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Eric J. Reiner, Adrienne R. Boden, Tony Chen, Karen A. MacPherson and Alina M. Muscalu, Ontario Ministry of the Environment, Laboratory Services Branch, Toronto, Ontario Canada,
Persistent halogenated organic pollutants are chemical compounds of anthropogenic origin that resist degradation and accumulate in the food-chain. The analysis of these compounds requires complex sample preparation and analytical procedures using sensitive and selective state-of-the-art instrumentation to achieve the desired selectivity, accuracy and detection limits. This article reviews advances in the analysis of persistent halogenated organic compounds over the last century.
An important goal in the fieid of analytical chemistry is to achieve continual improvement in the analysis of persistent toxic pollutants. Halogenated organic compounds represent an important group of pollutants. They are used in a wide variety of applications such as flame retardants, fire suppressants, heat-transfer agents, surfactants and pesticides, mainly because of their chemical inertness and sfability. As a result of this stabiiity, many of these halogenated organic compounds are persistent in the environment, toxic and bioaccumulative in the food chain, and are consequentiy associated with adverse effects on human health and the environment. The Stockholm Convention on Persistent Organic Pollutants (POPs) (2001)' is an international treaty that focuses on the elimination or reduction of a number of these compounds or groups of compounds, which include pesticides, industrial chemicals and unintentionally produced POPs. The list of the original twelve compounds or groups of compounds and second group of nine is summarized in Table 1, along with an additional group of three compounds currently being reviewed for addition. The persistence and toxicity of these compounds as weil as many thousands of others^^ has driven the discovery and development of new analytical equipment and techniques in the interest of protecting humans and wildlife. Sensitivity, selectivity, speed of analysis and cost (four key method attributes) need to be considered when selecting the most appropriate method of analysis. The proper extraction, preparation and instrumental techniques must be selected to ensure that the uncertainty of the technique meets the required data quality objectives and the method is fit for the purpose for which it was intended.'* Continuai improvement should be the prime consideration of any analytical laboratory with the key method attributes optimized for the test at hand. Halogenated organics have been produced by humans intentionally and unintentionally tor hundreds of years. The greatest challenge through the years has been finding analytical methods that are sensitive and selective enough to determine concentrations at levis low enough to protect humans and wildlife. The current standard for analysis of organohalogens is gas chromatography (GC) with an appropriate detector thai meets the required selectivity [e.g., mass spectrometry (MS) or electron capture detection (ECD)]. Unfortunately, methods capable of determining concentrations to meet the above criteria have only been available for the last few decades.
Reiner et al. of silver nitrate followed by gravimetric etermination of the silver halides that precipitate from solution. In the Stepanovv^ or Bacon^ method (early 1900s) the organic halide was reacted with sodium in the presence of ethanol and the chloride was determined using a Volhard titration (silver nitrate was added in excess which reacts with the chloride produced). The excess silver was back titrated with thiocyanate in the presence of Fe^"^, which forms a bright red complex with the thiocyanate when the excess silver was complexed. The Stepanow and Bacon titration methods reduced detection limits to the part-per-thousand range from the (ow percent levis previously achieved by the Carius method. Occupational exposure of industrial workers to organohalogens accelerated the need for new analytical techniques. Chloracne, first reported in 1899, is a disease caused by extensive exposure to halogenated organicsJ^ Chloracne resulting from PCN contamination was first reported by Wauer in 1918.^ Factory workers producing and using Halowaxes and other PCN formulations also exhibited nausea, anorexia, vertigo, jaundice and death. Substitutes, such as PCBs. were considered less toxic and replaced PCNs in many applications. However, by 1937 It was recognized that PCBs also caused similar effects and that factory workers often exhibited chloracne as well as the other effects listed above for PCNs." During the early part of the previous century occupational exposure was common. Warren Crummett in Decades of Dioxin^^ writes about his observations in 1943 on the first days at work as a chemist in a chemical plant saying: "I was scared. It appeared obvious to me that this is a high-risk place to work. Chlorine and nitrosyl chloride leaks into the plant occurred frequently. One day I unwittingly stepped into a pocket of such gas. The choking impact knocked me to the floor and I had to report to the health department for oxygen inhalation treatment. Almost all the procedures on this job were hazardous." Dichlorodiphenylthchloroethane (DDT) was first synthesized in 1874, but its insecticidal properties were not discovered until 1939. DDT was used to control mosquitoes for maiaria and lice for typhus during the Second World War.'^-^s J^^Q ^gg QJ DDT and other organochlorine (OC) pesticides skyrocketed in 1940s and 50s to control pests and increase crop yields. During that time DDT was analysed using a colorimetric method developed by Schechter et al.^^ where DDT and degradation products dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD) were subjected to fuming nitric acid to produce a tetranitro-DDT complex that is reacted with a sodium methylate-methanol reagent. The resulting compound can be determined with maximum adsorption al around 600 nm. Levels down to 10 pg (-10 ppm) could be detected. The Advent of Gas Chromatography Although not used for quantitative trace level analysis until the 1950s, the concept of chromatography had been reported many years earlier, by Tswett^'' and Day''^ who reported that dyes and crude oil fractions were selectively retained on solid substrates respectively. Other observations of selective gas adsorption and separation on c^bon and silica geP^ were also reported in literature during the first half of the 20th century. In 1941, fviartin and Synge,^'^who performed research on liquid-liquid partitioning experiments, reported that, "the mobile phase need not be a liquid but may be a vapour," and that, "very refined separations of volatile substances should
Figure 1: The first published gas chromatogram. Reproduced with permission, from James and Martin, Biochem J.. 35, 679-690 (1952). Copyright: the Biochemical Society (http:// 'AT'.vw biochemj org)
U
24 m S 12 6 20 Time (mtn) 1 30 1
y g
Figure 2: Unknown peaks m a GC-ECD organochlorine pesticide scan. Copyright (1972) Royal Swedish Academy of Science from AMBIO. by Sren Jensen Republished by permission of Royal Swedish Academy of Sciences/Allen Press Publishing Services.
Reiner et al.
therefore be possible in a column in which permanent gas is made to flow over gel impregnated with a non-volatile solvent." The practical development of gas chromatography (GC) was not realized until 1952^'"^^ when Martin and James were able to separate and quantify four organic acids on a 4 ft x 4 mm column packed with DC-silicone oil containing 10% stearic acid using N2 as the carrier gas. Figure 1 shows the first published gas chromatogram. The eluants were detected by titration with sodium hydroxide and phenol red indicator. The detection limit was 20 pg and the column had 700 plates with a peak capacity of 5 to 6 peak (i.e., 5 to 6 peaks could be baseline separated in an analytical run). Using GC, chemists could now separate chemical compounds at trace levels, but the challenge was to find an accurate, sensitive and non-discriminating detector. A number of different detectors were developed including the thermal conductivity detector (TCD). coulometric detector and the most important for determination of OC pesticides, the electron capture detector (ECD), The ECD. developed in 1960, was very sensitive towards halogenated compounds and could detect as little as 10"''^ moles. It was also very selective for electronegative compounds making it ideal for halogenated organics and organochtorine pesticides.^''
Silent Spring
The amounts of pesticides used in the late 1950s and early 1960s was excessive. OC pesticides could significantly increase crop yields by 40% or more. The use of pesticides was seen as positive even though they were highly toxic and persistent. In 1954 and 1956, the reproduction of salmon in the Miramichi River of New Brunswick, Canada, was almost eliminated by the spraying of nearby forests with DDT to control spruce bud worm. In 1962, 350 million pounds of pesticides were used in the US- One of every 12 acres was treated with
Figure 3: PCBs in a GC-ECD organochiorine peslicicle scan from various biological samples in Sweden. Copyright (1972) Royal Swedish Academy of Sciences from AMBIO. by Sren Jensen. Republished by permission of Royal Swedish Academy of Sciences/Allen Press Publishing Services.
p,o'-DOT Elk OIELDRIN
Table 1: Stockholm convention POPs. Category Pesticides Compounds Aldrin Chiordarw Dieldrin DDT Endrin Heptachlor Hexachlorobenzene (HCB)
BpDOE
M i rex Toxaphene Industrial chemicals Polychlorinated Biphenyls (PCBs) Polychlorinated Dibenzodioxins (PCDD) and Dibenzofurans (PCDF) PCBs Added (May 2009) HCB Chiordecone a-hexach lorocyctohexane Unintentional production
White-tailed eagle
tO
d . p p'DDE PIks
10
12
Perfluorooctanesulfonic acid (PFOS), its salts and perfluorooctanesulphonyl fluoride Tetrabromodiphenyl ether and pentabromodiphenyl ether Compounds under review Nominated for addition (Oct 2009) Short-chain chlorinated paraffin (SCCPs) Endosulphan Hexabromocyclododecane (HBCD)
L C * G C Europe February 2010
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Reiner et al.
pesticides. These treatments had a startling affect on wildiife in the US^^ and around the world.^^ That same year Silent SpringP a book by Rachael Carson describing the dangers and effects of pesticides, was published. The title of the book was in response to great numbers of bird deaths as a result of poisoning from their diet of contaminated insects and earthworms. Carson's book indicated that if levels of pesticides continued to increase, birds would eventually disappear and the chirping of birds may not have ever been heard again. By 1973, Dieldrin was detected in 96% of the samples in a food basket study and in 99.5% of humans tested at a lipid adjusted level of 0.3 28
In the analysis of OC pesticides in the early 1960s, a number of additional peaks were observed in the GC-ECD chromatograms. Figure 2 shows up to 14 unknown peaks that were initially suspected to be OC pesticide degradation products. Jensen analysed archived bird feathers dating back to 1888 and showed the unknown peaks were present prior to 1945 and, therefore, could not be originating from OC pesticides. He used gas chromatography mass spectrometry (GC-MS) to determine that these unknowns were a homologous series of unsaturated organic compounds that contained only carbon, hydrogen and chlorine with molecular weights of 324. 358, 392, 426.^ Figure 3 shows
Figure 5: Fast GC-TOF mass chromatograms from a 11 /-component PCB, OC pesticide and PAH standard, (a), Comptete7.3 min run (b) TIC from a 12 s window and (c) deconvolufed mass chromafograms
TIC: 117 compounds in 7.3 min ITiCl
"SianOarO run iimes a/e (in minutes) in square bracket m coiuiin to trie left FaEt GC run times are listed !o the right ano coirssponding time savings are in round brackets.
>:
C l
1e-t-006 100
JVJ
2,3,7,8-tetrachlorodibenzo-p-dloxin
15
200
KO
4O0
2,3,7,8-etrachIorodlbenzofuran
242
244
p.p'-lDE
3,3',4,4'.5-pentachlorobiphenyl (PCB126)
234 1^ ^' ^
236
^
242 -3
3/S
244
sa
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Reiner et al. chromatograms for a variety of wdlife from different food web levels. The interfering compounds identified as PCBs were present in every sample. Many early OC results were probably biased due to contribution from PCBs. Sample extracts had to be split into fractions to eliminate bias from PCB and OC pesticide overlapping peaks in packed column chromatograms. Extracts were cleaned and fractionated using open column chromatograpfiy. Rorisil is the most common Chromatographie adsorbent, but silica gel and alumina are also used. The majority of the PCBs and a few OCs (typically Aidrin) elute in the first fraction whiie the remaining OCs and some PCBs (typically the non-ortho substituted PCBs) elute in the second fraction.
Figure 6: Schematic for a GC x GC analytical system. Reproduced with permission from Focant et al.. Talanta, 63 1231-1240 2004, Copyrighi 2004 Elsevier_
Table 3(a): Summary of methods for anaiysisof halogenated organics (1800s-1980s). Method Date range Analytes Gravimetric Carius 1800s Halo-organics Halo-organics % level Hours $10 <$100 Titration Stepanow Bacon 1900 to 1940s Halo-organics Halo-organics Milligrammes Hours $10s SiOO's Photometric Schechter 1940s to 1950 Chromatograpiiic Thin Layer 1950 to 1970 Chromatographie Packed GC 1950 to 1980s PCB OC pesticides N=1000 n^=5 Microgrammes to nanogrammes (ECD) 2-3 days $1OOs $100000
DDT and metabolites OC pesticides DDT and related compounds Microgrammes Hours $10's $1000 OC pesticides Microgrammes Hours $10 $1OOs
Selectivity
Sensitivity Speed Cost per sampie (SUSD) Equipment cost (SUSD)
www.chromstographyonllne.com
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Reiner tal.
when the degree of toxicity varies significantly between isomers and congeners of a group of compounds.
quality objectives. The analysis of dioxins is one of the most challenging pursuits in analytioal chemistry and a benchmark for the analysis o other organohaiogens.^'''^^ The analytes of interest must be quantitatively extracted from the sample. Interfering compounds must be removed using a series of coiumn Chromatographie procedures such as silica, alumina, Florisil or carbon. The extract must then be concentrated to minute volumes to detect sub-picogramme (10"^^ g) levels in samples. Interfering compounds including non-toxic isomers and congeners must be separated and the toxic components detected using high resolution mass spectrometry (HRMS). The use of capillary chromatography with ECD or MS detection has been the standard for the analysis of organohalogens since the early 1980s. Capillary columns are produced in a variety of dimensions. The most common dimensions are 60 m or 30 m columns with 0.25 mm inner diameter (i.d,), 0.25 [}m film thickness (f.t.) and non-polar (dimethylsiloxane) or slightly polar (5% diphenlymethylsiloxane) coatings. Most analysts attempt to run all of their analyses on these phases because they provide good separation for the majority of compounds and the phases are inert to the majority of organohaiogens and other matrix coextractables. Analytical runs typically are 3 0 - 6 0 minutes in length.
Table 3(b): Summary of methods for analysis of halogenated organics (1980-preseni) Method Date range Analytes Selectivity n=50 Sensitivity Speed Cost per sample (SUSD) Equipment cost ($USD) Picogrammes to femtogrammes (ECD) 2-3 days $100s $100000 Chromatographie GC~ECD 1980 to present Stockholm List Chromatographie GC-MS 1960 to present Stockholm List N=10' n.=50 Picogrammes 2-3 days $1OOs $200000 Chromatographie GC-HRMS 1970 to present Stockholm List N=3X1O* n.=100 Picogrammes to femtogrammes 2-3 days S500-$1000 $500000 Ch romatog raph ic
GCxGC
2000 to present Stockholm List plus many additional organohalogens N,=10-, Nj=1000 n^=50x20-1000 Picogrammes to femtogrammes 2-3 days $500-31000 $150000 (ECD) $400000 (TOF)
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Reiner et al. required to obtain the minimum number of sampling points. The time-of-flight (TOF) mass spectrometer was the first to be combined with a gas Chromatograph.^^ Early models had unit mass resolution and were not controlled via a data system. New configurations can scan much faster and have reflectron designs that increase resolution significantty.^ Some data systems now enable deconvolution of overlapping peaks. As shown for the peaks plotted in Figure 5{c), the slope of the tangent of alt ions at a specific time can be determined and grouped. Compounds with varied differentials can be deconvoluted from one another. Figure 5(b) shows the total ion chromatogram (TIC) over a 10 s section of a standard containing over 100 OC pesticides. PCBs and PAH, There appears to be five peaks in the Figure 5(b) chromatogram, however, after deconvolution of the peaks is performed, nine peaks can be detected. Table 2 describes the potential time savings using fast GC. Additional time savings can be realized with analyte-specific columns. Columns for a variety of compounds including dioxins [DB-Dioxin (Agilent Technologies. Santa Clara, California, USA), Rtx-Dioxin2 (Restek, Bellafonte, Pennsylvania, USA)], SP-2331 (Supeioo. Bellafonte, Pennsylvania, USA) and BPX-DXN, (SGE, Austin, Texas, USA)]; PCBs [HT-8 (SGE) and Rtx-PCB (Restek)]; and OC Pesticides [Rtx-CLPestiddes (Restek)] have been developed. These columns have been designed to separate critical pairs of coeluting analytes and minimize the number of coelutions seen on dimethyl s iioxane or 5% diphenylmethylsJioxane columns. In past years, the adoption of fast GC has been sluggish as older GC ovens couid not heat at high enough ramp rates, coiumns were not readily avaiiable in fast GC dimensions (i.d. < 0.18 and f.t. < 0.2) and some regulatory methods were not flexible enough to allow the use of microbore coiumns. The number and phases of columns available in dimensions capable of doing fast GC has increased significantly in the past few years and newer GCs are all capable of fast oven heating. Analytical Challenges Coelution of analytes for the analysis of all groups of halogenated organics presents a significant analytical challenge. There currently is no single GC column that can separate all the components of compound groups such as PCBs. PCNs. dioxins/furans, or OC pesticides in a single analytical run. GC-MS or GC-HRMS is currently the method of choice for dioxins/furans, dioxin-like PCBs and PCNs. OC pesticides and PCBs are also routinely determined using dual column analysis with BCD detection. Multidimensional or comprehensive two-dimensional chromatography (GCxGC) is a relatively new technique that can analyze samples on two different GC phases in the same analysis.^^"^^ In GCxGC, two different Chromatographie columns are connected in series through a modulator, which traps the analytes eluting from the primary column and re-injects them in small compressed packets onto the secondary columns. Figure 6 shows two coeluting peaks eluting from the primary column [6(a)], the resulting modulated packets eluting from the secondary column [6{b)] and the corresponding two-dimensional colour intensity plot or three-dimensional contour plot [6(c)] illustrating the data. GCxGC has a number of advantages over single column techniques. When orthogonal columns are coupled in series (coiumns that provide separation through different physical and chemical properties, e.g.. boiling point/polarity versus shape selection) separations are ordered in Chromatographie space. Thus, different compound groups tend to separate into distinct ordered bands of peaks eluting at about a 45'' angle relative to each other. This spatial ordering of compound class peaks aids in the separation, identification and classification of multi-component compound groups (e.g., PCBs. PCNs, dioxins). As indicated earlier, mass spectrometers cannot separate isomers. congeners or homologues with identical mass to charge ratios. GCxGC provides much greater Chromatographie resolution and peak capacity than single column systems. The GCxGC peak capacity is the product of the individual peak capacities of the primary and secondary columns and is typically on the
LC*GC Europe February 2010
Figure 7: GC < GC-ECD chromatograms of sludge and sediment samples containing a variety of different halogenated organics (CBZ = chlorobenzenes, PCDEs = polychlorinated diphenylethers, BDEs = brominated diphenylethers)
1"Drmension{s)
68
Reiner et al. order of 1000 peaks or more. With such great separating efficiency, a simple detector such as ECD can be used. Figure 7 shows the GCxGC chromatogram of a number of halogenated organics. GCxGC can also be used as screening method for variety of haiogenated compounds. Polychlorinated alkanes (PCAs) including short chain chlorinated paraffins (SCCPs) are a very challenging group of compounds to analyse.^^ They have replaced PCBs in many applications. There are many thousands of congeners and PCAs often appear as a plethora of indistinct peaks creating an unresolved hump in one-dimensional chromatograms (similar to that seen for complex hydrocarbon mixtures). In twodimensional chromatograms, they appear as structured bands and can easily be identified and quantified. Polychlorinated terphenyls (PCTs) manufactured as Aroclors where used in similar applications as PCBs, but also as synergistic agents for the application of Lindane.^" Not normally detected in conventional analyses, PCTs are often observed in GCxGC chromatograms of sludges and sediments. [See Figure 7(c) and as confirmed using GCxGC-TOF-MS in Figure 8.] The majority of the halogenated organic compounds listed in Table 1 are lypophilic and have similar physical and chemical properties. They can be extracted together and the extract can be cleaned using common procedures.^^'^^ Silica, alumina and Florisii are classical procedures used to remove iipids and other polar matrix compounds.^'' This results in Ehe ability to collect similar compounds (halogenated POPs) in the same extract and creates the potential for one analytical system to identify and quantify them in a single analytical run. Hytylinen^^ has reviewed a series of novel sample extraction and Chromatographie techniques that can be used to simplify and speed up analyses. It is necessary that responsible authorities invest in manpower and equipment to facilitate an unbiased search for pollutants at an early stage by systematic analysis. These are the measures that should be taken if the damaging and perhaps irremediable effects of a substance are to be discovered before and not after it has entered the environment. This applies especially to substances that accumulate and are highly persistent, as we have learnt from the history of PCBs. Unfortunately, since 1972 there have been numerous troubling discoveries of other chemicals in the environment, in humans and in wildlife. These include brominated compounds^^^*-' (polybrominaed diphenylethers, hexabromocyclododecane), chlorinated compounds^^"^-^ (chlorinated diphenyl ethers, Dechlorane Rus and other Dechlorane compounds) and fluorinated compounds^^"'^ (PFOS, PFOA). Regulations such as EU No 850/2004 and the Stockholm Agreement have been developed to reduce or eliminate the use of toxic, persistent and bioaccumulative compounds and reduce levels of these compounds in the environment. Many countries have drafted or are in the process of drafting regulations directed toward the virtual elimination of these compounds in the environment. Even so, the number of chemicals used in commerce and industry increases exponentially every year. Many of these compounds and their degradation products find their way into the environment enabling them to weave their way into every living thing. The ultimate goal would be to develop analytical methods that can analyse all POPs in a single sample extract as well
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Reiner et al. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 5Z. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70 71. 72. 73. 74. 75. 76. 77 78 C.A. Cramers and P.A. Leclercq.;. Chromatogr. A., 842,3-13(1999). K Mastovska and S.J. Lehotay, J Chormatogr. A.. 1000, 153-180 (2003). M.S^ Klee and L.M. Blumberg, J.Chromatogr. Sei.. 47, 83-91 (2002). E. Reiner el al, Organohaogen Compd. 66. 825-832 (2OO'l). P Sandra and F David J Chromatogr Sa., 40. 248-253 (2002). J. Cochran, Chromaiogr Sa. 40, 25d 268 (2002). E.J. Reiner et at, Organohaogen Compd.. 45, 17-20 (2000). K.A. MacPherson el al .Organohalogen Compd. 40. 19-23 (1999). 49. PA. Leciercq and C.A. Cramers, Mass Spectrom. Rev., 17, 37-49 (1998). N. Mirsetah-Kohan, W.D. Robertson and R,N. Compton, Mass Spectrom. Rev. 27.237-286 (2008), Z. Liu and J.B. Phillips. 7. Chromatogr. Sei.. 29. 227-231 (1991), J.B. Phillips and J. Xu, / Chromatogr. A.. 703, 327-334 (1995). M. Adahchour et al.. TrAC, Tends Anal. Chem . 25, 726-741 (2006). M. Adahchour et al., i. Chromatogr. A..^^S6. 67-108 (2008) L.R. Bordajandi et al.. / Chromatogr A.. 1186, 312-324 (2008). C. Danielsson et ai., J.Chromatogr. A.. 1086, 61-70 (2005), J.F. Focant et al., Talanta. 63, 1231-1240 (2004). J.F. Focant et al.. Anal Chem., 76, 6313-6320 (2004). P Haglund et al.. Anal Bioannal. Chem.. 390, 1815-1827 (2008). L. Mondello el a l . Mass Speerrom, ltev.,27. 101-124(2008). O. Panic and T. Gorecki Anal. Bioannal Chem., 386, 1013-1023 (2006). J.V Hinshaw, LCGC Norih America, 22, 32-40 (2004). E. Eljarra! and D. Barceio, TrAC. Anal. Chem.. 25, 421-434 (2006). E.J. Duda, J. Econ. Entom.. 50, 218-219 (1957). J Beer, J. Chromatogr A , 843, 179-198 (1999). S.PJ. Van Leeuwen and J. de Boer, / Chrom A., 1186, 116-182 (2008). S.K. Poole et a l . Anal. Chim. Acta. 236, 3-42 (1990). T. Hyotylainen, LCGC Europe, 22. 173-179 (2009). TM. Kolc et al., / Chromatogr Sa.. 47 83-91 (2009) C. de Witt, Chemosphere. 46, 583-624 (2002) M. Becket. T Phillips and S. Safe. Toxicol Environ Chem., i l . 189-200 (1991). E. Hoh. L. Zhu and R.A. Hites, Envrtm. Sri. Technol., 40, 1184-1189 (2006). L. Shen el al,. Environ. Sei. Tedinot.. 44,760-766 (2010), R, Renner, Environ. Sa. Technol.. 35, 154A-160A. J,P Giesy and K. Kannan. Environ. Sei. Technol.. 36, 146A-152A (2002), F Wania, Environ. Sei. Pollut. Res.. 6, 11-19 (1999). T. Meyer, F Wania and K, Breivik, Environ. Sa. Technol., 39, 3186-3196 (2005) K. Fenner et al.. Environ. Sei. and Technol.. 39, 1932-1942 (2005), Note: Organohalogen papers can be downloaded from, www.dioxin20XX,org
as separate and detect the toxic components at the low femtogramme levis. Over the last century, the advances in analytical methods have been extensive [Table 3{a) and Table 3(b)]. Single toxic components can be isolated from an indefinite number of other chemically similar compunds and accurately quantified at trace levels. Detection limits have decreased by over 10 orders of magnitude. Methods have become more sensitive and selective. Unfortunately, this has also resulted in analysts often being too focused at looking for only their specific compounds of interest. The newer methods: GCxGC and fast scanning detectors should enable us to look at many more compounds in cur sample extracts. We must develop these techniques as an analytical triage to assess what hazardous compunds may be present in the sample. There are many thousands of halogenated organic chemicals used by man and many others that are produced as unintentional by-products or degradation products that could potentially be more toxic than the parent compound. Considering how complex the environmental chemistry, fate and transport of these compounds a r e / ^ ' ^ it is vitai friat we continue to advance our analytical methods to better enable us to scan the environment for persistent toxic organic compounds.
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Dr Eric Reiner is a senior mass spectrometry research scientist at the Ontario Ministry of the Environment, Canada. He also serves as an adjunct professor at the University of Toronto and at the University of Waterloo. He has over 20 years experience in the analysis of halogenated persistent organics. Dr Adrienne Boden Is a dioxin and toxic organics scientist at the Ontario Ministry of the Environment. Canada. She performed her PhD studies in chemistry with a focus on environmental analysis at McMaster University. Her current work focuses on the GCxGC analysis of persistent toxic organics, Tony Chen s a senior toxics organic scientist at the Ontario Ministry of the Environment with 20 years experience in the analysis of OC pesticides. PCBs and PAH. Karen MacPherson is a senior dioxin scientist at the Ontario Ministry of the Environment with more than 20 years of experience in the analysis of Dioxin-like compounds and brominated flame retardants. Alina Muscatu. MASc. is a toxic organics technologist at the Ontario Ministry of Environment. She has 7 years experience in the analysis of PCBs. OC Pesticides. She has been working with G C K G C for over 2 years and is currently completing her PhD at the University of Waterloo. LC*GC Europe February 2010
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