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rid of the heat, and when someone solves that, you will be amazed at the throughput we can get’. Our histori- cal preoccupation with chromatogra- phy for quantitation and for structur- al analysis, will be replaced with the need for fast preparative separa- tions, possibly using displacement chromatography, and probably using new tailored preparative sorbents. One type of such tailored supports will be the development of low affini-

ty antibodies and corresponding im- munosorbents. Regnier quipped, ‘Nature never intended antibodies to be used in chromatography; nature’s antibodies are made to bind and nev- er let go’.

Dr. V. Berry was Associate Professor at Salem State College, Salem, MA, U.S.A. and President of SepCon Separations Consultants in Boston, MA, U.S.A.

Environmental analytical chemistry (including chemistry and analysis of environmental hydrocarbons)

A report on the 20th International Roland W. Frei Memorial Sympo- sium on Environmental Analytical Chemistry, and on the 4th Work- shop on the Chemistry and Analy- sis of Environmental Hydrocar- bons, held in Strasbourg, France, 17-21 April, 1990*.

This 20th symposium was opened by the chairmen Maurice J. F. Leroy, Pierre Albrecht, Ernest Merian, the new President of I.A.E.A.C. James F. Lawrence, Jean-Pierre Ribault from the Conseil de l’Europe, and J.-C. Bernier, Director of the School of Chemistry. Mtiller (Geel, Belgi- um) chaired a round table discussion on ‘Europe in 1992: consequences for the analysts’. Widmer (Ciba-Gei- gy, Basle) presented trends in instru- mental analytical chemistry, includ- ing sensor techniques.

Analytical technologies (including sampling and hyphenated metho&)

Tolg (Dortmund) reviewed new developments and explained why more powerful methods are needed in environmental trace analysis, e.g. for platinum emissions from car ex- haust catalysts. Lohleit (Darmstadt)

* For the report on the 19th Symposium, see TrAC, 8(9) (1989) 318-320.

used supercritical fluid extraction, particularly for plant, tissue, lard, polymer, soil, sediment, sorbent and aerosol samples, and to fractionate organochlorine compounds. Hennion (Paris) determined polar organic compounds in water using (multi- step) on-line liquid chromatographic preconcentration techniques. A spe- cial procedure was developed for triazines. Lesage (Burlington) char- acterized groundwater contaminants (e.g. coal tar, liquid wastes, hetero- cyclic compounds leached from in- dustrial lagoons into sand) using on- line thermal desorption GC-MS.

Nielen (Arnhem) used capillary zone electrophoresis (with its high number of theoretical plates, selec- tivity and speed, it is even better than SFC) in environmental analysis. Sub- stituted benzoic acids, surfactants, and/or metal compounds in aquatic samples are easily concentrated, cleaned-up and identified. Velthorst (Amsterdam) presented detection methods in liquid chromatography based on long-living luminiscence detection: lanthanides [e.g. Eu(II1) and Tb(III)] form reaction products. By direct or indirect excitation of la- belled substances one gets good spectra, achieving good compatibil- ity with HPLC eluents (and thus a complementary method to the fluo- rescence determination of reaction compounds with biacetyl or a quench-

trends in analytical chemistry, vol. 9, no. 8,199O

er). She has also used high resolution spectroscopy for the determination of hydrocarbons in environmental samples, for instance Shpolskii or energy selection spectroscopy, mi- cro-LC or TLC. A laser technique may be incorporated but very low temperature is required and no com- mercial instruments are available; however, spectral resolution, sensi- tivity and selectivity are excellent. Kettrup (GSF, Neuherberg and Pa- derborn) reported on thermal analy- sis mass spectrometry, off-line com- bustion experiments on fire retar- dants and fire protection polymers, following courses of fires (time-re- lated consequences, e.g. also in pres- ence of (brominated) flame-retar- dants, of plasticized PVC floors, or of polyurethane foams). Halogen- ated aliphatic compounds may be produced and controlled. Around 400°C a maximum of brominated fu- ranes are produced, which are com- pletely degraded at 800-1ooo”C.

Inorganic analytical chemistry (in- cluding speciation)

Brinkman (Amsterdam) reported on selective sample handling and de- tection for (in)organic trace-level analysis. Thiram and its derivative Cu(DTC),, and their decomposition products were studied by high-speed pre- and post-column techniques. Trivalent As, Sb and Bi can be sepa- rated (e.g. in urine) by the formation of stable complexes with diethyldi- thiophosphate. Immobilization and preconcentration with high sensitivi- ty is also employed in the study of an- tibody-antigen interactions (e.g. of /3-19-nortestosterone). He monitored pesticides and PCBs in Amstel river water by on-line LC-GC without overloading problems. McLeod (Sheffield, U.K.) used flow injection (FI)-ICP spectrometry micro- columns to study Cr(III)/Cr(VI) speciation in river samples. FI-AES and FI-ICP-MS are useful for mer- cury species.

Chau (Burlington) reported on re- cent developments in speciation and determination (GC-AAS, LC-FAA, LC-H (hydride) AA, and particular- ly GC-MIP (microwave induced plasma) of organometallic compounds in environmental samples. Interfac-

trends in analytical chemistry, vol. 9, no. &I990 247

ing is critical for progress. Bayona (C.I.D., Barcelona) studied organo- tin speciation in aquatic matrices using FPD, BCD or MS detection. Extraction efficiency and clean-up procedures (e.g. for seawater, sedi- ments and mussels) were explained and measurements at the Cataloni- an, French, Italian and Turkish Me- diterranean coasts compared. Do- mu-d (Bordeaux-Talence) discussed the determination of Pb, Se and Hg species by GC-AAS. Hydration and derivatization (e.g. by ethylation) gives additional information. Sam- pling (with a metal-free sampler), treatment, storage, determination, and automation have been opti- mized. At some river locations MBT dominated, at others TBT. Grain size and depth distribution were also studied (most TBT is found lo-25 cm below the surface). With sub-ng sensitivity it is possible to determine methylmercury ions in dolphin mus- cles by chromatography-AAS.

De Vitre (Geneva) presented lec- tures on in-situ speciation at the wa- ter-sediment interface and voltam- metric sensors for in-situ measure- ment of trace elements in water. Mathematical modelling, physical studies, separation, chemical leach- ing, and sequential leaching give in- formation on partitioning of trace metals, which is critical for bioavail- ability. Possible redistribution of ex- tracted species must be considered. In upper layers manganese predomi- nates, in lower ones iron. To differ- entiate between colloids and hy- drated free ions [e.g. between ‘FeS’, Fe(I1) and S(-II)] absorption prob- lems in voltammetry must be mini- mized.

Remote sensing, monitoring, and sen- sors

Woeste (Berlin) uses Lidar, a laser technique for monitoring pollution in the atmosphere. Three-dimensional measurements of NO,, SO, or 0, were discussed, e.g. in the atmo- spheres of East- (burning lignite) and West-Berlin (burning oil). Ozone concentrations near Zurich increase in the evenings, except during storms. Inversion studies are of special inter- est.

Niessner (Munich) reported on

chemical sensors for environmental analysis. A good sensor system can be expensive, and selectivity may not be so important because contami- nants often change. Indirect mea- surement (e.g. by photoacoustic spec- troscopy or fluorescence detection) may be useful. Monomolecular dis- tribution and aggregation can be dis- tinguished. Fibre-optical immuno, Raman, and laser-sensor arrays are new developments in the study of waste waters and wastes. Weil (Mu- nich) described a heterogenous im- munoassay for the determination of triazine herbicides, but in waste wa- ter one may get only informations on Atrazine equivalents. Van Emon (Las Vegas, NV) discussed immuno- assays for environmental contami- nants, particularly pesticides. Field portable methods enable the gener- ation of data in real-time.

Fate, distribution and metabolism of pollutants

Klockow (Dortmund) has studied forest-atmosphere interactions. In the Sauerland Forest (in the F.R.G.) H202 concentrations are higher than in open land. Diurnal variations take place. Terpenes and other natural organic compounds may interfere (destruction by ozone). Carreira (Athens, GA) discussed metal inter- actions with humic substances. Ther- modynamic lanthanide ion probe models are promising. In the case of unbound iron [Fe++, FeOH+, and Fe(OH),+] speciation was calculated by MINTEQA 2. Barcel6 (Barcelo- na) reported on the analysis and be- havior of organophosphorus pesti- cides. Samples were extracted (by a Florisil column), cleaned-up and sep- arated by GC-NID, GC-MS (NCl) , or LC-MS. Leachability is of course very different for various or- ganophosphorus pesticides, and dif- ferent organisms also have different LC,, values.

Ebdon (Plymouth) used HPLC- ICP-MS for trace metal speciation, e.g. of ferritin and metallothioneins @ITS). Cd-methionin profiles in raw and cooked pig kidney are different, because low molecular MTs are de- stroyed in the latter. He also distin- guished organotins and organoarsen- its in biological samples. Ramseier

(Geneva) detected and purified (by gel electrophoresis) cadmium-bind- ing proteins from earthworm intes- tines. Thermoresistant 15-kDa and 7.8-kDa proteins were character- ized. Lawrence (Ottawa) deter- mined the unknown marine toxins responsible for the 1987 incident (e.g. domoic acid, a neurotoxin) by extraction of shellfish, shell remov-

ing, rinsing, homogenizing, and liquid chromatography. Albrecht (Strasbourg) recommended care in interpreting correlations, and stressed that biotransformation, chemical transformation, and radical transformation (also in sediments and soils) must be considered. Valdes (Dortmund) has developed an economic determination tech- nique for sulfur dioxide for develop- ing countries, using the autoxidation of Co(I1) in azide containing medi- um.

Environmentally-important hydro- carbons

Grimalt (Barcelona) studied the atmospheric transport of aliphatic and aromatic hydrocarbons, compar- ing measurements from diverse loca- tions. He used an aerosol sampler and differentiated between natural background levels and anthropogen- ic contributions. Blchmann (Darm- stadt) discussed atmospheric sam- pling, SFE-GC, global distribution and seasonal variation of non-meth- ane hydrocarbons in the atmosphere. Relative measurements are more re- liable than absolute ones, and in the ppb range the analytical results may depend on the standards used. In February ethane, propane and bu- tane concentrations are highest; aro- matics, perchloroethylene, and CF,Cl, vary less, the latter was still increasing from 1984 to 1987. Zajc (Jtilich) spoke on ‘on-line’ and ‘in- situ’ control by photoelectric aerosol sensors of polycyclic aromatic hydro- carbons and nitrated polycyclic aro- matic hydrocarbons during waste combustion in a two-step fluidized bed incinerator. Profiles depend on oxygen-introduction into combus- tion: in zones of incomplete combus- tion more of the compounds are pro- duced.

Giger (EAWAG, Dtibendorf)

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made a field study on Mount Rigi (Switzerland), looking at scavenging and wet deposition of organic chemi- cals. Atmospheric chemistry de- pends on meteorologic physics (nu- cleation and impaction; in-cloud and below-cloud processes). He mea- sured phenols, nitrated phenols (from photochemically transformed phenols and from agriculture), and PAHs during winter. Some com- pounds are more soluble (and may be washed out), others tend to occur in particles. The study of events is more important than just monitoring. Ste- phanou (Heraclion) determined the occurrence and origin of biogenic an- thropogenic lipids in eolian particles above and in the Southeast Mediter- ranean by a GNW sampler for partic- ulates and by GC-MS or GC-FID.

Michaelis (Hamburg) differen- tiated aquatic organic carbon (‘hum- ic substances’) in various rivers. Some contain more lignins, others have a higher molecular weight or contain more ester groups. Tarradel- las (Lausanne) reported on sources and behavior of anthropogenic PAHs (mainly from atmospheric deposi- tion) in Swiss soils. Field and forest soils contain more PAHs than mead- ows. Accumulation is particularly observed in humic fractions, which are not yet well understood.

Chemometrics and validation Griepink (C.E.C. Bureau of Ref-

erences, Brussels) mentioned that up to about 1983 many measurements of Se, As and Mg compounds and pesti- cides were not reliable, leading to economic loss and impacting on the quality of life. Since 1985 accuracy has been improved in many cases; lo-16% of analytical laboratory costs should be spent on improving quality.

Feinberg (Paris-Grignon) dis- cussed factor analysis and clustering for assessing micro-contaminants. For an industrial area with heavy traffic, isoconcentration curves have been calculated, and cadmium and lead pollution data interpreted by re- gression analysis. Donaldson (Athens, GA) tried multispectral identifica- tion of unregulated pollutants by MS-IR or by MS-MS (in the U.S.A. about 2 million different compounds

have already been identified in envi- ronmental samples, but the number of sample compounds increase rapid- ly with decreasing concentrations). Blattman (Berlin) informed on the German food contamination mon- itoring programme (to which about 50 laboratories are contributing). Harmonization of sampling and ana- lytical quality assurance in differ- ently staffed and equipped laborato- ries are important, to compare bur- den states.

The 21st symposium will be held, together with a workshop on metal speciation 19-24 May 1991 in Jekyll

trends in analytical chemistry, vol. 9, no. 8,199O

Island, GA, U.S.A., and the 22nd symposium 9-12 June 1992 in Dort- mund, F.R.G. Discussions will focus on validated methods, transforma- tion within speciation, sensor devel- opments, analytical problems, the analysis of small samples (including cells and membranes), reaction stud- ies in fires, and transformations in wastes and in containers.

ERNEST MERIAN Dr. Ernest Merian is Secretary of the Zn- ternational Association of Environmental Analytical Chemistry, Zm Kirsgarten 22, CH-4106 Therwil, Switzerland.

Mass spectrometry in the health sciences

A report on the 2nd International

~~

Over 290 participants from 21 differ- ent countries recently travelled to the bustling Spanish city of Barcelo- na, immersed in its preparations for hosting the 1992 Olympic games, to attend this symposium. The meeting was organised by Professor Emilio Gelpi in a similar manner to the first symposium of this series and fea- tured about 200 presentations on all aspects of the subject. The format of the meeting, although a little unusu- al, was highly successful; morning sessions were taken up with oral pre- sentations by invited speakers, the rest of the time was devoted to poster presentations and to structured dis- cussion sessions on particular themes chosen from these posters. Emphasis on posters was such that even the lec- turers were expected to provide a poster to accompany their lecture and posters were on display for the whole of the symposium. A small ex- hibition was also featured, with most manufacturers displaying some of their latest equipment.

‘The 1990’s promise a decade of major advance in the application of

mass spectrometry (MS) to the more difficult research problems of protein and glycoprotein structure elucida- tion’. This remark by H. R. Morris (U.K.) captures the essence of this symposium and highlights the cur- rent excitement among mass spec- troscopists at the introduction of sev- eral new techniques for achieving ionization of large, labile biomole- cules. Electrospray ionization and the related ion spray (pneumatically assisted electrospray) are possible the most advanced of these tech- niques. These produce, in high yield, a range of multiply charged ions that are well within the mass range of a quadrupole mass spectrometer, even for molecules with molecular weights in excess of 100 kilodaltons. A. P. Bruins (The Netherlands) gave a very clear description of the technol- ogy involved in ‘forming ions, and several presenters, including R. D. Smith (U.S.A.) and S. A. Carr (U.S.A.), described a number of ap- plications, mainly to peptides in the 10 to 100 kilodalton mass range; Dr. Smith also showed that molecules as high as 1.06 million daltons were ca- pable of producing a signal. For mix- ture analysis requiring higher resolu- tion, extension of the method to sec- tor instruments is necessary. This has proved difficult as problems are en- countered in interfacing the atmos-