenation products are typically unsuitable for the traditional analysis carried out by gas chromatography combined with MS analysis7,8. An alternative approach is to characterize the changes in the chemical formula of the sample by utilizing ultra-high mass resolution MS techniques (e.g., FT-ICR MS). By coupling TIMS to FT-ICR MS, in addition to the isobaric separation in the MS domain, the ion mobility spectrometry (IMS) dimension provides the separation and characteristic information for the different isomers present in the sample9,10,11. Combined with an atmospheric pressure laser ionization (APLI) source, the analysis can be selective to the conjugated molecules found in the sample, allowing the changes that the PAHs undergo to be accurately characterized12,13.
In this work, we describe a protocol for the preparation of LEWAFs exposed to photo-irradiation in order to study the transformation processes of the oil components. We also illustrate the changes that occur upon photo-irradiation, as well as the procedure for sample extraction. We will also present the use of APLI with TIMS coupled with FT-ICR MS to characterize the PAHs in the LEWAF as a function of the exposure to light.

<table border="0" cellpadding="0" cellspacing="0" width="915">
	<tbody>
		<tr height="20">
			<td height="20" style="height:20px;width:228px;">Reagents</td>
			<td style="width:156px;"></td>
			<td style="width:156px;"></td>
			<td style="width:375px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">methylene chloride</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">methanol</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">toluene</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Na2SO4</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Crude oil</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Instant Ocean&#174;</td>
			<td>Aquarium Systems</td>
			<td></td>
			<td>33 ppt salinity with 0.45 &#956;m pore filtration&#160;</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Name&#160;</td>
			<td>Company</td>
			<td>Catalog Number</td>
			<td>Comments</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Equipment</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Suntext XLS+</td>
			<td>Atlas Chicalo Ill, USA</td>
			<td></td>
			<td>1500 w xeon arc lamp, light intensity of 765 W/m2&#160;</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Atmospheric Pressure Laser Ionization</td>
			<td>Bruker Daltonics Inc, MA</td>
			<td></td>
			<td>Note a 266 nm laser is used</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">TIMS-FT-ICR MS Instrument</td>
			<td>Bruker Daltonics Inc, MA</td>
			<td></td>
			<td>The set up we had consisted of a 7T magnet with an infinity cell</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Name&#160;</td>
			<td>Company</td>
			<td>Catalog Number</td>
			<td>Comments</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Software</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">DataAnalysis 4.2</td>
			<td>Bruker Daltonics Inc, MA</td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Python 2.7</td>
			<td></td>
			<td></td>
			<td>Requires Numpy, Scipy, Pandas, glob, oct2py, and os</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Octave 4.0</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

chemical analysis of water-accommodated fractions of crude oil spills using tims-ft-icr ms

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry&#8211;Fourier transform&#8211;ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

LEWAF analysis by TIMS-FT-ICR MS results in a two-dimensional spectrum based on m/z and TIMS trapping voltage. Each of the samples, taken at different time points, can therefore be characterized based on the changing chemical composition, as observed by the distribution of chemical formulas and the isomeric contribution identified by the IMS (see Figure 1). Typically, the m/z information can be utilized to assign elemental formulas to the analyzed peaks....

Watch this Scientific Journal Video about Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS at JoVE.com

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS

The low-energy water-accommodated fraction (LEWAF) of crude oil is a challenging system to analyze, because over time, this complex mixture undergoes chemical transformations. This protocol illustrates methods for the preparation of the LEWAF sample and for performing photo-irradiation and chemical analysis by trapped ion mobility spectrometry&#8211;FT-ICR MS.

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system ...

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