7/30/2019 Muy viejo.pdf

1/8

Dossier- Luminescence spectroscopyFluorescente techniques for the determinationof polycyclic aromatic hydrocarbonsin marine environment: an overview

J.J. Santana Rodnguez" and C. Padrn SanzDepanmenr of Chemisrry. Faculty of Marine Sciertces. Universie of Las Palmas de G.C.. 5017 Las Palmas de G.C., pain

Polycyclic Aromatic Hydrocarbons (PAHs) arecompounds of great environmental interestbecause of their potential carcinogenic andmutagenic a~tivi ty nd their frequent occurrencein the enViKmment, above al1 in the marine envi-ronment.Therefore it is an important to establishsimple, sensive and reliable methods for thedetenninition of these COrnpoUndS. In this workwe report an overview on the application of flu-w r e pw nw tGSiiques i o ire sudy and detenni-naon of PAHs in marine samples: water,sediments and organisms. Canventional fluores-cence spectroscopy, synchronow fluorescentespectroscopy, Shpol'skii fluorescence spec-troscopy and high performance liquid chro-matography (HPLC) with fluorescence detectionconstitute the most interesting analytical tech-niques for the determination of these pollutants.

In the last few years, there has been an increasing interestin the types and concentrations of orgaic compoilnds prr-sent in marine environment. Among them, notable interesthas been shown in PAHs pollutants, as dernonstrated by thehigh nurnkr of recent papers in this field.

PAHs are a class of organic cornpounds. which areincluded in the wider family of polycyclic aromatic com-pounds (PACs). These compounds have shown carcinogenicandfor mutagenic activity in laboratory expenments withanirnais. PACs are generally formed during incomplete com-bustion or pyrolysis of organic matter occumng in a varietyof natural processes or hurnan activities. Consequently.PAHs are ubiquitous pollutants, which are present in al1environmental cornponents. Specifically. the presence ofFAHs has keii repvea in marine environment: sea water[5-9. 29-33], sediments 12.3.35-511, and plankton, seaweedand filter feeding organisms [52-7 11.

These pollutants can enter in the oceans by rnany routes,including petroleurn spills. runoff from roads, sewage, efflu-ents from industrial processes, and fallout from the atmos-phere. Sixteen of them are included in the list of prioritypollutants by US Environmental Protection Agency (Tab. 1)[!). Tha: is wh y n~iiioring iieir presence anci persisrence

1s the m& envim~m~lta]robJem,d nd isessentid 10h danalytical mehods capable to identify and quantify thesepollutants in the environment.In the last few years, important advances have been madein improving existing analytical methods and developingnew techniques for anaiysis of PAHs in marine environment,many of them appearing in scientific and technical joumalsand symposiurn proceedings.From h e v ar i~ usmn!ecu!ar spectrnmet_rir techniqi'escompared. one singularly important vend can be seen: theabsorbency and fluorescence spectra of the PACs contain farmore information than those for the other classes of com-pounds. This is especialiy w e for the PAHs, where many

Table l. Lis1 of priority pollutants PAHs considered byEPA (Environmental Protection Agency), their carcinoge-nity and ocurrence:H y d r o c a h n Molecular Carcino- Occurrencec

formula genicitpNaphthaleneAcenaphteneAcenaphtyleneFluorenePhenantreneAnthraceneFluoranthenePyreneBenzo(a)anthraceneChryseneBenzo(b)fluorantheneBenzo(k)fluorantheneBenzo(a)pyreneOibenzo(a,hjanlhraceneBenzo(g h,i)peryleneIndeno(l.2.3-cd)pyrenea) Reference [ I ]b) +++ or ++ = strongly carcinogen;+ = carcinogen; - = not cat-cinogenC) E = Environment (water. air. tobacco smoke, gasoline and dieselexhaust);F = Foods; S = Curing smoke

ANALUSIS, 2000,28,No80 DP C8nces.Wiley-VCH 2 W

7/30/2019 Muy viejo.pdf

2/8

Luminescence spectroscopy

structures have spectra with a dozen or so maxima. Thesernaxima as well as the intervening minima, form a uniquecharacteristic pattem of wavelengths and intensities. The pielecmn system also causes the PAHs to have a different flu-orescence and phosphorescence behaviour. Especially for then. T.rfins, Uie eiwironic ransiuons are determineci 'Dy the sizeand shape of the compounds. Electronically, the PAHs aresimple molecules whose spectra are only determined by themolecular resonante stmctures. Isomenc PAHs differ in thelocations of electronic density, because the shape of thePAHs are different, and in some cases they can even differin their numbers of aromatic rings.

Because of this fundamental reason and of the high sen-sitivity and selectivity of the chromatographic techniques,HPLC has been used predorninantiy. Single-wavelengthWabsorbency or fluorescence detectors have been applied forPAHs analysis. These m used to detect PAHs because thep i elecmn systems of PACs &termine ihp enegies ef thetransition in the electronic spectra.Between both specavscopic techniques above mentioned.the most sensitive is fluorescence spectroscopy because ofthe direct rneasurement of the emitted light intensity withlittle background or interference. The present overview iscentred on the methodologies which apply andlor includefluorescence in the analysis of PAHs in marine environment.

Fluorescence techniques

Conventional fluorescence spectroscopyConventional fluorescence spectroscopy involves generatingan emission specmm by scanning the emission wavelength.A,, while the sample is irradiated at a single excitation wave-length,L. Similarly, an excitation spectrum is obtained byscanning the excitation wavelength while recording theemission signal at a single wavelength. Furthermore, spec-trofluorimetry is a very simple method, which offers gener-ally very low detection limits and can be used with conven-tional instrumentation.-. This technique is very useful in quantitative analysis ofr ~ n sbecause of its nigh sensitivity, selectivity, swiftnessand relatively low cost. Moreover, it can be applied to deter-mine PAHs in many environmental rnarine samples.

The use of fluorescence spectroscopy as a detection tech-nique to determine PAHs in marine sediments was appliedby Vandenneulen er al. [2].After Amoco Cadk accident theimmediate behaviour and toxicity of freshly spilled cmde oilunder prevailing spill conditions in an inshore manne envi-ronment was examined. Authors simulated weathering stud-ies because weathering states of oil ranging from sheen oilto mousse have significant effects dunng oil-water and oil-sediment interaction.Observation of oiled sandy beaches suggest two mecha-nisrns of beach contamination: general penetration and con-

ANALUSIS, 2000,28, IV" 8O EDP Sciences. Wiley-VCH 2000

tamination of beach substrate by films of sheen oil (proba-bly partially ernulsified), and secondly the buriai of discretelayers of mousse. Depending on the timing of oiling withrespect to beach dynamics. large amounts of stranded oil canbe accomrnodated within beach sediments. The results ofthis investigation suggesteci that there may be some increasein toxicity with weathering, because PAHs become availablefor later long-term release.In the case of another kind of marine samples. Picer andHocenski [3] described a relatively simple, mpid and quitereliable procedure, based on the fluorescence of PAHs, forthe estirnation of petroleurn hydrocarbons in organisrns andmarine sediments. In this study lipophilic material wasextracted from the samples with n-hexane or n-pentane, con-centrated to approximately 1 ml, and benzene rnixtures.Thefluorescent material was cleaned by using a deactivated alu-mina column. and for the evaluation of the quenching mate-

n& tbA standard a&ii~~nm e w ws app!l&== im ofthe work was to improve the possibilities of estirnating cmdeoil pollution of sdiment and biota samples by using thestandard addition method.Applying fluorescence on solid organic substrate Vo-Dinhand White [4], investigated a simple technique based on sen-sitized lurninescence for detecting trace arnounts of polynu-clear aromatic compounds. They used anthracene as h e sen-sitizer designed to absorb excitation energy and funnel it toguest analyte compounds spotted on anthracene treated fil-

ter papr. Perylene, benzo(a)pyrene and fluoranthene mix-tures were anaiyzed. Results indicated that anthracene canimprove the fluorescence signal of perylene andbenzo(a)pyrene. No fluorescence sensitization was observedfor other compounds, such as fluoranthene.As showed above, fluorescence spectroscopy is a tech-nique applicable to the determination of PAHs in solidphases as sediments or marine organism tissues. It existsalso a large number of works and publications in which thistechnique is applied to determine PAHs in marine watersamples.Vapu Tervo [5 ] detemined h e total amount of petroleumhydrocarbons (oil) from 52 seawater samples col1ected at 19

stations in the Gulf of Finland. The samples were analysedashore by fluorescence spectroscopy. The mean concentra-tions obtained for "light oil" were 1.6-7.3 pgll and for"heavy oil" 0.5-1.6 p@l n the whole investigation ara.Law (61also applied this technique to samples of water,sediment and oil following the wreck of the Amoco Cadizin 1978. Samples were collected between Apnl and Junefrom the Brittany coast and westem English Channel andwere analysed for petroleum hydrocarbons by means of flu-orescence spectroscopy, gas-liquid chromatography and gaschromatography-mass spectrometry. The concenuations ofhydrocarbons found in these samples. 2-200 pgA, were sim-ilar to those found in previous oil-spill studies.As well, after the oil spill accident at Mitsubishi OilRefine- in Kurashiki city, Ochi and Okaichi 171 measuredoil residues by fluorescence spectroscopy in sea water of

7/30/2019 Muy viejo.pdf

3/8

7/30/2019 Muy viejo.pdf

4/8

Luminescence spectroscopy

the analysis of binary and temary rnixtures of these PAHsadded to seawater.As well, B6ckelen and Niessner [16] probed the applica-tion of several non-ionc surfactants for the extraction andenrichrnent of PAHs from aqueous media. Developing aspectroscopic method for the simultaneous detection ofPAH-mixtures by synchronous fluorescence in micellarmedium, they obtained recoveries up to 100 % with limitsof detection of 6.8 and 2.6 ng/l for benzo(k)fluoranthene andbenzo(a)pyrene, respectively.Synchronous fluorescence spectroscopy has also beenapplied to determine PAHs in other environmental sarnplessuch as marine organisms. For example, Ariese et al. [17]

defennined the uptake of PAHs by fish, screening the gailbladder bile for PAHs metabolites. They proposed synchro-nous fluorescence specuoscopy as a rapid screening tech-nique for the determination of conjugated 1-hydroxy pyrene,wich is a major rnetabolite in biie of fish exposed to PAHspolluted sediment The technique was applied to a meso-cosm study in which the uptake of PAHs by flounder(Plotichthysflesus)from polluted sedirnent was investigated.In a subsequent study, the method was applied to the south-ern Norih Sea and in Dutch coastai and inshore water 1181.Conventional and synchronous fluorescence spectroscopy,together with solid phase spectrofluorimetry, are adequatetechniques for determination of PAHs. The advantages of thelatter one are that only a little amount of a convenient solidsupport is needed for the preconcentration of the anaiytespresenting inherent fluorescence, and that fluorescence mea-

en;; czfi L c&+,r;e-j hr='Uyi; tkr solid phrUe.Applying these techniques to waters from different sources(tap, natural, waste and sea water), =lchez et al. [19] deter-mined by solid-phase spectrofluorimetry the content inbenzo(a)pyrene, benzo(a)anthracene and pyrene. wichexhibit native fluorescence in solution at trace leveis. Therelative fluorescence intensity was measured with thesePAHs fixed on Sephadex G-25 gel after packing the gelbeads in a 1 mm silica cell. By recording the synchronousspectra at dlfferent values of AL, benzo(a)pyrene,benzo(a)anthracene and pyrene can be simultaneously deter-rnined in the presence of other PAHs.

Shpol'skii spectroscopy is especially suited for the qualita-tive analysis of PAHs at trace levels as it combines the sen-sitivity inherent to fluorescence methods with the specificinformation that can be obtained in infrared spectroscopy. Itrnakes use of frozen n-alkane matrices at cryogenic temper-atures to considerably reduce band broadening which is thecause of the lirnited identification power of room tempera-tcre f l xmsrence. 7he PhHs wci'py schstitutionrr! sites inthe n-alkane crystal resulting in largely identical surround-ings. The appearance o the Shpol'skii spectrum may varyif different n-alkanes are employed, because the fit of thePAH within the crystal is critical. A Shpol'skii spectrumconsists of a number of narrow lines with a fui1 width athalf maximum of 0.1-0.0 1 nm. ese lines are suitable for

identification purposes because they form a fingerprint of theindividual PAHs.Ewaid er al. 1201 applied the technique to the study ofmarine sediments and demonstrated that high resolutionspectrofluonmeuy at 4.2 K n n-alkane matrices can be usedto identify polycyclic aromatic hydrocarbons denved fromtriterpene, which occur in the organic matter of marine andterresmal sediments.Gamgues et al. [21-231 used this technique for the analy-sis of several methylated-PAHs series in marine samples:organic material. sediments and cmde oils. The analyticalresults were compared with those reponed by other method-ologies and were found to be in quite good agreement, thus

demonsuating the reliability of high resolution Shpol'skiispectrofluorimetry. Also, Hofstraat et al. [24] determinedPAHs in harbour sediments by means of Shpol'skii fluo-rimetry and showed it was an appropriate analytical methodfor the quantitative and qualitative detennination of PAHs insuch samples. Moreover, they concluded that this techniqueyields low limits of detection comparable to hose obtainedby a standard procedure based on HPLC with fluorimetricdetection.Applied to other marine sarnples, Anese et al. [25] inves-tigated the applicability of high-resoiuuon Shpol'ski spec-trofluorimetry to the direct analysis of polycyclic aromatichydrocarbons in tern and mussel samples. The sensitivity of

the measurements suffered considerably from the largeamounts of interfering substances (e.g. fatty components) inthe crude extracts, resulting in a poor-quality Shpol'skiimatrix and a high sarnpie absorbency. ~evertneiess, fter athorough study of these limiting factors, optimum conditionscould be defined and a number of PAHs were detecteddirecily without any sample clean-up.Shpol'skii spectroscopy cannot be used for on-line detec-tion in HPLC. since the solid matrix precludes compatibil-ity with flow systems. Therefore Shpol'skii fluonmetry wasapplied by Mastenbroek er al. [26] as an independent iden-tification methoci to rhe upgrade rouune hYiS aalysis oPolycyclic Aromatic Hydrocarbons. HPLC combined withfluorescence detection is routinely used in the Dutch WaterQuality Survey to determine the PAHs content of marinesrd:r??mrsmp ! e s . !E fhis su!y, t!is m&n

7/30/2019 Muy viejo.pdf

5/8

7/30/2019 Muy viejo.pdf

6/8

Luminescence spectroscopy Dossier

detection wavelength of PAHs (due to absence of aromaticgroups in the surfactant molecule) and second, it is charac-terized by a short retention time (due to its polar character).SedimentsDunn [351 performed a very complete investigation con-ceming PAHs concentration in several marine samples, bytrying to determine the relationships existing between thelevels of a range of PAH isomers in three different kinds ofmarine samples: sediments, bivalve molluscs and algae. Forthis reason, he applied a method based on reversed phase\iquid chromarography and fluorescence detection.

Also. Obana ef al. [36] studied some PAHs(benzo(a)pyrene, dibenzo(a,h)anthracene, and 3-metyl-cholanthrene), which are carcinogens for marnrnais after invivo hydroxylation by mixed function oxidases. Comparedto other separation techniques, the development of HPLChas pennitted to anaiyze PAHs with good separation andhigh sensitivity, and to simplify the pre-treatment processes.in the study, ten PAHs were determined in sediments, oys-t e n , and wakame seaweeds by HPLC with a fluorescencedetector.This methodology was also appiied by Smith ei al. 1371to the determination of PAHs in sediments, seawater andclams from Green Island, the most visited coral island of theGreat Barrier Reef in Australia. Results showed that only

sdiments near powerboat moonngs were found to containiow, Dut measurabie amouns of severdi iiiiierei PAs, incontrast to the baseline amounts found at other locations.The presence of several PAHs at measurable levels stronglysuggsts that their origin was due to fue1 spillage andorexhux! emlrs i c~ s .In an investigatbn of marine sediments from the AdriaticSea, Guuella and Paolis [38] evaluated PAHs contamina-tion. During a naval cmise from Tneste to Ban they col-lected thirty two sarnples and determined PAHs in the finesediment fracton. i h e quantification of PAHs content in thesamples was performed also with HPLC and tluorescencespectroscopy.Beltrn et al. [39] applied also a HPLC method with flu-orescence detection to the detennination of the sixteen PAHsconsidered as the mosi pollutants by EPA in reference tornaiine sediments (HS-3. NRCC). he method consisted onHPLC determination of PAHs using isocratic conditions.with spectrofluorhetric detection and prograrnmation ofwavelengths.The oganic contaminant analyses in the environmentrequire complex procedures with severa1 steps, such asextraction, punfication and quantification. In the case ofsolid samples, the extraction is often performed by reflux ofwgmir, :dve?%.?%is !~er,h.c! s !mg (severz! h ~ r s !nd sn!-vent-consuming (several 'hund reds of mL). Microwave-assisted solvent extraction (MASE), represents an interestingalternative method for organic contaminants extraction.

As an example of application, Kay el al. 145) develo@a MASE technique for the extraction of PAHs in marhe sed-irnents. Optimum conditions for this technique wereobtained by using the mixed-leve1 orthogonal array designprocedure. A comparison between tiie Soxhlet extraction andMASE rnethods showed that although both techniques gavecomparable results on certified reference materials (HS-2and HS-6),he MASE technique allows one KI se less sol-vent and it is also time-saving and cost-effective, withoutaffecting the extraction efficiency. The optimum MASEtechnique was coupled to two anaiytical techniques: HPLCwith both UV and fluorescent detectors as in other previousstudies (46-501, and GC-MS for the quditative and quanti-tative detennination of PAns in rne cenied reerence mate-r i a l ~ nd real samples (rnarine sediments).Another methodology focussed on microwave assistedextraction was applied by Letellier et al. [SI] and used toextract PAHs from environmental matrices. The procedurewas validated on marine sedhnenf the standard referencematerial (SRM 1941a). The concentrations obtained by thismethod were in agreement with the cenifed vaiues and theconcentrations rneasured using Soxhlet extraction.OrganismsA large number of papers related with the application ofHPLC with fiuorescence detection to the PAHs analysis inmaiine organisms has been published [52-611. Among them,cnistaceans [56] are the most widely investigated. Indeed,they can concentrate a high leve1 of PAHs probably becauseof the absence of aryl hydrocarbon hydroxyase in thesespecies. In fact, scientists of several speciaities have pro-posed the use of indigeneous bivalve rnoiluscs in order toserve as biocontrollers of the detection and quantification ofenvironmeii@ipo[[aaip& i i i ~ ~ u u i i i ~--'..A;-- ----;-n"mncc i l ~ i i i v ~ ~ ~ ~ ~ ..--, ~Au t h ~fact that they are permanent inhabitants in sp ecific locationsand have a tendency to concentrate environmental contami-nants, bivaives.have been widely investigated far such stud-

In this line of investigation, Hanus er al. 1621 describedan HPLC procedure for the determination of thineen PAHcompounds in oysters at the ppb level. Recoveries obtainedfrom spiked samples were generally close to 80 8 . n a par-ticular investigation, Mix and Schaffer [63] focussed on thedetermination of PAHs present in clams of the C o a Bay inOregon (USA). In such a study, the concentrations ofbenzo(a)pyrene were rneasured in clarn populations fromfour different internareal Coos Bay regions. It was shownthat the PAM concentrations in hose clams living close toindustrialized areas were higher than the others living faraway from these areas and that, in general. the PAM con-centration was higher in spnng-summer time than dunngautumn and winter. The same investigarors also discovered1641 that the most hydrosoluble PAHs are those which areconcentrated in major proponion in such organisms.

Musjal and Uthe 16-51described a simple. npid and eas-ily automatizable merhod for the determination of PAHs incmstaceans. The method was based on the combination of

7/30/2019 Muy viejo.pdf

7/8

Dossier Luminescence spectroscopychromatographic techniques such as G C and LC for theidentification and separation of Ihese compounds and fluo-rescence spectrometry for quantification. The proposedmethod was vaiuable for individual measurements of PAHsin a range of concentration of 0.25-10 ng PAHsIg tissue.

A technique? ongindly developed to investigate the pol--. .lution of Dutch coastai water with metals and PCBs, wasmodified by Boom [66] for determining the pollution ofmarine organisms with PAHs. The method was based on thehydrolysis of tissue with 4 M sodium hydroxide, exuactionwith hexane, clean-up with 10 % deactivated aluminiumoxide and quantitative determination with reversed phaseHPLC and fiuorescence detection. It gave satisfactory resultsfor the analysis of PAHs in mussels.Trying to determine the bioconcentration factors forpetroleum hydrocarbons, PAHs and biogenic hydrocarbonsin Mytilus edulis, Murray e t a l . [67] applied aiso this tech-nique. PAHs were quantified by reverse phase HPLC with

programmed-wavelength fluorescence detection. The resultsshowed that the bioconcentration factors for PAHs were sim-ilar to those found for total hydrocahns where the majorhydrocarbons source was oil, whereas, at other sites, the bio-..-r--,-r:~.. C,.A.-~C C - r D A U r . r a r a sn r r rA~r mnnn;+iirlaCWIICSIIU~LIUII 1 a C t u l a IVI X ~ I A J \.AL. a 1 LULA VI I I I ~ ~ A I L U U L .lower than those determined for petroleum and for hydro-carbons originating from algae.

Perfetti er al. [68] proposed modifying the method fordetermning of PAHs and producing very clean seafoodextracts in less than haif the time requested previously. Afteralkaline digestion of seafood, PAHs were partitioned into1.1.2-uichlorotrifluoroethane. The resulting exuact wascleaned up by solid-phase extraction on alumina, silica andC,, adsorbents, and then analyzed by gradient reversed phaseliquid chromatography with programmable fluorescencedetection. Average recoveries of twelve PAHs from five dif-ferent matrices (mussels, oysters, clams, crabmeat. andsalmon) spiked at low ppb levels ranged from 76 to 94 %.The authors obtained results which were in good agreementwith the analyses of a mussel standard referente materialobtained from the National Institute of Standards andTechnology (NiST).

A variant of this methodology (LUfluorescence) was pre-sented recently by Bouzige er al. , [70]. The authors evaiu-ated a new immunoaffnity solid phase extraction (SPE)methodology based on antigen-antibody interactions whichwas optirnized for the selective extraction of PAHs in van-ous complex environmentai matrices. This imrnunosorbent(1s) consists of anti-pyrene antibodies immobilized on a sil-ica suppor! EAU i., use6 as r c!assicd SPF smben?.Th e rrics-reactivity of antibodies for analytes structuraily related withpyrene ailows the simultaneous extraction of the pnorityPAHs included in the US EPA priority lists. Losses due tothe volatility of h e two- or three-ring PAHs were avoidedby coupling the extraction on-line and using the antipyreneIS with LC.The sensitivity of fluorescence associated withthe selectivity of IS allowed the quantification of individualPAHs in contarninated or surface water below the 0.02 pgfllevel. Off-line extraction procedures were also set up for the

extraction of PAHs from complex solid environmental matri-ces, such as sludge or mussel extracts. The high selectivityprovided by the antibodiespermitted the extraction of PAHsand elimination of a great number of interferents in only onestep.Investigating h e PAHs pllutim in beep-sea envimnmen!(1500-1800 m depth), Escartin and Pone 1711 developed aisoa methodology based on the measurement of bile PAHsmetabolites in deep-sea fish. The authors selected fivespecies from the NW Mediterranean for the study. Bile crudesarnples were directiy analyzed by HPLC-fluorescence at theexcitationlernission wavelengths of benzo(a)pyrene(3801430 nm). The results obtained con fm the long-rangetranspon of PAHs to the deepsea environment, subsequentexposure of fish inhabiting those remote areas, and fish abil-to metabolize and excrete them through the bile.

Fazio, T.; Howard..W., In Po l~ cy li c rumatic Hvdmrarbons;Bjorseth, A-, Ed.; Marcel Dekker. New York, 1983; pp 464-468. aVandenneulen, J.H.; Buckley, D.E.:Levy. E.M.:Long, B.F.N.; NIX - I ---- m . nr-11- nr- a,-- D-11 D. . , J t m o . --?IVLCMCII. r,, WGIIS, T.U. IVIUI. ru11. DUU. AY I Y , I ~ o ) . L-.Piecer. .M; Hocenski, V. VI" Journes irud. Pollurioris, OCannes, C.I.E.S.M. 1982, pp 177-182. --mVo-Dinh,T.; White. D.A. J . Ani. Chem.Soc. 1986.58(6). 1 128. O

ETervo, V. Fin. Mal: Res. 1978. 244, 215. iELaw, R.J.Mal: Poli. Bull. 1978, 9(11) . 293. -Ochi,T.: Okaichi,T. Tech. Bull. Fac. Agr: Ka ga wa Univ. 1979. 330(2) , 157. --0stgaard. K.; Jensen, A. Inreni. J. Environ. Anal. Chem. 1983, 0mE14, 55.OSantana, J.J.; Sosa, 2.: Afonso. A.: Gonziez, V Fresenius J.Anal. Chem. 1990, 337. 96. nUebel, U., Kubitz, J., Anders, A.J. J. Planr. Phyiol. 1996, 148, -586. lLloyd, J.B.F. Anakst. 1980. 105. 97 . -nSantana, J.J.; Sosa, 2.; Afonso. A.: Gonziez, V. Anal.Chim.Acto. 1991. 255, 107. 3OSantana, J.J.; Sosa, Z.; Afonso. A .: Gonzlez,V. Talanta. 1992,39(12). 1611.Bermejo A.; Hernndez, J.; Santana, J.J. Fresenius J. AMI.Chem. 1992, 343, 509.Santana, J.J.; Hemndez, J.; Bernal, M.M.;Bermejo, A.Analysr. 1993, J18, 917.

Bkkelen, A.; Niessner, R. Fresenius J. Anal. Cheni. 1993,346, 435.Ariese F., Kok, S.J., Verkaik, M.. Gooijer C., Velthont N.H.,Hofsuaai J.W. In Shpol'skii specrroscopv and ~c h r o n o u s p u -orescerice specrmscop?: (B io ) moniroring of PAHs and rheirmerabolires; Ariese. F.. Ed.; Academish Proefschrift. VrijeUniversiteit, Febodruck Enschede. Amsterdam: 1993: pp. 129-142.Ariese F.. Dick k Hofssraat 43V C. Ve1ihmt N,H.I n Shpol'skii spectroscops arid s~i ch mn ou s~u or esc en cepec-iroscopy: (B io ) moniroring o f PAHs and the ir merabolires:Ariese. F. . Ed.;Academish Proefschnfi, Vrije Universiteit,Febodruck Enschede, Amsterdam: 1993; pp. 143- 163.

ANALUSIS, 2000, 28, N o8 DP Sciences.W~ley-VCH20W

7/30/2019 Muy viejo.pdf

8/8

Luminescence spectroscopy

Vilchez, J.L.; del Olmo. M.; Avidad, R.; Capitan-Vallvey. L.F.Analwt. 1994. 119. 12 11.Ewald. M .; Moinet. A.; Sa liot, A.; Albrecht, P. Am. Chem. Soc.1983, 55, 958.Garrigues, P.; Ewald, M. Org. Geochem. 1983, 5(2 ) ,53.Ganigues. P.; de Sury. R.; Bellocq, J.; E wald, M. Analusis.1985. 13f2) .81.Garrigues, P.; Ewald M. Intern. J. Envimn. Anal. Chem. 1985,21 . 185.Hofstraat, J.W.; van Zeijl. W.J.M.; Ariese, F.; Mastenbroek,J.W.G.. Gooijer, C.; Velthorst N.H. Mar Chem. 1991.33.301.Ariese. F.; Gooijer, C.; Velthorsf N.H.; Ho fsc raa ~ .W. Anal.Ch im A c ta 1990, 232, 245.Mastenbroek J.W.G.; &ese. F.; Gooijer, C.; Velthorst, N.H.;Hofstraat. J.W.; van Zeijl, WJ.M. Chemosphere 1990, 21(3) ,377.Kozin. L; Gooijer, C.; Velthorst, N.H.; Hetlou, J.; Zitko, V.Chemosphere. 1996, 33(8). 1435.Ho fst raa t J.W.: Jansen, H.J.M.; Hoornweg , G. PH.; Gooij er,C.; Vel thorst, N.H.; Cof ino. W.P. Intern. J. Envimn. Anal.Chem. 1985. 21 , 299.Lee , R.F.; Gardner. W.S.; And erso n. J.W.: B laylock , J.W.;Banvell-Clarke. J. Environ. Sci. Technol. 1978. 12(7),832.McKay, J.E; Latham, D.R. Anal. Chem 1980, S 2 ( l l ) , 1618.El Harrak, R.; Calull, M.; Marc, M.; B o m l l , F. Int. J.Envimn. Anal. Chem. 1996, 64, 47.Brouwer. E.R; Hermans. A.N.; Lingeman, H.; Bnnkman, U.A..in. J. Chromnsogr.A i% , 9, 45-37.Sicilia. D.; Rubio, S.; Pkrez-Bendito, D.; Maniasso. N.;Zagatto, E.A.G.Anal. Chitn. Acta. 1999, 392. 29.Garca Pinto, C.; Prez Pavn, J.L.; Mor eno Cordero , B. Anal.Chem. 1994. 66. 874.Dunn. B.P. In Poynuclear Aromatic Hydrocarbons: Founhlnternational Sp po si um on Analysis. Chemisrry and Biology.Battelle Press: Columbus, Ohio, 1980; pp 367-377.Obana, H.; Hori, S.; Kashimoto. T. Bull. Environm. Contam.-loxicoi. i981, 26 , 6i3.Smith, J.D.; Bagg, J.; Sin, Y.O. Aust. J. Mar Freshw. Res.1987, 38 , 501.Guzzella. L.; de Paolis. A. Mar: Poll. Bull. 1994, 28(3).159.R - l t A m 1 1 . E-- R . ca.;+m-~ 1. J. 1 ;n PL -M 1. D-1" .d. L . A .W . , s U"L J -y . br,cw,,'. 'x A\=&.Technol. 1996, 19(3), 477.Garca, A.I.; Gonzlez, E.B.; Alonso. J.I.G.; Medel, A.S.Chmnatographia 1992, 33, 225.Codina, C.; Vaquero. M.T.; Comellas, L.; Puig, F.B.Chtvmarogmphia 1994, 673, 2 1.

44. Brown, D.W.; McCain, B.B.; Horness. B.H.; Sloan. C.A.;Tilbury , K.L.; P ierce, S.M.; Burro ws, D.G.; Chan. S-L.;Landahl, J.T.; Kraihn. M.M. Mar. Poll. Bull. 1998,37(1-2).67.45. Kay, K.; Keong. M.; Kee, H. J. Chmmatogr. A. 1996, 723,259.46. Zobe l, H.; Ruppel. ELoborPrMis 1993. 3, 30.47 . Grosse-Rhode, C.; Kicinksi, G.C.; Ketuup, A. J.High Resol.Chmmarogr. 1990. 15. 3415.48 . Smith. J.D.; Bagg, J.; Wrigely , 1. Warer Res. 1991, 25. 1145.49. Ma nio tt, P.J.: Carpenter , P.D.; Brady, P.H.;McComick. M.J.;.Grif fiths , A.J; Hatvan i, T.S.G.; Rasde ll. S.G. J. Liq.Chmmatogr 1993. 15, 3229.50. Dong, M. W.; Duggan, J.X.; Stefano u, S. E - GC Inteniatl'onal1993, 11, 802.51. Letellier, M.; Budzinski, H.; Ganigues. P. LC-GCIntemational. 1999, 12(4), 957.52. Ten Hu lxh er , T.E.; Vrind, B.A.; Van den Heuvel, H.; Van derVelde, L.E.; Van No ort, P.C.M.; Beurskens, J.E.M.; Gov ers,H.A.J. Envimn. Sci. Technol. 1999. 33(1), 126.53 . Bravo , H.A.; Sala zae, S.L.; Botello , A.V.; Mandelli, E.F. Bull.Envimn. Conram. Toxicol. 1978. 17. 171.54 . Brown. R.A.; Pancinov, R. J. Environ. Sci. Technol. 1979, 13,878.55. Chester. S.N.; um p. B.H.; He& H.S.;May, NE.;W k S.A.Anal. Chem 1978, 50. 805.56. Dunn, B.P.; Fee, J. J. Fish. Res. Board Can. 1979, 36. 1469.57. Eaton. P.; Zitko, V. l n t e r n a t i o ~ lCouncil for the Erplorationof the Sea, 197858.' Hert, M.; lusek, C.S.; Miller. K.M. Envimn. Sci. Tech. 1980,14 , 465.59. Pancin ov, R.J.; Brown, R.A. Environ. Sci. Tech. 1977, 11, 989.69. Payne, j.E Xar. Foii. Buii. iW7 , 8 , ii2.61. Zitko, V. Bull. Envimn. Confam. Tox. 1978, 14. 624.62. Hanus, J.P.; Guerrero. H.; Biehl, E.R.: Kenner, C.T. . Assoc.

Ofi nal. Chem. 1979, 62(1) ,29.63. Mix. M.C.; Sch~Fe:, R.L. Mzr. F?~? . i r c l x os . 1983, 9. !93.64. Mix, M.C.; S cha fer , R.L. Mar: Poll. Bull. 1983.14(3), 94.65. Mu sial, C.J.; ~ t h e ,.F.J.Assoc. O$ Anal. Chem. 1986.69(3),462.66. Boom. M.M. Intern. J. Environ Anal. Chem. 1987. 31 , 251.67. Murray, A.P.: Richardson, B.J.;Gibbs, C.F. Mar: Poll. Bull.1991, 2 2 0 2 ) . 595.68. Perfetti, G.A.; Nym an. PJ.; Fisher, S.; Joe. F.L.; Diachenko,G.W. J. Assoc. O# Anal. Chem. 1992, 739 , 872.69. Bum s, K.A. Mar: Poll. Bull. 1993, 26(2) , 77.

42. Nez . M.D.; Cen trch. F. Anal. Chim. Acta 1990. 234, 269. 70. Boo zige , M.; Pichon. V.; Hennion , M.C. nvimn. Sci. Technol.43. Van de Nesse, R.J.; Ho ogland , G.J.M.; de Mo el, J.J.M.; 1999, 33(11). 1916.Gooijer, C.; Brinkman, U.A.Th.; Veithorst, N.H. J. Chrom. A 71. Escarin, E.; Porte, C. Environ. Sci. Technol. 1999. 33(16J ,IW?,552. e!?. ??:O.

ANALUSIS, 2000, 28, N" 8Q EDP Sciences. Wiley-VCH 2000