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The Official Magazine of The OceTHE OFFICIALa MAGAZINEnog OF THE OCEANOGRAPHYra SOCIETYphy CITATION Farrington, J.W. 2014. Organic chemicals of environmental concern: Water sampling and analytical challenges. Oceanography 27(1):214–216, http://dx.doi.org/10.5670/oceanog.2014.24. DOI http://dx.doi.org/10.5670/oceanog.2014.24 COPYRIGHT This article has been published inOceanography , Volume 27, Number 1, a quarterly journal of The Oceanography Society. Copyright 2014 by The Oceanography Society. All rights reserved. USAGE Permission is granted to copy this article for use in teaching and research. Republication, systematic reproduction, or collective redistribution of any portion of this article by photocopy machine, reposting, or other means is permitted only with the approval of The Oceanography Society. Send all correspondence to: [email protected] or The Oceanography Society, PO Box 1931, Rockville, MD 20849-1931, USA. DOWNLOADED FROM HTTP://WWW.TOS.ORG/OCEANOGRAPHY SPECIAL ISSUE ON CHANGING OCEAN CHEMISTRY » ANTHROPOCENE: THE FUTURE…SO FAR Organic Chemicals of Environmental Concern Water Sampling and Analytical Challenges BY JOHN W. FARRINGTON Comprehensive two-dimensional gas chromatograph of heavy fuel oil from the Container Ship Cosco Busan. Reprinted from Oceanus 49(1). Image courtesy of Karin Lemkau, ©Woods Hole Oceanographic Institution 214 Oceanography | Vol. 27, No. 1 A detailed understanding of the biogeo- the surface to avoid surface slick con- Takada, 2014, in this issue). Organic Chemicals of chemical cycles of organic chemicals taminations. Eventually, in situ pumping In the early days, the gas chroma- of environmental concern (OCEC) in systems employing glass fiber filters for tography columns in routine use could the ocean requires measurement of particulate matter sampling and sorbent not resolve these mixtures of PCBs Environmental Concern their concentrations in the water col- materials to sample the dissolved phase and PAHs into individual compounds umn (Farrington and Takada, 2014, were developed for sampling both surface to allow quantitative measurements of in this issue, and references therein). and deep waters (e.g., Petrick et al., 1996). each of the components. Beginning in Obtaining these measurements remains Deployment time to pump a thousand the mid-1970s, gas chromatography– a major challenge. Those of us who or more liters of deepwater samples can mass spectrometry–computer systems have attempted low concentration be 10 hours or longer. This may be the (GC-MS) or mass spectrometry- OCEC measurements in open ocean reason that very few high-quality deep- computer systems did allow quantita- seawater know that research vessels water samples for OCEC measurements tive measurements of several of the can be considered a floating cloud of have been obtained. Another reason may PAHs and entered into frequent use contaminants of the same or interfering be the focus on the continental shelf and in the 1980s (Giger and Blumer, 1974; compounds, as is true for trace metals coastal ecosystems where OCEC concen- Hites and Biemann, 1975). (Froelich, 2014, this issue). trations are the highest and pollution has Progress in the development and use Surface water and surface films or been severe in some locations. of high-resolution capillary gas chroma- slicks can be sampled from inflatable Clean samples were and are just the tography columns then improved the rafts deployed from research vessels to beginning of the challenge. Obtaining separation of individual compounds and, travel upwind well away from the ship, or OCEC quantitative data for all samples— when coupled with mass spectrometry- surface waters can be sampled with great from deep, surface, continental shelf, computer systems or selective detectors care from the deck of the ship by pump- and coastal waters—involves extraction such as electron-capture detectors for ing through specially cleaned tubing or of samples with various organic solvents halogenated compounds, provided a through intake systems mounted in the followed by column chromatography, powerful means to quantify many, but bow of the ship (e.g., De Lappe et al., thin layer chromatography, and high not all, components of OCEC complex 1983). In the 1970s, most subsurface, performance liquid chromatography mixtures such as PCBs. The application deeper (below 10 m) water samples for (HPLC) to separate classes of OCECs of multidimensional gas chromatogra- OCEC analyses were obtained from from the myriad other compounds phy using two GCs and high-resolution lowering standard Niskin bottles, large (e.g., lipids) in the extract. However, capillary columns with different internal 90 L or 160 L stainless steel or anodized some of the OCEC classes enter the liquid phase coatings provided the means aluminum Bodman bottles (Bodman environment as complex mixtures of for separation and quantitative measure- et al., 1961), or similar large samplers, individual chemicals. For example, ments of individual components in PCB all cleaned with care and lowered, open, PCB commercial mixtures contain of mixtures (e.g., Duinker et al., 1988). through the surface slick, with the atten- up to 50 individual chlorobiphenyls, Comprehensive two-dimensional dant risk of the slick and its components and the mixture of medium and higher gas chromatography is now available contaminating the interior of the bottle molecular weight hydrocarbons in (Frysinger et al., 2003) and is being and eventually the deepwater samples. petroleum, including polycyclic aro- applied to several environmental samples Boehm (1980) was among the first matic hydrocarbons (PAHs), contains to report on the use of large Bodman hundreds of individual compounds John W. Farrington ([email protected]) bottles modified to enter the surface (Erickson, 1997; see Example Chemical is Dean Emeritus, Woods Hole Oceanographic ocean closed and then opened under Structures box in Farrington and Institution, Woods Hole, MA, USA. Oceanography | March 2014 215 to provide quantitative measurements of (2014, in this issue), to synthesize data time-of-flight mass spectrometric method and software for inventorying persis- individual components of complex mix- and conclusions from different studies tent and bioaccumulative contaminants tures of organic chemicals in the envi- into a more comprehensive view of the in marine environments. Environmental ronment, including OCEC in samples biogeochemical cycles of OCEC in the Science and Technology 46:8,001–8,008, http://dx.doi.org/10.1021/es301139q. from marine ecosystems. Techniques marine environment. Kujawinski, E.B., M.C. Kido-Soule, are now available for isolating sufficient D.L. Valentine, A.K. Boysen, K. Longnecker, and M.C. Redmond. 2011. Fate of dis- quantities of individual OCEC, for REFERENCES persants associated with the Deepwater example, an individual PAH, to measure Bodman, R.H., L.V. Slabaugh, and V.T. Bowen. Horizon oil spill. Environmental 1961. A multipurpose large volume water sam- Science and Technology 45:1,298–1,306, an individual compound’s C-14 activity. pler. Journal of Marine Research 19:141–148. http://dx.doi.org/10.1021/es103838p. The data enable discernment of organic Boehm, P.D. 1980. Evidence for the decou- Petrick, G., D.E. Schulz-Bull, V. Martens, pling of dissolved, particulate and surface chemicals with a fossil carbon source, K. Scholz, and J.C. Duinker, 1996. An in-situ microlayer hydrocarbons in northwestern filtration/extraction system for the recovery such as PAH from fossil fuel combus- Atlantic continental shelf waters. Marine of trace organics in solution and on par- Chemistry 9:255–281, http://dx.doi.org/ tion versus PAH from recent forest fires ticles tested in deep ocean water. Marine 10.1016/0304-4203(80)90029-8. Chemistry 54:97–105, http://dx.doi.org/ (Reddy et al., 2002). Ultrahigh-resolution De Lappe. B.W., R.W. Risebrough, and 10.1016/0304-4203(96)00029-1. mass spectrometry and liquid chroma- W. Walker II. 1983. A large-volume sam- Reddy, C.M., A. Pearson, L. Xu, A.P. McNichol, pling assembly for the determination of B.A. Benner Jr., S.A. Wise, G.A Klouda, tography with tandem mass spectrometry synthetic organic and petroleum compounds L.A. Currie, and T.I. Eglinton. 2002. has been applied recently to quantify a in the dissolved and particulate phases of Radiocarbon as a tool to apportion the seawater. Canadian Journal of Fisheries key ingredient in a dispersant used at the sources of polycyclic aromatic hydro- and Aquatic Sciences 40(S2):s322–s336, carbons and black carbon in envi- Deepwater Horizon oil spill (Kujawinski http://dx.doi.org/10.1139/f83-337. ronmental samples. Environmental Duinker, J.C., D.E. Schulz, and G. Petrick. 1988. et al., 2011). Added to this is the report of Science and Technology 36:1,774–1,782, Multidimensional gas chromatography with http://dx.doi.org/10.1021/es011343f. recent coupling of two-dimensional gas electron capture detection for the determination chromatography to time-of-flight mass of toxic congeners in polychlorinated biphenyl mixtures. Analytical Chemistry 60:478–482, spectrometry and new software to inven- http://dx.doi.org/10.1021/ac00156a021. tory OCEC in environmental samples Erickson, M.D. 1997. Analytical Chemistry of PCBs, 2nd Ed. CRC Lewis Publishers, Boca Raton, FL, (Hoh et al., 2012). 667 pp. Thus, clean sampling capabilities exist. Farrington, J.W., and H. Takada. 2014. Persistent organic pollutants (POPs), polycyclic aromatic High-resolution analytical chemical hydrocarbons (PAHs), and plastics: Examples of methods are available. Yet, very few stud- the status, trend, and cycling of organic chemi- ies have combined these new methods cals of environmental concern in the ocean. Oceanography 27(1):196–213, http://dx.doi.org/ to obtain open ocean deepwater data for 10.5670/oceanog.2014.23. OCEC. Significantly more field sampling Froelich, F. 2014. In praise of marine chemists. Oceanography 27(1):88–91, http://dx.doi.org/ campaigns and accompanying high- 10.5670/oceanog.2014.12. quality analyses are needed if we are to Frysinger, G.S., R.B Gaines, L. Xu, and C.M. Reddy. 2003. Resolving the unresolved have a much needed understanding of complex mixture in petroleum contami- the biogeochemical cycles of OCEC in nated sediments.
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