ISSN:0144-557X    

DOI:10.1039/AP98522FX033

出版商:RSC    

年代:1985

数据来源: RSC

ISSN:0144-557X    

DOI:10.1039/AP98522BX035

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 253 Historical Biography Robert Boyle (1627-1691): A Foundation Stone of Analytical Chemistry-in the British Isles Part Ill.* American and Dutch Connections 0. Thorburn Burns Department of Analytical Chemistry, The Queen’s University of Belfast, It is appropriate at the time of the presentation of the second Robert Boyle Gold Medal to I. M. Kolthoff (born Almelo, The Netherlands, Feb. 11, 1894), doyen of American analytical science in both research1 and teaching,z to review Robert Boyle’s Dutch and Ameri- can connections. The Dutch connections Professor I. M . Kolthoff were a visit, correspondence to and from Holland and by publication of his works in Holland. The American connections were by correspondence, advice and by the terms of his will.The Dutch Connections Robert Boyle3-6 was in Holland from the end of February to the beginning of April, 1648. He had gone to view the country and also to accompany his brother Francis and his sister-in-law back from The Hague.6a Certain aspects of his stay at The Hague are recorded in the collection of essays Occasional Reflections.7.8 These include “Upon a Court’s being put into Mourning” (Hague, 1648) ,8a “Upon the Shop of an Ugly Painter well stor’d with Pictures of very hansome Ladies” (at The Hague),gb and about his return journey he wrote, “Looking through a Perspective Glass upon a Vessel we suspected to give us chase and to be a Pyrat” (sailing betwixt “Roterdam” and “Graves-end” on Easter day 1648).8c At Leyden he saw a camera obscura.9 It is probable that he also visited the anatomy school because Hartlib thanks Boyle for his “new dis- coveries in anatomy and enquires of other useful and ingenious knowledge” in his letter dated May 9, 1648.1Oa When in Amsterdam he visited Menasseh ben Israel,12 “the most famousest of the modern Rabbies.” He mentions him several times in his w0rks.13~14 In his reflection “Upon the eating of oysters” he notesgd “that in Holland it is usual, as I have seen myself, to mingle sheep’s dung with their cheeses, only to give them a colour and a relish.’’ Possibly more acceptable to modern tastes are the “vast benefit Hollanders derive from the best way of salting or pickling herrings”15 or their ways of preserving brisket.16 The correspondencelOJ1 to and from Holland was mainly from British people temporarily abroad.Letters were re- ceived from, for example, J. LockelOb (Amsterdam, October 10, 1687), S. Col- presseloc (Leyden, August 30,1668; April 3, 1669), Ja. Dalrymplelod (Leyden, October 29, 1685; March 2, 1686) and Joseph HilllOe (Rotterdam, April 20, 1685). One letter exists from the dis- tinguished Dutch microscopist Leuwen- hoek,10f (Delft, August 6, 1687). This referred to earlier letters written to the Royal Society and enclosed a new letter to the Society with observations about a corn mite. However, the main scientific news from Holland came to Boyle via corre- spondence with Oldenburg. Oldenburg17 was Secretary of the Royal Society and kept up a vast and almost extant corre- spondencelg with scientists and philos- ophers in Europe as well as dealing with much of Boyle’s literary affairs, including translations into Latin.Bishop Burnet wrote from The Hague’Og twice in 1686 and in the second letter referred to “Mr de Tournes of Geneva, who reprints all the Latin trans- lations of your works . . . is a very worthy man.” Less kind things were said about Dutch publishers, which is a pity, since many of the Dutch editions are now regarded amongst the most interesting of the continental editions, as the engraved titles to the Leers editions of Sceptical Chemist19 (Fig. 1) and Spring and Weight of the Air20 (Fig. 2) illustrate. The printed title pages of the Dutch editions normally contain a device, printer’s device (see Fig. 3 for Elsevier) or other ornament; all are small in size, mainly 12” (i.e., 4.8-5.0 X 2.8-2.9 in in size) with a few 8”.Boyle’s Belfast BT9 5AG, Northern Ireland problems with the Dutch booksellers con- cerned pirate editions. Part of the prob- lem might be a result of Boyle’s indecisive action. On September 18, 1665, Olden- burgloh wrote, “Seeing you give me no authority to endeavour to deter the Dutchman from printing their book of Colours, I think I ought not to appear in the business.” Fig. 1. Engraved title page to the Latin edition of The Sceptical Chemist, A. Leers, Rotterdam, 1668. The top figure is allegorical; the six smaller partitions contain alchemistical figures The matter. came up again: October 10, 1665,lN along with other news from Holland, that Spinoza21 “hath written to me concerning M. Huygen’s trans- migration into France. .. . The same Spinoza expresses a very great respect for you and presents his most humble service, and is displeased that the Dutch stationers will, in spight of our teeth, sell off one of their own Latin impressions of their Ilk- tory of Colours before the translation made here can be sent thither.’’ * For Part I, see Anal. Proc., 1982, 19, 222, and for Part 11, Anal. Proc., 1982, 19, 288.254 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Fig. 2. Engraved title page to the Latin edition of Spring and Weight of the Air, A . Leers, Rotterdam, 1669 Huygens met Boyle on his many visits to London22 and remained in a friendly relationship. However, the exchange of civilities almost invariably took place via a third party, Moray or Oldenburg.Olden- burg wrote further good adviceloj: to hasten the Latin translation as “John Crook has done with the History of Cold, to which he has also received an answer from his corresponding booksellers in Holland that they will take off the whole Latin impression. And this is the only way I know to prevent foreign trans- lations. . . .” In a letter of January 14, 1667,’Ok he wrote of the good notice he had received from Michael Behm, Consul of Dantzick, of De Fuiditate and De Coloribus. De Fluiditatis23 (Fig. 4) is interesting bibliographically and has been, at one time, wrongly considered a separate work.24a It is in fact the second half of Physiological Essays which was set up as two tracts with full title pages by Commelinus (Amsterdam 1687). Later that year Boyle complained to Oldenburg (December 29th, 1687)101 “.. . that two books of mine recently published in Hol- land viz the PhysiologicaZ Essays and the Book of Colours, without any notice taken, as I am informed either that they were ever printed in England, or so much so translated out of English. . . .” Boyle’s works were popular in Holland and via the Dutch book trade as they are the bulk of the continental editions of Boyle, the other main group being those from Geneva, of De Tournes. The Dutch editions in Latin are as follows: Spring and Weight of the Air (Vlacq, The Hague, 1661; Leers, Rotterdam, 1669),24b Certain Physiological Essays (Elzevir, Amster- dam, 166724~; Commelinus, Amsterdam, 1667),24d The Sceptical Chemist (Leers, Rotterdam, 1662, 1668),24e Experimental History of Colours (Schagen, Amster- dam, 1667; Leers, Rotterdam, 1671),24f Hydrostatical Paradoxes (Leers, Rotter- dam, 1670),24g Origine of Formes and Qualities (Amsterdam, 1671) ,24h Cosmic- all Qualities of Things (Schultzen, Amsterdam, 1671),*4i Origine and Ver- tues of Gems (Schultz, Amsterdam, 1667),24j Essay of Effzuviums (Lopez, Leyden, 1675) ,24k Mineral Waters (Boutesteyn, Leyden, 1699; Schoonwald, Amsterdam, 1712).24* Those in Dutch were High Veneration To God (Bos, Rotterdam, 1698)24” and Final Causes and Vitiated Sight (Swart, Amsterdam, 1688) .24n T E N T A hl I N A av 4 3 D A nr PHYSIOLOGICA Divcrfs Trmporibus S: Occa- i b i i l u s conkripti i R 0 B L R T O BOY L E, Nobifi Anglo, tun, rj!Qcnr H I S T O R I A F L U I D I T A T I S € 1 F I R M I T A T I S.EX An,Olico in Latinurn sermonm T’mjtata. J M S T E L O D v l MI, Apud Danielem Elzeviriurn. C I S I 2 c L X V X X . Fig. 3. Title page to the Latin edition of Certain Physiological Essays, D . Elsevier, Amsterdam, 1667, with printers device It is of interest to note that in the author’s preface to the “Experiments” subjoined to the second English edition of The Sceptical Chemist (1680) Boyle states that ten later impressions of the first edition (1661) had been reported to exist up to that time; only four are recorded in Fulton.24e However, Boyle finally heeded Oldenburg’s advice about early trans- lation as most of his later books appear in London Latin editions the same year, except for one, Rarefaction of the Air, which came out in Latin240 in 1670, a year before the English edition,25 1671. The high regard in which Boyle was held is perhaps best summarised by the famous Dutch chemist H.Boerhaave,26 in his inaugural address after his appoint- ment to the Chair of Chemistry at Leyden in 1718. “Boyle, who passed his days in experimenting and spent much money on the promotion of science, courageously took upon himself the task of executing what the great mind of Francis Bacon had conceived. For his work he received a well-deserved reward, and he became famous especially for his work in chem- istry. It was thanks to his chemistry that he was useful to the physicians, and so he was loved and honoured by both.” The American Connections Robert Boyle was deeply religious and was appointed by the King in 1649 to be a Governor of the “Corporation for the Propagation of the Gospel in New England.”bb He took these duties seri- ously during his life, and arranged for their continuance as part of the balance of his estate left to “pious and other good works.” These included “propagating the gospel among the Heathen Nations of New England and other parts of Ameri- ca.”& Dealing with the estate was com- plex27 and was arranged by the executors to be effected via the Company for the Propagation of the Gospel in New England, the President and fellows of Harvard College, and the President and masters of the College of William and Mary, Virginia.Boyle achieved a great reputation and influence among the American colonists and they kept him informed of their affairs and sent him news of scientific wonders and strange events.Much of this correspondence, indexed by Maddison, l1 is readily available in “Works . . .”.lo John Winthroplom (one of the original Fellows of the Royal Society), Governor of Connecticut, wrote from Boston on October 27, 1670, about a mysterious slaughter of fish in a pond which the H I S T O R I A FLUIDITATIS E T F I R M I T A T I S . A # l ) o Y e ROBERTO BOYLE Nobile An& A M S TEL OD A MI; Apud CASPARUM COMMELINWM- M DC LXVIL Fig. 4. Title page to the very rare Latin edition of the second half of Certain Physiolog- ical Essays, The History of Fluidity and Firm- nesse, set up as a separate tract, C. Comme- linus, Amsterdam, 1667, with deviceANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Indians attributed to its having been struck by lightning.He also gave him news of Mr. Elliot, the missionary sup- ported by Boyle. William PennlOn (Philadelphia, August 5 , 1683) described the character of the Indians and their dealings with them and commented “Of plants here are excellent for medicine and cure of wounds. Some chemists intend an observation upon them. ” John Claytonloo (Virginia, James City, June 23, 1684) referred to Boyle’s work on Noctiluca and described the firefly. Dr. William AverylOp wrote (Boston, November 9, 1682) concerning alchem- ical experiments and also on smallpox. A letter from Boyle crossed in the post because in Avery’s letter, May 1 1684,lOq he thanks Boyle for his letter of October 16, 1682 “for the letter with the useful book.” The nature of the book was not stated but it was important for he says “coming into my hands have laid me under a deep obligation.” There are again reports of alchemical experiments and medical matters.The alchemical experi- ments and medical sections refer to items in Starkey’s Pyrotech. It is probable that‘ the book Boyle sent to Avery was Receipts Sent to a Friend in America (1688) although Fulton24 has not identi- fied the “friend” nor has the original been seen.24~ Birch state@ that Medical Experiments. . . 1692 was a second edi- tion of “Receipts . . .”; he also gives the Preface to the 1688 book omitted from subsequent ones. The Preface28 also ref- ers to “the inquisitive Dr. W. A.,” hence it is reasonable to deduce that the book in question was Receipts or its manuscript version.The choice of the President and fellows of Harvard to deal with the execution of some of the items in Boyle’s will was most appropriate as a one-time President, Leo- nard Hoar, was a friend of Boyle, as was the first Harvard graduate to achieve a reputation in chemistry, George Stirk or Starkey. Hoar deserves a special place in the history of chemistry in America29 because in a letter to Boyle, December 13, 1672,1°r he outlined his plans for the development of Harvard to include “a chemical laboratory for those philos- ophers, that by their senses would culture their understandings, are in our design to spend their time of recreation in them; for readings or notions only are but husky provender. . . .” However, the labora- tory was not built and throughout the greater part of the seventeenth century there appears to have been no formal instruction in chemistry, although the Harvard Commencement ( i .e., Degree Day) Theses and Quaestiones30.31 prior tQ 1687 do contain chemical topics, as part of natural philosophy. Starkey, in Pyro- techny Asserted and Illustrated (1658) ,32 asserted that “In the year of our Lord 1644 I first began the studie of Chemical Philosophie.” If true, his studies must have been individual and private. Another documentary connection of Robert Boyle with Harvard is the letter, undated but 1633,33 from his protCgC Caleb Cheeshahteaumacuk, who was the earliest Indian graduate of Harvard in 1665. The largest amount of correspondence from America with a single person was that with John Elliot,34 the devoted and extraordinary missionary to the Indians.Boyle was his main support in his efforts to convert them to Christianity, to trans- literate their dialects and to make the Bible accessible to them. Eliot wrote describing his work and the heartbreaking difficulties, addressing Boyle in terms such as “Right honourable, right chari- table, and indefatigable, nursing father.’’ Another extensive correspondence was with the Commissioners of the United Colonies of New England.35 Two of the Governors and General Court of New England wrote to thank Boyle for his services to the Nations and in speaking on their behalf to the King, John Edecott6e in 1664 and John Leverett6f and others in 1676. The charitable objects of Boyle’s will concerned with propagating the gospel among the “Heathen Nations of New England” were deemed to have failed.Following a suit in Chancery the funds were devoted to a topic as near the original idea as possible, namely “the conversion and religious instruction, and education of the Negro slaves in the British West India Islands.” To enhance funds a selection from Boyle’s Occasion- all Reflections was published, together with memoirs of the author,36 which brings us full circle to a record of the Dutch visit. 1. 2. 3. 4. 5. 6. 7. References Laitinen, H. A., and Meehan, E. J . , “The Scientific Achievements of Izaak Maurits Kolthoff,” Anal. Chem., 1984, 56, 248A. Laitinen, H. A., “I. M. Kolthoff to be Honoured for Excellence in Teaching,” Anal. Chem., 1982,54, 1463A.Birch, T., “The Life of the Honourable Robert Boyle,” A. Millar, London, 1744. This was included in collected works. “The Works of the Honourable Robert Boyle. In Five Volumes. To which is prefixed a Life of the Author,” A. Millar, London, 1744. “The Works of the Honourable Robert Boyle. In Six Volumes. To which is prefixed a Life of the Author.” A New Edition. J. and F. Rivington et al., London, 1772. “Life,” Ref. 5 , Volume I, pp. i-ccxviii. (a), Volume I, p. xlv; (b), Volume I, p. lxviii (for the Charter see pp. cli-clviii); (c), Volume I, p. clx; (d), Volume I, p. cxxxvi; (e), Volume I, p. ccxiv; (f), Volume I, p. ccxvi. Boyle, R., “Occasional Reflections Upon Several Subjects . . .”, W. Wilson for H. Herringman, London, 1665. .8. 9. 10. 11. 12. 13. 14. 15.16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 255 Ref. 5, Volume 11, pp. 323-460. (a), Volume 11, p. 438; (b), Volume 11, p. 458: (c), Volume 11, p. 365; (d), Volume 11, p. 451. Ref. 5, Volume I, p. 302. “Letters from and to Mr. Boyle,” Ref. 5, Volume VI, pp. 35-672. (a), Volume VI, p. 77; (b), Volume VI, p. 542; (c), Volume VI, pp. 555-556; (d), Volume VI, p. 621; (e), Volume VI, p. 661; (f), Volume VI, p. 668; (g), Volume VI, p. 625; (h), Volume VI, p. 194; (i), Volume VI, p. 200; (j), Volume VI, p. 224; (k), Volume VI, p. 262; (I), Volume VI, p. 71; (m), Volume VI, pp. 581-582; (n), Volume VI, pp. 658- 659; (o), Volume VI, pp. 659-660; (p), Volume VI, pp. 610-612; (q), Volume VI, pp. 612-614; (r), Volume VI, Maddison, R. G. W., “A tentative index of the correspondence of the honourable Robert Boyle FRS,” Notes Rec.R. SOC., 1958, 13, 128. Ref. 5 , Volume 11, p. 280. Ref. 5, Volume 11, p. 301. Ref. 5, Volume V, p. 183. Ref. 5, Volume 111, p. 409. Ref. 5 , Volume 11, p. 108. Hall, A. R., in Gillespie, C. C., Editor, “Dictionary of Scientific Biography,” Volume X, Scribner, New York, 1974, Hall, A. R., and Hall, M. B., Editors, “The Correspondence of Henry Olden- burg,” Volumes I-IX, University of Wis- consin Press, 1965-1973, Volume X, Mansell, London, 1985. Boyle, R., “Chyrnista Scepticus . . .”, A. Leers, Rotterodami, 1668. Boyle, R., “ V i Aeris Elastica-,” A. Leers, Roterodami, 1669. Meinsma, K. O., “Spinoza et son cercle,” J . Vrin, Paris, 1983. Maddison, R. E. W., “Robert Boyle and Some of his Foreign Visitors,” Notes Rec.R. SOC., 1951,9, 1. Boyle, R., “Historia Fluiditatis et Firmi- tatis,” C. Commelinum, Amstelodami, 1667. Fulton, J. F., “A Bibliography of the Honourable Robert Boyle,” Second Edition, Oxford, 1961. (a), p. 24; (b), p. 18; (c), p. 23; ( 4 , p. 24; (e), p. 31; (f), p. 45; (g), p. 54, (h), p. 57; (i), p. 62; (j), p. 69; (k), p. 77; (I), p. 107; (m), p. 105; (n), p. 127; (o), p. 65; (p), P. 118. Ref. 5, Volume 111, pp. 495-510. Lindeboom, G. A., “Herman Boer- haave: the Man and his Work,” Methuen, London, 1968. (a), pp. 115- 116. Maddison, R. E. W., “Life of the Honourable Robert Boyle,” Taylor and Francis, London, 1969, pp. 283-288. Ref. 3, Volume 5, p. 312. Cohen, I. B., “The Beginning of Chem- ical Instruction in America-a Brief Account of the Teaching of Chemistry at Harvard Prior to 1800,” Chymia, 1950, 3, 17. Lane, W. C., “Early Harvard Broad- sides,” Proc. Am. Antiquarian SOC., 1914, 24, 264. Walsh, J . J., “Scholasticism in the Col- onial Colleges,” New England Q., 1932, 5 , 483. Starkey, G . , “Pyrotechny Asserted and Illustrated,” R. Daniel for S. Thomson, London, 1658, p. 76. See Turnbull, pp. 652-653. p. 200.256 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 G. H., “George Stirk, Philosopher by MA, USA, 1936. Colony of New Plymouth in New Fire,” Trans. Colonial SOC. Massn- 34. Ref. 3, Volume 6, Appendix V to England,” Boston, 1859. chusetts, 1949-51, 38, 219. “Life,” pp. ccv-ccxiv, 10 letters. 36. The Hon. Robert Boyle’s “Occasional1 A facsimile is in Morison, S. E., “Har- Pulsifer, D., “Acts of the Commission- Reflections’’ with a preface etc. by J. vard College in the Seventeenth Cen- ers of the United Colonies of New Weyland, T. Cadell et al., London, tury,” Harvard University, Cambridge, England. Volume X of Records of the 1808. 33. 35.

ISSN:0144-557X    

DOI:10.1039/AP9852200253

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

256 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Obituary Hans Wolfgang Nurnberg Analytical chemists will be saddened to learn of the sudden death, at the age of 55, of Professor Nurnberg, Head of the Insti- tute for Applied Physical Chemistry at KFA Jiilich, the West German nuclear centre, and Professor of Physical Chem- istry at Bonn University. He is survived by his widow, Ute, two sons and one daughter. Wolfgang Nurnberg was educated at Bonn, coming there under the influence of Professor von Stackelberg, who instilled in him an interest in polaro- graphy which lasted throughout his life. He joined the newly formed KFA in 1961, first working as a guest scientist on new polarographic techniques at AERE Har- well for a short period before returning to KFA to form a central institute concerned with the analytical problems of the new research centre. Later, he became Head of the larger Institute for Applied Physical Chemistry and in this position he initiated much novel work involving electrochem- ical techniques in fields such as environ- mental research and bioelectrochemistry , as well as directing more conventional analytical work connected with nuclear reactor projects.Nurnberg was especially well known for his pioneering work on environmental problems, and for his work in the field of environmental contamina- tion he received, in Holland, the Ock-van- der-Grinten Prize. Shortly before his death he gave an invited paper on his recent work at the “Bishop Symposium,” which was held in Exeter earlier this year. He was a member of the Advisory Board of The Analyst and similarly connected with five other journals. His publications include about 300 papers and he was the Editor of several reference books on topics of interest to analysts and environ- mentalists. Wolfgang Nurnberg was very much a leader and an innovator, with a forceful personality and much shrewdness in the identification and pursuance of research topics of future importance.He also recognised the importance of fundamen- tal work in the context of applied physical chemistry. He travelled extensively, receiving many invitations to speak abroad and driving himself much too hard to satisfy these requests. That he should die from a heart attack while travelling to Canada is not surprising to his friends. He will be sadly missed by his colleagues and by his many friends.GEOFFREY BARKER Recent Developments in the History - of Chemistry Edited by C. A. Russell This book is intended primarily to inform chemists of recent progress in the history of chemistry. It originated from an initiative of the Historical Group of the Royal Society of Chemistry who for some considerable time had been aware of a rising surge of interest amongst chemists in the history of their subject. Yet there was also considerable frustration in obtaining reliable and up-to-date information, in understanding recent trends and in perceiving the relevance to specific problems of some of the less obviously “chemical” writing of the last few years. Those with whom the Group was in touch included chemistry teachers wishing to introduce-perhaps only occasionally-historical elements into their school curricula.Others who expressed both interest and frustration were members of university and polytechnic chemistry departments, chemists in industrial research and those who had taken early or normal retirement. These are the readers for whom this book has been published, although it is hoped that professional historians of science may also find it to be of interest and value in its general surveys of the literature. Brief Contents: Chemical Biographies; Chemical Education and Chemical Institutions; Chemistry to 1800; General and Inorganic Chemistry; Organic Chemistry; Physical Chemistry; Analytical Chemistry; Biochemistry; Instruments and Apparatus; Industrial Chemistry; Chemistry by Location in Western and Central Europe; Appendix I Periodicals for The History of Chemistry; Appendix II Some Useful Addresses; Author, Subject and Themes Indexes. Hardcover 344pp 0 85186 917 3 Price 427.50 ($36.00) RSC Members f 12.00 Ordering: Non-RSC Members should send their orders to: The Royal Society of Chemistry, Distribution Centre, Blackhorse Road, Letchworth, Herts SG6 1 HN, England. RSC Members should send their orders to: The Royal Society of Chemistry, Membership Officer, 30 Russell Square, London WC1B 5DT. The Royal Society of Chemistry Burlington House, Piccadilly London W1V OBN

ISSN:0144-557X    

DOI:10.1039/AP9852200256

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 257 Fossil Fuels The Annual Chemical Congress of the RSC was held in the University of St. Andrews on March 26-28th, 1985. The Analytical Symposium was on the subject of Fossil Fuels, and the following are summaries of seven of the papers presented at that Symposium. Clean Gasoline From Coal G. 0. Davies Coal Research Establishment, Stoke Orchard, Cheltenham, Gloucestershire GL52 4RZ The last decade has brought a rapid rise in the price of oil and the cost of the crude barrel has risen by a factor of ten. This might have been expected if there had been a world-wide shortage of oil, but apart from a few periods of crisis during the mid 1970s it has been an age of plenty. Even during the last few years of constant warring in the Middle-East there has been a general glut.The price of oil therefore has not been forced up by the normal market forces of supply and demand, but more by the rapaciousness of the oil producing countries who, through their cartels, especially OPEC, have raised the price of oil to that which customers in the Western World find difficult to pay. There now seems to be little competition between the oil producers to control market prices and the only real competition will come from alternative fuels. As a direct source of energy coal and gas are natural alternatives, coal in particular as there are vast reserves evenly distributed throughout the world. However, if these alterna- tive fossil fuels are to get into real competition with oil then they must be able to provide all the commodities that are currently obtained from petroleum.To do this viable methods for the conversion of coal or natural gas into liquid distillates are required. Transport fuels are made almost exclusively from petroleum distillates and there has been considerable interna- tional activity over the last decade to produce alternatives, especially by the liquefaction of coal. Here in the UK a direct coal liquefaction process has been developed at the Coal Research Establishment, Cheltenham, and distillates obtained from coal by this processing have been used to prepare premium grade gasoline, jet and diesel fuels.'-2 The premium gasoline, like its petroleum derived counter- part, contained lead and a high level of benzene (7-10%). Plans have already been made to eliminate lead from all gasolines by 1989 and there is currently a strong lobby from environmental and health protection agencies to limit the benzene content in commercial gasolines.3 This paper describes briefly the primary coal liquefaction, details the distillate refining necessary to produce clean gasoline from coal and assesses the performance of the fuel for modem engines.Primary Coal Liquefaction-the NCB LSE Process The NCB process has been described in detail in a number of publications.1.2 Briefly, the process converts coal into distil- lates in two stages, Fig. l. In the first stage dry crushed coal is extracted with a high boiling oil at approximately atmospheric pressure. Undissolved coal and mineral solids are separated by hot filtration and the clean coal extract solution is fed to a catalytic hydrocracker, where at about 420°C and 170 bar hydrogen pressure, the coal extract in solution is converted into distillates. The total hydrocracker product is distilled to remove light products boiling in the gasoline - gas oil range (IBP 300 "C), leaving the higher boiling oils for recycling to the extraction stage.The process has been developed at the Coal Research Establishment using a small integrated plant that has a nominal coal input of 24 kgd-1. Some views of this plant are shown in Figs. 2 and 3. The plant operates in long continuous runs, up to 84d when reliable yield data are obtained, and considerable Steam and power Steam and generation power to process - - - SNG Hydrogen Gas - recovery separation - LPG ' A, Gas IBP- 170 "C r * gasoline and chemicals r 170-300 "C Hydrocracking Fractionation + diesel and = Coal + solvent extraction Fig.1. NCB liquid solvent extraction process258 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Table 1. Typical yields from LSE processing UK Bituminous Coal to process Coal to services 100 0 USLignite . 83 17 Total (dmmf)* 100 100 Products from liquefaction- Heterogas 8 Hydrocarbon gas 16 Pitch and filter cake 38 Hydrogen consumption 6 Distillate product 44 Final products- LPG Gasoline Jet fuel Diesel fuel 6 17 15 13 Thermal efficiency, 70 66 * dmmf = dry mineral matter free. 25 11 42 27 5 2 15 13 12 63 Fig. 2. NCB LSE extraction plant at CRE and reformed. This resulted in the cyclohexane being conver- ted into benzene.Although benzene has a high blending octane number it is not really desirable in gasoline because of its potential toxicity. Cyclohexane is environmentally acceptable but unfortunately it has a very much lower blending octane rating than benzene, and the RON (Research Octane Number) of the lightest naphtha is only 80. The second naphtha fraction contains all of the alkylcyclohexanes, which convert to alkyl- benzenes during reforming and have high octane numbers. The upper boiling limit of the second naphtha was set at 170°C to avoid the inclusion of two-ring compounds, such as tetralin and decalin. These compounds convert to naphthalene during reforming and naphthalene is not a suitable component for premium gasoline as it has a very low octane number and can cause blockages during carburation. Fig.3. NCB LSE hydrocracking plant at CRE amounts of distillates are collected for refining to produce transport fuels. Some examples of yield data for a UK bituminous coal and a North American lignite are given in Table 1. Secondary Refining of LSE Distillates The primary distillate products from the CRE LSE plant are described by the data given in Table 2. There will be some variation in these properties as the processing conditions and the feed coal change but they are considered to be typical of products derived from direct coal liquefaction processes, e.g., H-Coal, SRC, Exxon. The fractions defined in Table 2 could not be used directly as transport fuels as they do not comply with pump grade specifications, and some secondary refining of these primary products is necessary.A secondary refining scheme suggested for the NCB LSE distillates is shown in Fig. 4. The refining begins with an accurate fractionation of the distillates. Two light naphtha fractions that boil in the range C5-83"C and 83-170°C are taken. The lightest of these naphthas contains most of the cyclohexane produced in the primary conversion. In early gasoline preparations from LSE distillates a wide range naphtha, Cs-170 "C, was hydrotreated Table 2. Properties of LSE distillates Naphtha fraction Mid-distillate Nominal boiling rangePC 58-175 Yield, mass Yo coal to 15 process 175-310 30 Element- Carbon, % m/m 86.3 88.2 Hydrogen, % 13.0 11.3 Nitrogen, p. p. m. 175 870 Oxygen, % mlrn <0.1 ND Paraffins, % mlrn 10.4 Naphthenes, YO mlm 54.6 33 (By FIA) Aromatics, Yo m/m 35.7 67 (By FIA) Sulphur, p.p.m.6 39 PNA analysis- Major components- Cyclohexane Hydronaphthalenes Methylcyclopentanes Hydroanthracenes Methylcyclohexanes Et hylbenzene Naphtha Hydrotreating and Reforming These processing techniques have been developed for pet- roleum refining to produce high octane blending components from various refinery streams. As the platinum catalysts used in reforming are sensitive to sulphur most reformer feeds have to be hydrotreated to reduce the sulphur content to below 1 p.p.m. Continuous hydrotreating and reforming units have been built at CRE to investigate the adaptation of these petroleum refining methods to coal derived naphthas. A photographicANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 259 LSE light - hydrocarbons LSE primary distillates (80-300 "C) 1 - - Hydrogenator Mid-disti I late u (175-300°C) t t Cat.97 RON If - cracker iL Gasoline Blending D 96 RON 1 I t I 90 RON Fig. 4. LSE distillate refining scheme view of this equipment is shown in Fig. 5. In the hydrotreater metered amounts of naphtha and hydrogen gas are passed through a pre-heater to vapourise the liquid feedstock before passing to a catalyst packed reactor. The CRE plant has a reactor capacity of 500 ml and can operate at temperatures up to 400 "C at 50 bar hydrogen pressure. The catalysts used have been standard petroleum hydrodesulphurisation types in extruded pellet form with nickel - molybdenum impregnated on to alumina support material. After reaction the products are cooled to condense the liquid naphtha from the gas.The gas is mainly hydrogen and is re-cycled. The liquid naphtha is stripped of dissolved gases before feeding to the reformer. Some results from a typical hydrotreatment are given in Table 3. Table 3. Hydrotreating of LSE naphtha. Operating conditions: pressure, 30 bar; temperature, 350°C; LHSV 2.0 h-1 Paraffins, o/o m/m 7.9 7.2 Naphthenes, Yo m/m 60.1 61.8 Aromatics, %m/m 32.3 31.3 Carbon, YO m/m 86.3 86.5 Hydrogen, Yomlm 13.0 12.6 Nitrogen, p.p.m. 175 2.2 Sulphur, p.p.m. 6 0.2 Feed Product Mass balance 100 99.6 ~~~~ ~~~ ~~~~ ~ ~~ As a process, reforming involves three major reactions when applied to a petroleum naphtha. Firstly, catalytic dehydrocycli- sation, whereby aliphatics are converted into cyclic hydrocar- bons; secondly, dehydrogenation that converts naphthenes into aromatics; and thirdly, hydrocracking, which reduces the average molecular size by cracking in the presence of hydrogen.All of the reactions can be catalytically promoted by a single catalyst. However, as coal derived naphtha is highly cyclic and has a relatively low upper boiling-point, the major reaction to be promoted is dehydrogenation and catalysts with high selectivity in this respect have been used. The reforming unit at CRE has a total catalyst reactor capacity of 1.5 1. The reactor incorporates a pre-heating section of inert pellets above 250 ml of reforming catalyst. The liquid naphtha feed stock is vapourised in the pre-heating zone before passing to the catalyst, which is held at 450-550°C.The reforming reactions are carried out under a hydrogen pressure of 30-40 bar in order to reduce carbon deposition and extend catalyst life. The reforming catalyst used was supplied by Universal Matthey Products and is used commercially in one of their proprietary reforming processes. After reforming the total products are cooled to condense the reformate and most of the gas, which is mainly hydrogen, is re-cycled. Obviously with dehydrogenation reactions taking place hydrogen is evolved and excess gas must be removed from the system. The liquid reformate is passed to a stabilising stripper before being used as a gasoline blending component. The results from reforming various naphthas from LSE processing are given in Table 4. The first column shows the result of reforming a full range naphtha when the benzene content of the reformate was 12%.By taking a "heart-cut" from the naphtha (83-170 "C) as feedstock for reforming, the benzene content of the reformate was reduced to 1%. Table 4. Reforming of LSE coal naphthas. Operating conditions: catalyst, UMP; temperature, 480 "C; pressure, 25 bar; space velocity (LHSV), 2.0 h-1 Full range naphtha Heart-cut naphtha (C7170 "C) (85-170 "C) Feed Product Feed Product Paraffins, Yo m/m 19 8 12 9 Naphthenes, YO m/m 43 3 63 2 C6 aromatics, % m/m 1 12 Aromatics, YO mlm 38 89 25 89 1 Hydrogen, YO 13.4 10.3 13.4 10.2 Research octane No. 92 103 91 105 - Mass balance Naphthdreformate, YO 100 95 100 94 Hydrocarbon gas, YO 3 4 Hydrogen, o/o 2 2 ~ ~~ Catalytic Cracking The refining scheme for LSE distillates shown in Fig.4 indicated that the gasoline yield could be supplemented by cracking a portion of the mid-distillate fractions that have logically been earmarked for producing jet or diesel fuels. This possibility arises because the distillate yield pattern from LSE processing, 4 gasoline, 8 jet fuel and 5 diesel fuel, does not260 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 ~~ ~ Table 5. Catalytic cracking of LSE mid-distillates M. W. Kellogg (USA) Feed properties- Boiling range/"C 17G252 Hydrogen content, '/o m/m 13.6 Saturates, Yo V/V 85.7 Olefins, % VIV 6.3 Aromatics, YO V/V 8.0 Cracking conditions- TemperatureI'C 538 Catal ys t/oil 5.6 Yiela!s- Gas H2, C1-C3, Yo m/m 2 Gas C,+, % mlm 6 CT180 "C gasoline, Yo m/m 58 84 Conversion (- 180 "C products), % Gasoline properties- Sp.gr. 0.76 RON 100 Benzene, % 2.7 Crosfields (UK) 180-265 13.5 98 0 2.0 505 4.0 8 10 58 78 0.7741 85.4 0.8 match the current transport fuel market in Europe which is approximately 66% gasoline, 15% jet fuel, 19% diesel. Samples of hydrogenated LSE mid-distillates have been hydrocracked in the research laboratories of M. W. Kellogg Company at Houston and by Crosfields at Widnes. Some results from both laboratories are given in Table 5. Fig. 5. Second refining plant at CRE them to be equivalent in all respects to 4-star petroleum fuel. The levels of emissions were in many instances less than those observed with petroleum fuel, Table 8. Conclusions American petroleum companies who have been involved in the LSE Light Naphtha The yield data for LSE processing given in Table 1 shows a hydrocarbon gas yield of 16%.Much of this gas is produced during hydrocracking and has to be stripped from the hydrogen Table 6. Gasoline blending components available in LSE processing Specific gravity, 60160 O F Vapour pressurelbar Distillation IBP1"C IO-3OYo VOl/"C 50% Vol/'c 7&90% vol/"c FBP1"C Research octane number Reformate 0.8488 0.074 89 11 1/121 131 145/163 199 101.4 Motor octane number 89.5 FCC gasoline 0.7737 0.261 53 75/89 105 1271 155 167 85.4 c 77.6 Light naphtha 0.7503 0.315 63 71-78 75 7718 1 93 79.7 74.4 (1) Light naphtha 0.6974 0,752 36 44/45 55 74195 105 77.2 74.4 (2) re-cycle gas. The re-cycle gas in the CRE plant also carries with it a considerable amount of C4-C7 hydrocarbons, which are useful gasoline blending components.A synthetic naphtha was prepared to represent these hydrocarbons for the final gasoline blend. LSE Gasoline Blending and Testing The blending stocks available from LSE processing and distillate refining are described in Table 6. Blending was carried out by Associated Octel at their Engine Test Labora- tories at Bletchley. The proportions of the various stocks were calculated to make a fuel with low benzene content and an RON of 96, a minimum requirement for future premium non-leaded gaso- line. These blending proportions are given in Table 7. This fuel was checked in a CFR engine by Associated Octel when the RON was determined as 96 and the MON as 86. The amount of fuel prepared was not sufficient for a complete engine test.However, previous work1 with leaded gasolines prepared from LSE distillates, which had a 98 RON, showed Table 7. Gasoline blends and engine performance Blend A, parts by mass Composition- Reformate 100.0 Light naphtha 1 28.0 Butane 13.3 Benzene, '/O 2.3 Specific gravity 60/60 O F 0.796 Light naphtha 2 0.2 FCC gasoline 0.0 Estimated quality- Vapour pressurejbar 0.80 Distillation- Recovery, '/o V/V at 70 "C Recovery, o/o V/V at 100 "C 8.5 29.0 Engine tests- Octane quality Research method 96.9 Motor method 84.0 Blend B , parts by mass 100.0 12.5 0.0 14.2 24.8 2.7 0.799 0.88 8.5 22.0 96.9 84.3ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 261 Table 8. Engine performance tests with LSE gasolines. Tests by Associated Octel Ltd. Ford Cortina 1.6 L Austin Metro 1.3 L Reference Coal derived Reference Coal derived fuel gasoline fuel gasoline Emissions in urban cycle/g per test HC 3.62 2.96 4.71 4.68 co 31.4 15.4 13.1 6.7 COZ 373.5 377.1 397.9 398.7 NO, 3.69 4.60 2.51 3.26 Fuel consumption in urban cycle/l per 100 km 10.42 10.72 8.85 8.69 Fuel consumption at constant 90 kph/ 1 per 100 km 7.35 7.21 5 .OO 5.06 development of coal liquefaction have often stated that if coal can be converted into distillates boiling in the C+I5O0C range then conventional petroleum refining methods could be used to prepare any commercial grade of transport fuel. Our work at CRE has demonstrated this possibility and has shown that by modification the processes can also produce the clean fuels currently being demanded by new environmental standards. References 1. Davies, G. o., and Gavin, D. G., Preparation and Performance of Coal Derived Transport Fuels,” ECSC Round Table Conference, Brussels, 1983, Report EUR-9118. 2. Davies, G. O., and Freese, R., Preparation and Performance of Coal Derived Diesel Fuels, CIMAC Conference, Helsinki, 1981. “Consequence of Limiting Benzene Content of Motor Gaso- line,” Concawe Report No. 13/83. 3.

ISSN:0144-557X    

DOI:10.1039/AP9852200257

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 261 Forward Planning and Quality Control in Coal Production M. J. Annetts and T. M. Aitken National Coal Board, Scottish Area Laboratory, Scientific Department, 160 Glasgow Road, Edinburgh € H I 2 8LT Matching production to market demands in terms of quantity, quality and cost requires forward planning. To establish the location of coal seams, develop access to them and develop and control extraction make time scales very long and plans vulnerable to many complex effects, including market vari- ations, economic, political and governmental changes. Fore- casting is therefore extremely difficult, the plan target often changing before full implementation. Flexibility and adapt- ability are necessary in planning and compromise is an important control mechanism.The best aid to flexibility and effective compromise is intimate knowledge of the quantity, properties and accessibility of the coal within known seams. Quality is a complex term, with a different meaning for each application. It is the relationship between measured and desired values of a particular property or set of properties of the coal and has to be considered at all stages of planning and operation in coal production. Properties Many important properties of coal are related to and are some measure of its rank, rank being a measure of the maturity of coal. These include carbon, oxygen, hydrogen, volatile matter, calorific value, coking properties and moisture. Volatile matter and coking properties are used to determine rank and hence the main use.Other properties, not necessarily dependent upon rank and not wholly properties of the coal substance, are many and varied, their significance depending on the usage of the coal. The more important practical parameters are ash, moisture, calorific value, sulphur, chlorine and ash fusion and these can affect the value of the product. Ash content is often regarded as the measure of coal quality. Mineral matter, inseparable from the coal substance, accounts for the inherent seam ash, but in mining operations material from the seam roof, floor, partings and intrusions within the seam add to the incombustible material. Most of this adven- titious ash can be removed by density separation in washing processes. Inherent ash contents range from <1 to 20%, with an average between 5 and 7.5%.Current deep mining methods produce run of mine (R.O.M.) ash values between 25 and Considerable amounts of moisture can be added to coal during mining and preparation operations, the total moisture content being considerably increased from the inherent seam moisture and having a significant effect on the heat value of the mined coal. Excess moisture in small coal can also create handling and shipment problems. Control during mining and preparation is limited. As most coals are currently used in combustion processes the prime indicator of quality is calorific (heat) value. On the pure coal substance this value is reasonably constant within a restricted range of coal rank, so that the variability of ash and moisture content is significant in terms of quality assessment and has a direct bearing on the value of the coal.Sulphur content is a quality parameter in the coking market and recent environmental considerations make it more signifi- cant for most uses. Heavier contaminations of pyrites can be removed by washing processes but intimately mixed pyrites and organic sulphur compounds are difficult to remove. Seam selection and blending provide the only method of control. In British coals, sulphur ranges between 0.5 and 5.0%0, with an average around 1.940, the lowest being in the Scottish and South Wales coalfields. Chlorine content is a quality parameter in some combustion processes, having been related to fireside corrosion and tube fouling in boiler plant at levels >0.5%0.Chlorine varies between a trace and 1.2%. Higher chlorine coals occur mainly in the central coalfields, and generally, chlorine content increases with increase in depth. No suitable economic process 40%.262 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 is available to reduce chlorine in mined coal, so control by seam selection and blending will continue. Ash fusion temperature is significant in combustion processes to prevent undesirable clinker formation or, alterna- tively, in processes requiring molten slag such as slagging gasifiers. The composition of the ash affects fusion tempera- ture, so that the value for the coal seam may differ from the run of mine product which includes extraneous dirt, often more significant to the fusion temperature. Most elements are present in coal seams in small or trace amounts and interest in specific trace elements is growing as health and pollution considerations develop.These elements may be involved in the quality equation at some future time. Exploration In order to establish and maintain long-term plans, the location, quantity and quality of economically workable coal must be known. The NCB has an exploration team, which is complemented by Area Geological teams collecting data on new reserves, mainly by surface drilling and seismic surveys. Nucleonic down-hole logging techniques are employed to confirm seam position, thicknesses and strata densities and laboratory studies of recovered cores are used to assess quality. The laboratory analytical data establish the rank and potential usage and also provides useful information for coal preparation and marketing.Other characteristics determined on associated rocks are used to assess such matters as indendive sparking and gas emission potential for consideration along with many other factors in planning safe practical mining operations. Underground exploration by means of samples taken from seam exposures in shaft sinkings, cross-measure drifts, head- ings and coal faces, together with drilling and in-seam seismic surveys, provide much information to enhance seam mapping. Thus, exploration should produce essential information for use in the decision making processes for new sinkings and extensions to existing mines. These processes are fraught with additional problems covering projected capital and operational costs, potential life, available markets, manpower, trans- portation and environmental effects, all having their impact on the over-all lengthy time scale.Short Term and Operational Planning and Control Once decisions are made and new mines and major extensions developed, the producing Areas have to formulate plans for up to 5 years ahead. For this shorter-term planning, detailed information on the seams to be worked is essential to provide the correct amounts of coal meeting the required specification for the available markets. Expected mining costs and coal preparation requirements also have considerable influence on the plans. The underground exploration work is used extensively to enhance the surface exploration data in the general working area.The more detailed information on seams allows decisions to be made on the optimum position and depth of cut within the seam needed to produce the required tonnage and quality. Ash content is one of the main parameters of quality at this stage and, depending on the selected market, sulphur, chlorine and ash fusion may be significant. Because of the heterogeneous nature of coal it is necessary to continue seam sampling throughout the operating life of the mine in order to assess the effect of seam variations in quality, thickness, partings and possible intrusions. With this infor- mation and a measure of the dirt produced from drivages, roadway maintenance and any roof or floor taken with the coal, R.O.M. quality can be forecast. This can be compared with actual R.O.M.quality and control applied if deviations occur. In-seam seismology can give an early warning of faulting or intrusions within the seam, so that preparations can be made to deal with excess dirt. Machine guidance systems are available to control cutting horizons within seams, limiting extraneous roof or floor dirt. The measurement of R.O.M. quality is currently achieved by sampling and laboratory analysis. Rapid and semi- automatic methods of quality monitoring in terms of ash have been applied with limited success, using variations in density to indicate ash changes. Nucleonic methods are currently under development to monitor the R.O.M. product directly on-belt. Control of quality at this point enhances the value of the product by reducing losses incurred in winding dirt.It also reduces the washing and preparation requirement with addi- tional cost benefit. Final Product Control As the bulk of output is used in the power generation field and general steam raising processes, the calorific value (CV) of the product supplied to the customer is the main consideration. Ash and moisture content have the greatest effect on the “as supplied’’ CV and their measurement allows “as supplied” CV to be calculated and control applied. Mechanical sampling systems are in operation at most major outlets to provide samples representative of the whole product. To eliminate the time delay in sample preparation and analysis, instrumentation has been developed over recent years to monitor the sample stream for ash and moisture content and, with some computation, CV.This information can be used for plant control and blending operations. Nucleonic techniques are used for ash measurement and microwave techniques for moisture. Sulphur monitoring using nucleonic techniques has also been applied on a limited scale. Opencast Mining Opencast mining provides a better opportunity for planning and quality control. The relative ease of drilling for core samples allows more extensive information to be collected for short term and operational planning without incurring exces- sive costs. Each prospect can be fully drilled to provide fairly accurate information on the number and quality of seams and the amount of coal available. As seams are exposed the ease of sampling simplifies selection and extraction proportioning to achieve the required quality.Dirt from the seam roof and floor is easily minimised, limiting washing requirements particularly as a large proportion of the product is produced as power- station fuel. Opencast mining provides a flexible source of output. Sites are relatively short lived compared with deep mines but are easier and cheaper to exploit. If sufficient prospecting is carried out, sites can be operated to meet market fluctuations and cushion the effect on deep mine operations. As only about 12% of output is from opencast mining, control of the rate of production is important to preserve flexibility without losing the cost benefits. End User Control The resources of coal have their own particular properties and little can be done to modify these.If user quality requirements cannot be reasonably met within the scope of existing operations, process modifications are required to utilise the available product. The Clean Air Act was a dramatic example, which generated the smokeless fuel industry, conversion processes being developed to continue coal usage. The additional processing costs influenced the development of appliances to burn coal smokelessly . The development of fluidised bed combustion provides not only a more efficient combustion process but also has the ability to reduce pollution by retaining undesirable combustion products in the ash bed. This enables quality constraints to be relaxed. For the future, gasification and extraction processes areANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 263 being researched and will be applied as economics and environmental constraints dictate.These will make their own demands on quality, although emphasis is placed on using as wide a range of coal quality as possible. Conclusions Marketing and environmental constraints, together with new processes and the need to be economically viable, will place greater demands on coal extraction planning and quality control. The measure of quality will become more complex as additionaI parameters need to be considered, The measurement and control of run-of-mine quality reduces the amount of dirt mined and transported and the load on coal cleaning and preparation facilities. This can improve profitability and ensure consistent product quality. The measure of “quality” has influence within the various planning and control stages to ensure that the industry operates efficiently to produce products that meet the customer’s needs. Analytical Methods in Organic Geochemistry G.Eglinton, R. P. Evershed,” J. P. Gill and C. S. Hein Organic Geochemistry Unit, School of Chemistry, University of Bristol, BristolBS8 ITS This paper reviews the developing role of analytical methods, especially mass spectrometry, in organic geochemistry, as illustrated by the study of fossil porphyrins (petroporphyrins), Tetrapyrroles occur ubiquitously in the geosphere. As porphyrins, they are found in older rocks and petroleums, where they occur as complex mixtures dominated by DPEP, and aetioporphyrins (see Fig. 1) mainly as nickel and vanadyl metalloporphyrins, in amounts varying from zero to several thousand parts per million.The rocks in which they occur range in age from a few million years to cu. three thousand million years. The evidence indicates that the chlorophylls are the major sources. Alfred Treibs laid the foundations for this area of geochemistry in the mid-1930s.2 4 I sensitive, if rather limited, evaluation of metalloporphyrin fractions and can be useful in preliminary assessments. EIMS, and especially high resolution EIMS, have been used skillfully by Bonnett and co-workers475 to demonstrate that a range of metalloporphyrins ( e - g . , iron, manganese and gallium), in addition to those commonly recognised (nickel, V=O and copper), are present in geological materials. A series of gallium porphyrins is believed to be present in certain coals as Ga-OH complexes.Knowledge of the structures of individual petroporphyrins is advancing rapidly, largely through the intensive application of chromatographic techniques for separation and of spectro- scopic techniques, particularly NMR and mass spectrometry , Chlorophyll-a DPEP-5 Metallo- DPEP Aetio-Ill Fig. 1. In the geosphere, the deoxyphylloerythroaetioporphyrins with the 13,Eethano ring (DPEP-5) and the aetioporphyrins (e.g., aetio-111) are major components, usually as metallo derivatives (e.g., nickel and V=O). Chlorophyll a is the putative ultimate biological source for most petroporphyrins’ Electron Impact Mass Spectrometry Electron impact mass spectrometry (EIMS) has long been used in the analysis of porphyrins and metalloporphyrins (e.g., reference 3).Some idea of the complexity of petroporphyrin mixtures can be gained from summed mass spectra obtained by probe analyses. Thus, the vanadyl petroporphyrin fraction extracted from a petroleum (such as Boscan) reveals, in addition to the major aetio and DPEP type porphyrins, three minor porphyrin series apparently possessing further degrees of unsaturation in their f$-pyrrole substituents. These minor series may include tetrahydrobenz-DPEP, benz-aetio and benz-DPEP type structures. The molecules present fall into series from C23 to C46. The ions of the biologically significant DPEP series are prominent. The technique gives a quick and * Present address: Department of Biochemistry, University of Liverpool, P.O.Box 147, Liverpool L69 3BX. for structure determination (Fig. 2). The complexity of petroporphyrin extracts can be adduced from the HPLC analysis of the corresponding free-base petroporphyrins (Fig. 3). Demetallation of the metalloporphyrin concentrate with methanesulphonic acid affords the free petroporphyrins, which chromatograph well over microparticulate silica. The extent of the analytical problem for minor and trace components is clear. LC - MS analyses with this degree of separation would seem both technically feasible and scientifically desirable. Chemical Ionisation Mass Spectrometry Chemical ionisation mass spectrometry of mixtures of free porphyrins (using methane) provides spectra wherein the molecular ions are enhanced and are virtually the only ions observed.However, with hydrogen - CIMS partial hydrogena- tion at the mew positions in the porphyrin ring occurs, forming porphyrinogens. Ions appear in the lower mass region, corresponding to tripyrrolic, dipyrrolic and monopyrrolic264 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Oil/ rock 1 1 Extract + @ee P Frse P free P Other, TCC, HPlC, Crystallisation, etc. Fractions and single P 4 + Derivatisation, etc. f * + i El FD-MS MS-MS GC-MS NMR CI LSiMS HRMS LC-MS UVhisible DCJ FA5 X-ray, etc. Ti. 2. Extraction, separation and characterisation of petroporphy- rins. fetroporphyrins fp) can be obtained by solvent extraction of petroleums and ancient sediments. Chromatography affords concen- trates of both free porphyrins and metalloporphyrins (e.g., nickel and V=O), usually as complex mixtures' fragments.6 The value of the hydrogen - CIMS technique lies in the information that can be obtained concerning the aikyl substitution around the porphyrin ring.The dipyrrolic ions are especially useful in this regard. The pattern of fragment ions (e.g., Table 1) may allow the substitution around the macro- cyclic ring to be deduced. Maxwell and colleagues at Bristol have used this technique, together with NMR studies on sing€e, pure petroporphyrins trapped from HPLC fractions.' The method works with both aetio and DPEP-type porphyrins. In other work at Bristol, Evershed and colleagues have investigated the application of the hydrogen - CIMS method to metalloporphyrins.8 Recently, hydrogen - CIMS of metallo- porphyrins has been performed using tandem mass spec- trometry (hydrogen - CIMS/MS).9 It has also been demon- strated that ammonia reagent gas provides mass spectra similar to those obtained using hydrogen.10 Table 1.Dipyrrolic even mass ions observed in the hydrogen CI spectrum of octaethylporphyrin mlz R R' Intensity ratio 258 H H 3 272 Me H 3 286 Me Me 1 Gas Chromatography - Mass Spectrometry (GC - MS) Gas chromatography and GC - MS of underivatised alkyl porphyrins and of metalloporphyrins is possible but is not really a practicable solution to their anaiysis.l'J2 An answer to these problems has been sought through derivatisation of the porphyrin ring system. One solution was provided by Boylan and Calvin13 in 1967 in the form of the silicon(1V) derivative, protected on both sides of the ring by axial trimethyisiloxy groups.The derivatives are relatively easy to prepare, more volatile than the free or metalioporphyrins, and have, in consequence, considerably shorter retention times. At Bristol we also investigated the use of the related bis(t- butyldimethylsiloxy) derivatives. 14915 The introduction of the much more bulky t-butyl group confers enhanced stability to laboratory handling and chromatographic conditions, but the increased relative molecular mass does bring a small penalty in longer retention times. However, the advantages of these TBDMS derivatives greatly outweigh the disadvantage. I I I I I 0 10 20 30 40 50 Ti me/min Fig. 3. HPLC trace of free-base petroporphyrins obtained by demetallation of the vanadyl petroporphyrin fraction from Boscan crude oil.Chromatography is over silica with spectrophotorne tric detection at 400 nm. Two major components of known structure are indicated. 1 The complexity of the petroporphyrin mixture reflects the raised temperatures of oil generation. Boscan petroleum (Venezuela) is known for its high concentration (several thousand p.p.m.) of vanadyl porphyrins Efficient GC - MS analyses of petroporphyrin mixtures require good gas chromatography; in addition, the spectra of individual components must be relativeiy simple so that single ions carry sufficient signal. The TBDMS derivatives exhibit mass spectra which have three principal ions: M+, M - 57+ (loss of t-butyl) and the base peak M - 131+ (loss of the TBDMSO group). Manual assignment of these ions is facili- tated and, indeed, deconvolution of GC - MS peaks in terms of contributions from different porphyrins can be carried out by computer programs. Fig.4 iiiustrates a GC - MS run of a mixture of geological porphyrins (petroporphyrins) , as their TBDMS derivatives, with n-alkanes as retention index stan- dards. Mass chromatography, plotted against a common KRI Kovhts retention index Fig. 4. Computerised gas chromatography - mass spectrometry of Boscan crude oil petroporphyrins as their bis(r-butyldimethyl- siloxy)silicon(IV) derivatives. The inset structure shows the bis(r- butyIdimethylsiloxy)silicon(IV) derivative of DPEP, the major com- ponent of the sample, which comprises >SO% of the marked peak. The total ion current trace has been plotted against Koviits retention index, using software operating on the retention data for co-injected n-alkane standards14.15 (Kocdts retention index) scale, can be used to follow the distributions of different types of petroporphyrin.It is clear that many components co-elute or are poorly resolved from one another. Fortunately, substantial deconvolution of these traces can be accomplished through detailed study of individual scans. We find that the carbon number range C34--C42 of co-injected n-alkanes encompasses most of the petroporphyrin distributions. Scans at 1-s intervals do allow deconvolution but faster scans (e.g., about 0.1 s) would give improved resolution. The procedure has been set out and illustrated in a number of papers both published and in the press.14-15 The GC - MS data for the Boscan petroporphyrins reveal several different series of peaks corresponding to a range of petroporphyrin isomers at each carbon number. The carbon number of each componentANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 265 can be plotted against KRI, revealing over two hundred points which fall on series of almost straight lines roughly parallel to each other (Fig. 5).Some of these correspond to the major series of petroporphyrins, DPEP, aetio, etc. Co-injection of standard compounds obtained .through synthesis and by isolation from geological mixtures allows these alkylporphyrins of known structure to be plotted on the same diagram. Individual porphyrins within, say, the aetio series, fall on lines corresponding to a series of homologues or pseudo- homologues, where an increment of a methylene group gives a standard increment in retention index.We are currently using this approach to examine the petroporphyrin fractions extrac- ted from a number of oil shales and other geochemically significant samples. c 4- ?2 37t ii 35 ’“1 i. 34 25 26 27 . . 1 ’ : . * . a . . . I I I I I I I 28 29 30 31 32 33 34 Carbon number 35 36 Fig. 5. A Kovats plot of KRI versus carbon number for each porphyrin component [as the (TBDMSO),Si(IV) derivatives] of Gilsonite bitumen. At least 123 compounds are present. The points appear to lie on near parallel lines, proposed to represent pseudo- homologous series. The GC - MS data were obtained under the conditions of Fig. 4 Multimolecular Analysis GC - MS analysis of petroporphyrin mixtures exemplifies the general problem of complex mixture analysis.The goals are to determine the qualitative and, hence, possibly, the quantita- tive composition of the mixtures. This requires separation, then molecular characterisation and finally quantification, i. e. “multimolecular analysis.” The results from a GC - MS analysis need to be seen in parallel with the data relating to the source of the sample, such as its geochemical or environmental provenance and the analytical procedures used to prepare the fraction, which may have introduced molecular discrimination. The analyst’s aim must be to bring multimolecular information determined in the GC - MS analysis into a common data base, wherein is stored the other information mentioned above (see Fig.6). The desired end result is improved understanding of the biological origins and geological histories of the petro- porphyrins. 16 Multimolecular analysis presents a general information problem in analytical chemistry, brought about by the capa- bility of instruments to provide data on hundreds, if not thousands, of compounds per analysis. Some form of com- puterised data handling is essential if the underlying signifi- cance of these data is to be discerned. This challenge relates not only to GC - MS but also to LC - MS and, in fact, to any analytical technique affording multimolecular analyses. We are seeking to meet this challenge through automated analysis and the transfer of the resultant multimolecular data directly into the data base through on-line transfer.Automated multicomponent interpretation of petroporphy- rin GC - MS data has been successfully performed at Bristol. This is achieved by entering, into an appropriate library, the KRI and mass spectral characteristics for known petroporphy- rin constituents. These compounds may subsequently be determined in unknown GC - MS data by a reverse search software package. Resultant multimolecular informatian (i. e. , compound listings) is output by this software in a format specifically designed for inclusion into a data base of organic geochemical information. This data base, created using a commercial data base management system on a large main- frame computer, serves to facilitate subsequent multi-sample analysis. Petroporphyrin distribution information, gathered by the reverse search method and entered into the Bristol data base, was used in multi-sample correlation and in graphical analysis.17 - - - - - - - - _ - _ - - Sources of samples- Geochemical and Analytical procedures t environmentst information 1 I I 1.- Analytical information + + Compound abundance Muttimolecular analyses4 information L----7------J Common database Correlation Statistical Graphics manipu tat ion Fig. 6. Multimolecular analysis-the information problem. Three main sources of information: (i), the provenance of the samples; (ii), the analytical procedures; and (iii), the multimolecular analyses them- selves are all of importance to the geochemist. Access to this information, held in a data base, facilitates secondary analysis using software packages (data base management systems), which allow the analyst to manipulate all three together16 Applications of Petroporphyrin Analysis Analyses of petroporphyrins extracted from sediment samples taken from bore holes have begun to clarify the picture concerning the origin and fate of these compounds in the geosphere.The pattern is that of simple petroporphyrin distributions with very marked DPEP dominance in the young, immature sediments, grading into much more complex distri- butions dominated by aetioporphyrins in mature, deeply buried source rocks. Deep burial is normally accompanied by raised temperatures, about 30 “C km-1 being a value typical of subsiding basins (e.g., the North Sea). Metalloporphyrins are found in quite deeply buried (e.g., 3-4 km) sediments, surviving well into the so-called oil generation window.With very deeply sourced hot oils ( e . g . , 200 “C at 5 km depth) the surviving metalloporphyrin content is normally very low, owing to thermal destruction and general graphitisation of the organic matter. Probe EIMS can be used directly to assess total porphyrin fractions for their relative content of DPEP and aetio homologues, while GC - MS procedures provide much more detailed information. One molecular parameter of thermal experience that has been found to be relatively easy to measure is the percentage of DPEP/(DPEP + aetio). Barwise and colleagues at BP, Sunbury-on-Thames, have demonstrated that this parameter plots linearly downhole against accepted measures of thermal maturity, such as vitrinite reflectance.18-19 However, vitrinite reflectance is dependent on gross che- mistry, whereas the porphyrin maturity parameter is more specific and exemplifies the growing number of molecular parameters that can be used to assess the thermal experience of buried sediments. Colleagues at Bristol20.21 have pioneered the study of several such measures, which are now widely used in the oil industry in the exploration for petroleum. Useful molecular markers include steroidal and triterpenoidal hydro- carbons, where the relevant stereochemical parameters are readily measured by GC - MS techniques. We thank Mr. C. L. Saunders, Mrs. A. P. Gowar and Ms. Lynne Dyas for assistance with MS facilities. We are much indebted to the Natural Environment Research Council for their support of the mass spectrometry and computing facilities266 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 at Bristol (GR3/2951, GR3/3758).We are also most grateful to the British Petroleum plc, Exploration Division, for their continuing support under the EMRA scheme, and the Univer- sity of California, San Francisco, for a NASA sub-contract. References 1. Evershed, R. P., Barwise, A. J. G., Eglinton, G., and Maxwell, J. R., Interdisciplin. Sci. Rev., in the press. 2. Treibs, A., Angew. Chem., 1936,49,682. 3. Budzikiewicz, H., in Dolphin, D., Editor “The Porphyrins,” Volume 111, Academic Press, New York, 1978, pp. 395-461. 4. Bonnett, R., and Czechowski, F., Nature (London), 1980, 283, 465. 5. Bonnett, R., Burke, P.J., and Reszka, A., J. Chem. SOC. Chem. Commun., 1983, 1085. 6. Shaw, G. J., Eglinton, G., and Quirke, J. M. E., Anal. Chem., 1981,53,2014. 7. Wolff, G. A., Chicarelli, M. I., Shaw, G. J., Evershed, R. P., Quirke, J. M. E., and Maxwell, J. R., Tetrahedron, 1984,40, 3777. 8. Evershed, R. P., Wolff, G. A., Shaw, G. J., and Eglinton, G., Org. Mass Spectrom., in the press. 9. Sundararaman, P., Gallegos, E. J., Baker, E. W., Slayback, J. R. B., and Johnston, M. R., Anal. Chem., 1984, 56, 2552. 10. Jiang, X.-Y., Szente, A. W., Tolf, B. -R., Kehres, L. A., Burneberg, E., and Djerassi, C., Tetrahedron Lett. 1984, 25, 4083. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. Marriott, P. J., Gill, J. P., and Eglinton, G., J. Chromatogr., 1982, 236, 395. Marriott, P. J., Gill, J.P., Evershed, R. P., Eglinton, G., and Maxwell, J. R., Chromatographia, 1982, 16, 304. Boylan, D. B., and Calvin, M., J. Am. Chem. SOC., 1967,89, 5472. Marriott, P. J., Gill, J. P., Evershed, R. P., Hein, C. S., and Eglinton, G., J. Chromatogr., 1984, 301, 107. Eglinton, G., Evershed, R. P., and Gill, J. P., Org. Geochem., 1984,6, 157. Eglinton, G., in Nash, S., Editor, “Science and Uncertainty,” Science Reviews Ltd., 1985, pp. 192-219. Hein, C. S., Gill, J. P., Evershed, R. P., and Eglinton, G., Anal. Chem., in the press. Barwise, A. J. G., and Park, P. J. D., in BjorPry, M., Albrecht, P., Cornford, C., De Groot, K., Eglinton, G., Galimou, E., Leythduser, D., Pelet, R., Rullkotter, J., and Speers, G., Editors, “Advances in Organic Geochemistry 1981 ,” Wiley, Chichester, 1983, pp.668-674. Barwise, A. J. G., in Brooks, J., Editor, “Petroleum Geo- chemistry and Exploration of Europe,” Blackwell Scientific Publications, Oxford, 1983, pp. 309-315. Mackenzie, A. S., and Maxwell, J. R., in Brooks, J., Editor, “Organic Maturation Studies and Fossil Fuel Exploration,’’ Academic Press, New York, 1981, pp. 239-254. Mackenzie, A. S., Brassell, S. C., Eglinton, G., and Maxwell, J. R., Science, 1982, 217, 491. Some Aspects of Oil Spillage Characterisation S. J. W. Grigson Institute of Offshore Engineering, Heriot- Watt University, Riccarton, Currie, Edinburgh EH 14 4AS W. R. Scotland and 1. Soutar” Department of Chemistry, Heriot- Watt University, Riccarton, Currie, Edinburgh EH 14 4AS In the UK, the record for successful detection of the pollution source in cases of oil contamination of the marine environment is less than impressive.1 The problems of identification of the party responsible for pollution in the many cases encountered each year are considerable and have their origins in, inter alia, the number and diversity of oils imported into British terminals, the large number of independent authorities responsible for detection and prosecution and the absence of a recognised forensic methodology of court competent analytical techniques.In the latter context we have devised an analytical strategy based mainly upon a combination of computerised gas chromatography - mass spectrometry (C - GC - MS) and computerised luminescence spectroscopy, which provides an extremely powerful tool for oil spill fingerprinting.As part of an SERC financed research programme, the Institute of Offshore Engineering and the Chemistry Department of Heriot-Watt University have been evaluating the best means of application of C - GC - MS and luminescence spectroscopy to real-life oil spill situations and the effects of weathering upon the resultant spectra. In this report some results obtained using the most basic methodology that we have adopted involving these two approaches are described. Development of an Analytical Methodology In consideration of the techniques available for the character- isation of petroleum hydrocarbons the methods can be broadly classified into chromatographic and spectroscopic and those utilising features of both. Chromatographic techniques include thin-layer chromatography (TLC) , gas chromatography (GC) and high-performance liquid chromatography (HPLC) .Spec- troscopic methods include atomic-absorption spectroscopy, infrared spectroscopy and ultraviolet absorption and fluores- cence spectrosopy . Many of these methods are susceptible to the effects of * To whom correspondence should be addressed. weathering in the marine environment and require compensa- tory artificial weathering of suspect sources for the successful matching of source and pollutant. It is desirable, in adoption of an analytical procedure for fingerprinting, that methods be chosen to complement one another (in extension of the classes of components of the oils under surveillance) and that the spectra obtained be as little affected by weathering of the oils as possible.Luminescence Techniques Luminescence measurements are attractive in analytical chemistry as a result of their high sensitivity, reasonable selectivity and application to the aromatic content of a complex mixture of hydrocarbons (important owing to its toxic nature and stability towards weathering). The direct examination of mixtures of oil in water is possible in favourable circumstances when using luminescence techniques.2 Fluorescence Analysis Conventional fluorescence spectroscopy has been popular in its application to oil spill fingerprinting for some years. The adoption of the technique by the US Coastguard as part of a basic and routine analytical procedure involving, in addition, the use of TLC, IR and GC measurement,3 has been validated by the considerable identification success record following pollution incidents in US coastal waters, However, a conven- tional fluorescence spectrum merely represents one section across a three-dimensional matrix determined by the intensity dependence upon twin wavelength parameters of emission and exitation.The subjectivity imposed by the choice of a single excitation. The subjectivity imposed by the choice of a single excitation wavelength can lead to the exclusion of valuable conventional fluorescence spectra are valuable as a rapid means of discrimination between some suspect sources but are severely limited as a differentiating arbiter between hydrocar- bon mixtures of similar composition.4-6ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 267 L I I I I I I I I I 200 300 400 500 200 300 400 500 Emission wavelengthinm Fig.1. diagram of pollution sample (100 yl 1-1, cyclohexane, 298 K) ( a ) , Total fluorescence contour diagram of bilge sample (100 yl 1-1, cyclohexane, 298 K); and ( b ) , total fluorescence contour Synchronous Excitation7 The method of synchronous scanning fluorescence spectro- scopy samples the total fluorescence emission matrix in a different manner to conventional emission spectroscopy. The sample is illuminated with monochromatic radiation of an energy such that a constant difference in wavelength, AA, is maintained between that of emission and excitation. The resultant spectra are more structured than conventional scans and consequently exhibit enhanced discriminatory potential in qualitative analysis of complex mixtures.The ability to vary AA results in an additional degree of selectivity and the series of synchronous scans generated at various AA values constitutes a collection of sections, angled at 45” to the wavelength axes, across the intensity matrix. The technique is rapid and capable of some differentiation between oils which contain similar distributions of aromatic con~tituents.~.8 Total Fluorescence Spectroscopy Representation of the whole three-dimensional intensity mat- rix realises the full potential of the fluorescence technique in its basic format. For quantitative analysis and rapid visual discrimination between fluorescence fingerprints, a contour representation of the topographical features of the emission matrix is most attractive.The total fluorescence contour representation, exemplified in Fig. 1, has been shown to offer a high degree of discrimination between the large number of oils studied in our laboratory.6.8 Furthermore, the technique has been success- fully applied, as described below, in real life oil spill incidents and to other oils subjected to varying types and degrees of weathering.’ Initial criticisms of the approach as being too time consuming (although valid during development stages, where manual digitisation of data for presentation to an off-line computers takes place) are no longer applicable. Commercial fluorimeters are now available, interfaced to minicomputers or data stations of sufficient capability to generate contour representations.Methodology In summary, the basic fluorescence methodology adopted in our laboratory for oil characterisation involves the sequential application of: ( a ) , conventional fluorescence spectra; (b), synchronous scanning; and ( c ) , total fluorescence. In many instances the techniques ( a ) and ( 6 ) are sufficient to exclude suspect sources from further analysis, whilst (c) can provide very persuasive evidence of the implication of a source in a given incident. It should be noted that, in common with many other analytical techniques, the fluorescence approach is not reliable in differentiation between oils of very similar aromatic composition. In particular, North Sea crudes from proximate fields are not separable by this technique. As a consequence, we have employed ancillary emission spectroscopic methods, such as phosphorescence spectroscopy,lO low-temperature fluorescence and selective quenching/enhancement of excited states in order to enhance the differentiation between oils afforded by the basic fluorescence approach.The usefulness of phosphorescence techniques employing oils dispersed in low temperature glasses has prompted interest in room tempera- ture phosphorescence induced, for example, in micellar media. This technique might enjoy some useful development into a method whereby both fluorescence and phosphorescence contour characteristics are simultaneously sampled provided that some initial stability problems, not evident from the literature,ll can be overcome. Computerised Gas Chromatography - Mass Spectrometry Gas chromatography has seen much application to oil spill fingerprinting.Much of the early work relied upon a compari- son of n-alkane and isoprenoid (pristane and phytane) distribu- tions. Problems concerned with the effects of weathering resulted in the use of artificial weathering to simulate the chromatograms obtained in the event of prolonged exposure in the marine environment and in the adoption of detectors other than the flame ionisation detector so that components of greater stability to degradation might be observed. (For a recent review, see reference 12.) Computerised GC - MS can be used to study both the aliphatic and aromatic components in petroleum and, as a combination, considerably extends the analytical potential of GC or MS used in isolation.Of particular relevance to oil spill fingerprinting is the distribution of “biological marker” com- pounds, including the steranes and triterpanes.13.14 Despite the very low concentrations of such compounds in oil, C - GC - MS can be used via selective ion monitoring to study their distribution variations, which form the basis of the fingerprint- ing technique.15 Fig. 2 shows a characteristic mass fragmento- gram of a pollutant and its source. In addition, distributions of other compounds stable to weathering, such as alkyl homologues of aromatics, can be used to characterise an oil. Applicability of the Oil Spill Fingerprinting Methodology The basic approach using both fluorescence and C - GC - MS, outlined above, has been validated in a number of trials including real-life spills, marine weathering tests, biodegrada- tive studies and artificial weathering.Two examples will serve to ilustrate the success achieved to date. Artificial weathering A sample of a North Sea crude was subjected to a high degree of weathering in an outdoor tank. Fluorescence and C - GC -ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 I Time - Time - Fig. 2. ( a ) , Sterane fingerprint (mlz 217) of bilge sample; (b). sterane fingerprint (mlz 217) of pollution sample MS information was obtained by sampling at regular intervals. The fluorescence contour diagrams and synchronous scans retained the essential features of the fingerprint for the unweathered oil (in contrast to the conventional spectra), whilst the sterane and triterpane fingerprints were unaffected by weathering.These results held true under weathering conditions which considerably degraded the pristane to phytane ratio often used in GC fingerprinting. Real oil spill case study A number of real oil spill samples (supplied by various commercial, public and government sources) have been examined, including those involving crude oils, fuel oils and oily bilge waters. An example of one such study involved the oil pollution of a dock and two suspect sources, one the bilges of a ship. Fluorescence analysis showed that the conventional spectra, synchronous scans and contour diagrams (Fig. 1) of the dock and bilge samples were virtually identical. Sterane (Fig. 2) and triterpane fingerprints from the bilge and dock samples were also virtually identical, implicating the bilge waters of the ship as being responsible for the pollution.Conclusions The use of fluorescence spectroscopy and C - GC - MS is an extremely powerful combination in the interrogation of the suspect sources of a pollution incident. The work described is a summary of a research programme funded by the SERC Marine Technology Directorate. The programme has now terminated and it is the opinion of these authors that further refinements of the analytical techniques described could lead to further discriminatory power and deterrence in instances of deliberate oil spillage. Given the desire, the current UK record in identification of oil pollution could be improved. The forensic evidence to enhance such an endeavour could be provided by a strategy similar to that outlined above.References Annual Reports of the Advisory Council on Pollution of the Sea ACOPS, London, 1977-1983. John, P., McQuat, E. R., and Soutar, I . , Analyst, 1982, 107, 221. Bentz, A. P., Anal. Chem., 1976, 48, 485A. John, P., and Soutar, I . , Anal. Chem., 1976, 48, 520. John, P., and Soutar, I . , Chern. Brit., 1981, 17,278. John, P., and Soutar, I . , Znt. Environ. Safety, 1981, 148. Lloyd, J. B. F., J. Forensic. Sci. SOC., 1971, 11, 83. John, P., and Soutar, I . , in Crump, G. B., Editor, “Petroanaly- sis ’81 ,” John Wiley/Institute of Petroleum, Chichester, 1982. Soutar, I . , in Pethrick, R. A , , Editor, “Polymer Yearbook,” in the press. Corfield, M. M., Hawkins, H. L., John, P., and Soutar, I . , Analyst, 1981, 106, 188.Cline Love, L. J., Skrilec, M., and Habarta, J. G., Anal. Chem., 1980,52, 754. Van Vleet, E. S., M . T.S. Journal, 1985, 18(3), 11. Pym, J. G., Ray, J. E . , Smith, G. W., and Whitehead, E . V., Anal. Chem., 1975, 47, 1617. Brassell, S. C., and Eglinton, G., in Albaiges, J., Editor, “Analytical Techniques in Environmental Chemistry,” Per- gamon Press, Oxford, 1980. Albaiges, J . , in Albaiges, J . , Editor, “Analytical Techniques in Environmental Chemistry,” Pergamon Press, Oxford, 1980. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. The Effects of Oil Spills on Land and Water A. Nelson-Smith Department of Zoology, University College of Swansea, Singleton Park, Swansea SA2 8PP The effects of an oil spill are determined by the characteristics both of the oil and the environment into which it is released.Various types of organism respond in markedly different ways, and indirect effects may be of greater significance than direct ones, because relatively few of the hydrocarbons which make up petroleum and its primary products are markedly toxic. Their significance as pollutants is due partly to the large scale on which they may occur and partly because, in common with many other consequences of human activity, they present hazards which few organisms are adapted to deal with. Spills on Land On land, oil-spills do not usually create too widespread a problem. Their maximum volume will probably be relatively small and, within a properly planned industrial site, the spillage should be confined to the immediate vicinity of its source.Elsewhere, spreading is usually slow, restricted by local topography, and thus predictable. The most immediately obvious effect is likely to be on vegetation: light oils penetrate the structure of leaves and stems, while heavy ones cling to theANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 269 outer surface. In either event, any leaf significantly oiled will not recover, so survival of the plant depends on whether it has sufficient reserves to produce replacement foliage. Clearly, such a check may make a commercial crop unprofitable. Oil on the soil surface may, additionally, interfere with aeration and water uptake. Effects on terrestrial animals are mostly confined to those actually engulfed by the oil, although birds and small mammals eating intoxicated insects or worms, and grazers consuming contaminated vegetation, might suffer some ill effects.Light oils can migrate quite rapidly in light, sandy soils under dry conditions and will also flow into fissures or crevices. They might thus become entrained in groundwater and could then cause contamination, even at some distance from the spill. Humans can detect an oily taint at less than 1 p.p.m. for many types of oil, so it is unlikely that anyone would knowingly drink enough polluted water to affect their health. However, remedying the problem can be wasteful, costly and trouble- some. Spills in Water Many human settlements and lines of communication lie along valley bottoms, so that much of the oil spilt on land drains, either directly or eventually, into a stream or river.Here it is much more mobile, both moving with the water and spreading across its surface. The flow is confined between banks and is unidirectional so it is, at least, possible to predict where and when damage is likely to occur or, at best, to trap or divert the oil before it reaches a sensitive stretch. The situation becomes much more complicated as spilt oil or contaminated river water enters its estuary. Here, the rise and fall of tides result in a reciprocating motion of the water, so that a surface slick may oscillate up- and downstream for many days before escaping to the sea. Estuaries are important biologically because their rich mudflats and salt marshes provide food for resident fish or wildfowl and also export it to adjacent coastal waters.They offer nursery grounds for marine shell and fin fisheries, and often support valuable shell fisheries of their own. The greatest spill risk arises in coastal waters, where shipping lanes are concentrated and navigational hazards abound. This region is, however, of greatest importance to marine produc- tivity, supporting over 90% of the plants and animals in the seas. On such open waters an oil slick can move in any direction dictated by winds and currents. Components may evaporate, remain on the surface, become dispersed throughout the water column, enter living organisms or be incorporated into bottom sediments. Effects on Aquatic Organisms The effects of spilt oil on aquatic organisms can be divided broadly according to whether their mode of .action is mainly physical and exerted externally, or chemical and exerted internally.The first arises from the nature of crude oil and its heavier products. Small animals can readily become trapped in viscous globules which bind their limbs together and coat their sense organs, respiratory surfaces or other vital regions; a substantial spill may blanket larger plants and sedentary animals over a considerable area. A thick, dark oil film prevents gas exchange and excludes light. In strong sunlight it also absorbs heat. These effects may be particularly serious in small ponds, ditches and seashore pools, or in shallow tropical waters where corals and other organisms may already be near the upper limit of their temperature tolerance. Aquatic forms such as fish and the larger seaweeds have a slimy outer film to which fresh oil will not adhere, so they may avoid external contamination. Terrestrial forms require a smooth, waterproof covering which often, unfortunately, happens to be oleophilic.Birds bear feathers arranged in a precise manner which traps air, mainly to retain their high body temperature. During the frequent preening needed to keep this plumage in order, it is lubricated from an oil-gland at the base of the tail. This arrangement efficiently excludes water when swimming, but thick oils readily cling to the feathers, weighing the bird down, while thinner ones infiltrate and distort the plumage, allowing water to penetrate. In either instance the bird loses heat, which it is no longer able to make up by feeding.It may drown or die of exposure if heavily oiled; if only light contaminated, it will ingest oil whilst preening and poison itself. Most water-birds, encountering a patch of floating oil, would swim away from it or take off. Those which dive from the surface submerge when alarmed, re-surfacing nearby; if the slick is large or irregular, this behaviour is as ill suited to survival, in this unnatural predicament, as is the design of their plumage. Some sea duck even choose to alight in an oil-slick, apparently misinterpreting it as evidence of a fish-shoal. In the aquatic environment, oil can be ingested as such by organisms other than birds, particularly after it has become dispersed as small droplets. Many invertebrates feed by filtering small suspended particles from the water, often selecting them only on the basis of size, so that the oil can accumulate in the filtering mechanism or the gut itself.It may then enter the body tissues both of the filter-feeder and, subsequently, its predators. In addition, true solution or physico-chemical states akin to it account for the dispersion of a large proportion of oil spilt on water. The low aromatics are the most toxic components of crude petroleum and some light products and, at summer- temperatures, the solubility of benzene is nearly three times and, of toluene, nearly twice their acute toxicity to freshwater crustaceans such as crayfish. Toxicity of Oils A fundamental problem in establishing the toxicity of an oil or individual hydrocarbon of low aqueous solubility is to deter- mine how much of the substance is available to specimens in a bioassay tank and, then, how much has actually been taken up by each animal.In any case, such a value would be of use only in simple comparisons, as it takes no account of the complex and varied conditions in the natural environment. Crude oils of different types and petroleum products of similar trade description differ enormously in their toxicity, even by a standard test. However, an indication of the short-term impact of “typical” oils on marine life is that, at one extreme, growth and photosynthesis in planktonic micro-algae is markedly inhibited by additions of as little as 0.01-0.02 p.p.m.; such levels may also affect the development and hatching of fish eggs. At the other end of the scale, the toughest of seashore inhabitants may tolerate several per cent.of oil in their water for a few days or, alternatively, coating with the oil itself for an hour or so, provided that they have first been able to close themselves up. The main way in which hydrocarbons cause acute internal damage is probably by entering and disrupting structures which have a lipoid layer, particularly in mitochondria and nervous tissue. This interferes with metabolic and control mechanisms in a manner which is usually irreversible. Longer term direct effects may be caused at low concentrations by interference with the chemical senses used in locating food and home territory or in synchronising the release of sexual products. Ecological Effects On temperate-zone seashores, limpets occupy a key position, grazing away the sporelings of seaweeds only shortly after their settlement and thus keeping the rock surface free for such sedentary animals as barnacles and mussels.Although limpets can well resist such natural hazards as breaking waves, desiccation in wind and sun or attack by shore birds, they seem particularly sensitive to oil pollution. On some parts of the Cornish coast after the “Torrey Canyon” spill and the resulting intensive clean-up operations, scarcely a limpet remained alive; 6 months later, the rocks were uncharacteristically270 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 covered with annual green algae and, the following year, a heavy growth of the perennial brown algae had become established. Surviving barnacles were smothered and prospect- ing larvae found no sites for settlement; the snails and worms which normally prey on them also declined, to be replaced by the quite different community which lives amongst the algal holdfasts.Young limpets settled at the bottom of the shore, but were unable to make much impression until they had put on a year or two of growth. In Cornwall, it took about seven years before the affected shores returned to their previous state. The same changes have been noted, on a lesser scale, even on shores lightly polluted by oils alone. Significance of Marine Oil Pollution Perhaps the most obvious impact, from the human point of view, is on fisheries. Where the eggs, food and normal activities of commercially valuable shell and fin fish are disrupted, so must be their fishery.Over-exploitation and also, perhaps, long-term climatic changes have already gravely depleted many important stocks worldwide and it is clear that various forms of pollution have also made their contribution. Fin and shell fish readily acquire a taint from levels well below those at which they suffer serious harm; this may persist for several months, during which they are unsaleable. After well-publicised incidents, seafood sales have shown a marked decline, even when stocks have plainly not come from the affected area! The populations of auks and other seabirds most affected by oil have also shown a decline which corresponds to the increase in tanker shipping, although their connection is a matter of controversy. Birds have little direct economic value, but they are an immensely popular form of wildlife.In some regions, topshore vegetation is important in binding sand-dunes or mudbanks; in tropical waters, this function is taken over by mangroves along the shoreline or fringing coral-reefs offshore. Significant damage to these may lead to serious coastal erosion. Elsewhere, few people other than professional biologists pay much attention to the humbler forms of marine life but, unnoticed, they nevertheless make an essential contribution to our appreciation of the seaside. The economic value of the tourist trade was the main stimulus for the heroic efforts made to clean up (for example) both “Torrey Canyon” and “Amoco Cadiz” polluted shores. OECD studies of the cost of the “Amoco Cadiz” incident suggest that losses to the tourist industry well exceed the value of ship and cargo, while those to the seafood trade and non-commercial marine life were each assessed at only slightly less.World-wide, the cost of clean-up and incidental damage resulting from oil pollution from tankships is thought to average about 3% of the total cost of marine oil transport. I have also taken an interest in the effects of unusually severe winters on seashore life. In the southwest of Britain these have occurred, very roughly, at about 10-year intervals. Only a few species have been seriously affected and these have taken perhaps 5-7 years to recover. Mercifully, in only a few localities have serious oil spills occurred as frequently, even if at the time they made a greater impact.I suggest, very tentatively, that in the long term, the effect of such spills may be about the same as that of hard winters. The distinction is that, although we can do nothing about the weather, we should certainly try harder to control these oil spills. The Sampling and Analyses of Oily Water Effluents T. Palmer BP Oil Grangemouth Refinery Limited, P. 0. Box 30, Bo‘ness Road, Grangemouth, Stirlingshire FK3 9x0 Considerable amounts of water are involved in the oil industry and this may be from crude oil production (formation or production water) , shipping (ballast water) and refining (process water). Contamination by oil occurs through direct contact or by spillage. At each stage in the subsequent treatment process samples are taken for the determination of oil content.Sampling Methods of sampling aqueous effluent are well documented1.2 and these can be automatic or manual. In either instance care must be taken to ensure that the sample is representative of the effluent stream.if a meaningful oil content is to be obtained. Oil Determination Oil consists of many components that can be isolated and identified but not all are necessarily identifiable as “oil.” For effluent control purposes a single measurement of oil is required that is highly correlated with any hydrocarbon mixture which may be present. The commonly used laboratory technique is solvent extraction followed by infrared absorp- tion, but consideration has to be given to non-hydrocarbon (polar) organics, light aromatics (benzene, toluene or xylenes) and calibration.Infrared methods A recent CONCAWE survey3 recognised 15 separate infrared methods. These methods showed considerable variation, with the most significant variables being in the use of absorbent, the calibrant and the peaks measured. One method (Paris Com- 100 80 s $ 60 C 0 c 4- .- 6 40 20 n P CH3 100 1 20 i 3200 3000 2700 3200 3000 2700 Wavenum bericm - l Wavenumbericm - Fig. 1. Infrared spectrometry traces of effluent extracts (Freon): ( a ) , process water 1; ( b ) , formation water. Broken line, no absorbent treatment; solid line, after Florid treatment mission, 1979) advises air blowing “where appropriate” and this would remove light aromatics from the sample. A recentANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 27 1 Absorbance coefficents ‘ based on: Cetane 55.5% Pristane 33.3% I Toluene 11.1% Table 1.Results of oil in water analyses ’ CH2, CH3, CH Method IR1.l IR2.1 IR 2.2 IR3.1 IR 3.2 IR 4 IR 5 Gravimetrys Light aromatics6 Methodology used for IR measurement- IR method Absorbent Florisil Florisil Alumina Silicagel I 1.1 2.1 2.2 3.1 3.2 4 Alumina 5 Florisil Oil/mg 1 - 1 Formation water 15.2 6.2 6.6 8.1 7.0 12.2 11.8 1.7 3.8 Calibrant Crude oil Reference oil Isooctane 37.5% Benzene 25% Typical absorptivities Cetane 37.5% Ballast water 5.5 4.4 6.6 6.3 6.7 9.0 11.2 0.6 6.3 Process water 1 30.0 26.5 29.8 36.4 30.8 26.6 23.5 6.0 12.0 { :E:,CH3 CHZ, CH3, CH Process water 2 26.6 19.8 37.1 24.0 42.3 83.6 82.3 1.3 88.2 Method source IMCO 1978 AFNOR 1979 CONCAWE 1972 APHA 1980 Swedish Standard, 1979 DIN 38409-H19 1981 SCA(5) 1984 review4 has recommended the use of a blank in the infrared method.The area of the infrared spectrum utilised is that between 2700 and 3200cm-1 [Fig. l ( a ) ] with the CH2, CH3, CH (aromatic) peaks at 2930, 2960 and 3030 cm-1, respectively, being used. Oily effluents can contain polar organic material, which will be measured as oil unless removed by a suitable absorbent [Fig. l ( b ) ] . Subsequent calculation of oil concentra- tion requires the use of a calibrant which may be the known oil (oil in contact with the effluent), a reference oil or typical absorptivities. The SCA method5 uses a reference oil to calculate absorbance coefficients. Typical effluent analyses (Table 1 ) show that the results obtained are method dependent and any uncertainties must be investigated by alternative met hods.Alternative methods Gravimetry, chromatography and other spectrometric methods are also used in oil in effluent analyses. Gravimetry is the only direct method, but it is limited by loss of light ends, which can result in low results (Table 1). This is a possible measure of persistent oil. The residue can be used for subsequent separation and identification. Chromatography gives considerable information and is used primarily for investigational purposes. Calibration is necessary for quantita- tive work. A purge and trap method has been developed6 for the measurement of light aromatics in effluents (Table 1). Spectrometry offers several options including ultraviolet absorption and ultraviolet fluorescence as well as infrared absorption.Site monitors Portable analysers are available and for on-line measurements several light scattering - absorption monitors and ultraviolet fluorescence are used. In recent years solvent extraction monitors have been developed. Summary The common problems for all oil in water determinations are in obtaining a representative sample, in defining the oil to be measured and in the accuracy of the analytical result. Although sampling techniques are well established there is still scope for improvement in the routine analytical methodology. 1. 2. 3. 4. 5 . 6. References “Sampling of Liquid Effluents from Refineries,” CONCAWE Report 7/80, CONCAWE, The Hague, Netherlands, 1980. “Sampling of Oils, Fats, Waxes and Tars in Aqueous and Solid Systems,” “Methods for Examination of Waters and Asso- ciated Materials,” HM Stationery Office, London, 1983.“Determination of Hydrocarbons in Aqueous Effluents from the Oil Industry by Infra Red Analyses,” CONCAWE Report 1/84, CONCAWE, The Hague, Netherlands, 1984. “Methods of Analysis and Sampling of Oil In Water,” Pet. Rev., September, 1984, 39. “The Determination of Hydrocarbon Oils in Waters by Solvent Extraction, Infra Red Absorption and Gravimetry,” “Methods for Examination of Waters and Associated Materials,” HM Stationery Office, London, 1983. “The Analyses of Light Aromatics in Aqueous Effluents by Gas Chromatography,” Chromatographia, 1983, 16, 301.272 ANALYTICAL PROCEEDINGS. SEPTEMBER 1985, VOL 22 Radiochemical Pollution Due to Combustion of Coal and Coal Derived Fuels R.Blackburn Department of Chemistry and Applied Chemistry, University of Salford, Salford M5 4WT Origin of Radioactivity in Coal The primordial radioactive isotopes, uranium-238, uranium- 235, thorium-232 and potassium-40, occur in most rocks’ but the organic nature and vegetable origin of coals and lignites give them special status with regard to trace elements such as uranium and thorium, which could be incorporated in several ways, e.g., by uptake during life by coal-forming plants, by complexation in surface waters by phenolic complexing agents produced by decaying vegetable matter, or from percolating ground water after burial of the coal-forming mass. Incorpora- tion of purely inorganic minerals can also occur. The uranium and thorium content of coals is highly variable, even within the same seam.Generally speaking, coals with a high lignin content tend to be richer in uranium, the concentra- tion decreasing with the “rank” of the coal,2 but this trend is by no means universal, with brown coal and sub-bituminous varieties from the same region showing no differences.3 Some coals are allegedly rich enough to serve as uranium ore but most have uranium contents around 2 p.p.m. with thorium contents rather higher. We do not consider potassium-40 here because the determination of potassium presents no special problem. In nature 99.28% of all uranium is 2 3 W with 0.72% being 235U. Primordial thorium is wholly 232Th. The radioactivity associated with uranium and thorium and their daughters involves emission of both alpha and beta particles, together with fairly low energy gamma radiation.Although the total radioactivity in a large mass of mildly radioactive coal or lignite may be considerable it does not present either an external or an ingestion radiation hazard. However, coal is burned in huge amounts, for the most part in pulverised fuel fed power stations operating in the vicinity of large urban populations, and some of the incombustible residue (ash) escapes anti-pollution devices such as cyclonic and electrostatic precipitators and wet-scrubbers and is released from stacks. The ash partides have diameters up to 200pm, which straddles the respirable range 0.1-10 pm. Particles smaller than 10 pm have a long residence time in the atmosphere and once inhaled are less likely than larger particles to be removed by mucociliary action, leaving them free to penetrate deep into the lung.The coal intake of a 2000 MW(e) power station is typically about 4.6Mtyr-1, the ash produced annually being about 0.7 Mt. Escaping airborne ash amounts to about 4 kt yr-1. The fate of any radioactivity released as fine ash depends on a great variety of factors, e . g . , stack height, plume release height (which depends on weather conditions), degree of wash-out from the ash plume by rain, the type of area over which ash is deposited ( i e . , is it inhabited or used to grow crops, or raise stock? In this connection deposition at sea may be important if sea-food is an important element of diet). Camplin4 has applied standard radiological assessment tech-, niques to this problem, utilising the ESCLOUD~ computer simulation, which models the behaviour of a continuous discharge of radioactive material to the atmosphere.A similar study has been made by Corbett6.7 who has considered the risks arising from all aspects of the coal fuel cycle. Fractionation of Radioactive Elements According to Size of Ash Particles Most of the radioactivity associated with uranium and thorium is actually from the decay-chain daughters of the precursor isotopes uranium-238, uranium-235 and thorium-232. In undis- turbed coal these daughters are in secular equilibrium with each other, the activities of each member of the chain being equal. Many different chemical species are involved and the geochemical and biogeochemical behaviour of each daughter activity differs.In ash secular equilibrium cannot be assumed because the act of combustion completely releases one of the chain members, radon. The incombustible content of coal is such that there is approximately an order of magnitude increase in the specific activity of ash with respect to coal but in addition there is considerable evidenceB.9 to show that selective fractionation of radioactive elements occurs in ash, depending upon particle size. Fine ash, which has the greatest lung penetration, contains greater amounts (up to 5 times) of lead-210, uranium-238, uranium-235 , radon-226 and radon-228 than varieties which are coarser, although still within the respirable range. Recent measurements have shown an espe- cially high proportion of ash of -0.1 pm diameter.Analysis for Uranium and Thorium Sensitive analytical methods are required to obtain meaningful results for the uranium and thorium content of coal and ash and data are limited. One obvious method is to measure the radiation emitted from uranium and thorium and their daughters. In practice, this involves detection of either alpha or gamma radiation. If alpha particles are to be detected the total sample size that can be examined is very small, for the short range of alpha particles demands specially prepared thin sources, hence this procedure is lengthy and inconvenient. Much larger samples can be accommodated in and around gamma detectors and no special sample preparation is needed, but the fact that uranium and thorium and their daughters are ubiquitous background emitters in air and building materials makes very good shielding of the detector necessary.Coles et aZ.8 have successfully used low background, high resolution gamma spectrometry based on Ge(Li) detectors and Compton suppression techniques and the advent of similar “intrinsic germanium” (HPGe) detectors of fairly hikh efficiency has eased some of the experimental difficulties of measurement of natural radioactivity. In a decay series involving secular equilibrium it is sufficient to determine the gamma activity of any one member of the chain, as all are equal, and the uranium or thorium content of sample can then be calculated. Both uranium-238 and thorium- 232 emit photons of rather low energy, thus measurements are made on their daughters thorium-234, radon-226, lead-214, lead-210, bismuth-214 (for uranium-238) and actinium-228, lead-212 and thallium-208 (for thorium-232).Uranium-235 emits a gamma photon of convenient energy but the low isotopic abundance of this nuclide makes it difficult to determine total uranium by this means. However, the exis- tence of this emission makes it necessary to correct estimates made on radon-226, which has an emission at the same energy (185keV). It should be emphasised that such methods are based on the assumption of secular equilibrium, valid for undisturbed coal but not for ash. Even with coal, sample crushing may allow radon to escape and measurements of the activity of radon precursors thorium-234 and radon-226 may not agree with those from the radon daughters lead-214 and lead-210. The most systematic survey of UK coals is that of Hamil- ton,“) who suggests mean uranium-238 and thorium-232ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 273 activities of 18 and 17 Bq kg-1 (in the range 11-29Bq kg-1).Assuming a 15% ash content these values convert to 73-200 Bq kg-1 ash. (One milligram of uranium-238 and thorium-232 corresponds to 12.3 Bq and 4.06 Bq, respec- tively.) We have analysed ash from several widely separated generating stations in England and Scotland using a neutron activation technique of a special type. Ordinary thermal neutron activation consists of bombarding a nucleus with neutrons so that it undergoes the (nu) reaction, producing a nucleus heavier by one atomic mass and usually emitting a characteristic decay gamma photon by which it can be recognised and determined on a gamma-ray spectrometer.Unfortunately, the neutron flux frequently creates a very high background radiation due to activation of the major con- stituents of the matrix, making gamma spectrometry difficult. Our method makes use of the fact that uranium-235 undergoes neutron-induced fission and six of the fission product isotopes are “delayed” neutron emitters. These nuclides decay with a characteristic half-life, the process involving emission of neutrons. Thus, if a sample containing uranium-235 is neutron irradiated in a nuclear reactor, then removed from the source of neutrons and placed under a detector which recognises only neutrons, the signal indicated is a measure of the uranium-235 (and therefore total uranium) content of the ash.Even the longest lived “delayed neutron emitter” has a half-life of only 55 s, hence the detector and reactor must be close together. We have used neutron fluxes of 1012 n cm-2 s-1, irradiation times of 20 s, a transfer time by pneumatic tube of 2 s and a counting time of 50 s. Analysed uranium ore dispersed in silica was used as the reference. A great advantage was the fact that the sample could be repeatedly irradiated with neutrons and its neutron emission repeatedly re-measured. The technique has been used for several years but seems to us to be insufficiently utilised. Our results11 gave uranium-238 concentrations equi- valent to natural activities ranging from 77 to 190 Bq kg-l (of ash), totally consistent with those derived from Hamilton’s coal analyses. The Radiological Impact Assessment of the radiological consequences of coal burning demands complex theoretical models.The excellent reviews mentioned earlier,4?6 although using different methodology and assumptions, obtain values for the collective dose equi- valent and maximum individual dose equivalent which agree to within a factor of two or three. Both analyses agree to the extent that inhalation contributes more to the collective dose than ingestion; Corbett’s results suggest that ingestion is only marginally less effective, while Camplin’s ingestion contribu- tion is much smaller. Thorium and uranium isotopes are the significant radionuclides with respect to inhalation but polonium-210, lead-210, and protactinium-231 are responsible for the bulk of the ingested dose. The collective dose equivalent arising from 1 GW(e) yr of power from coal is -5 (Corbett) or -10 (Camplin), corre- sponding to -0.08 or -0.165 casualties if a risk factor of 1.65 x Sv- l for fatal cancers/serious hereditary defects is References assumed. 1. Krauskopf, K. B., “Introduction to Geochemistry,” Second Edition, McGraw-Hill, New York, 1979. 2. Lowry, H. H., Editor, “Chemistry of Coal Utilisation,” Supplementary Volume, Wiley, New York, 1963. 3. Marquard, W., Hoehle, R., and Schuh, U., Z. Gesamte Hyg. Zhre Grenzgeb., 1970, 16, 188. 4. Camplin, W. C., “Coal-fired Power Stations-the Radiological Impact of Effluent Discharges to Atmosphere,” NRPB Report R107, National Radiological Protection Board, Didcot, 1980. 5. Jones, J. A., “ESCLOWD,” NRPB Report R101, National Radiological Protection Board, Didcot, 1980. 6. Corbett, J. O., “The Enhancement of Natural Radiation Dosage by Coal-fired Power Generation in the UK,” CEGB Report RDIBIN4760, Central Electricity Generating Board, London, 1980. Corbett, J. O., “The Radiation Dose from Coal Burning; a Review of Pathways and Data,” Radiat. Protect. Dosimetry, 1983,4, 5 . Coles, D. G., Ragaini, R. C., and Ondov, J. M., Environ. Sci. Technol., 1978, 12, 442. Klein, D. H., Andren, A. W., Carter, J. A., Emery, J. F., Feldman, C., Folkerson, W., Lyon, W. S., Ogle, J . C., Talmi, Y., Van Hook, R. I., and Bolton, N., Environ. Sci. Technol., 1975, 9, 973. Hamilton, E. I., Sci. Total Environ., 1974, 3 , 3. Blackburn, R., J. Gueran. Radiar. Phys. Chem., 1979,13,145. 7 . 8. 9. 10. 11. Environmental Chemistry Vol. 3 Senior Reporter H. J. M. Bowen A review Of the literature published UP to the end of 1982. Disposal and Utilization of Sewage Sludge Possible Consequences of Sewage Sludge Disposal and Utilization and the Need for Monitoring Brief Contents: Tropospheric Ozone Ozone Sources i n the Unpolluted Troposphere Photochemistry of the Clean Troposphere Ozone Distribution in the Troposphere Sinks of Ozone in the Unpolluted Troposphere Tropospheric Ozone Budget Ozone Formation and Destruction in Polluted Air Elevated Ozone Levels Biological Effects of Ozone Analytical Techniques The Environmental Chemistry of Organotin Compounds Toxicological Patterns of Organotins Analysis of Organotins at Environmental Levels Modes of Entry into the Environment Aqueous Chemistry Transformations in the Environment Degradation of Organotin Compounds Determination of Heavy Metals in Sewage Sludge Analysis of Sewage Slud e Selected Procedures for &udge Analysis Inorganic Deposits in Invertebrate Tissues Metal Deposits Ligand Binding Silica Deposition Urates Specialist Periodical Report (1984) Hardcover 153pp 0 85186 775 8 Price f41 .OO ($74.00) RSC Members f27.00 RSC Members should send their orders to: The Royal Society of Chemistry, Membership Officer, 30 Russell Square, London WClB 5DT. Non-RSC Members should send their orders to: The Royal Society of Chemistry, Distribution Centre, Blackhorse Road, Letchworth, Herts SG6 1 HN, England. The Royal Society of Chemistry Burlington House Piccadill y London W I V OBN

ISSN:0144-557X    

DOI:10.1039/AP9852200261

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

274 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Equipment News Spectrometer Accessories A sequential spectrometer accessory (SSA), designed for use with the maker’s ICAP 9000 and ICAP 1100 simultaneous spectrometers, adds versatility of line selection and variable background correc- tion positioning for method development to the polychromators. It can be used for non-routine elements or those requiring special background correction points. The sequential spectrometer can also check the analytical accuracy when an interference is suspected, by determining an element already programmed into the polychromator at another wavelength. The SSA is useful for extending the concentration range of an element programmed into the polychromator and it can help the analyst to determine additional metals using one of hundreds of available plasma lines.An electrother- mal vaporisation accessory is a graphite furnace atomiser - aerosol deposition system for inductively coupled plasma spectrometers. Used with the makers’ ICAP-9000 instrument it improves detec- tion limits by as much as a factor of 50 over conventional nebulisation. It also simultaneously analyses microsamples for up to 48 elements, directly analyses solid samples for slurries and determines up to 48 elements in one sample at the rate of 2min or less for each sample. The elec- trothermal vaporisation accessory system includes the IL755 CTF controlled tem- perature furnace for sample vaporisation and the FASTAC I1 aerosol sample delivery system as well as software and an optional 114-place autosampler.The IL755 CTF uses a new graphite tube design, a delayed atomisation cuvette and an improved temperature sensor and con- trol system. Allied Instrumentation Laboratory (UK) Ltd. Autosamplers for Atomic-absorption Spectrophotometry Two autosamplers for the automatic Shi- madzu AA-670 instrument confer the capability of multi-element analysis for up to 8 elements sequentially without invol- vement of an analyst. The autosampler for the flame can take up to 50 samples including standards and blanks, and it features the programmable capability to load sequentially up to 8 methods from the AA-670 memory and carry out the operation. The furnace autosampler does the same and additionally has an auto- injector. V. A. Howe and Co. Ltd., 12-14 St.Ann’s Crescent, London SW18 2LS. Spectrophotometer The FTS-60 Fourier transform infrared instrument features a high-performance optical bench offering 110 mW of infrared power at the sample position, a spectral range of 10000-250 cm-1 and a maximum resolution of 0.5 cm-1. External ports are available for emission work and for con- necting to a dedicated capillary GC - IR accessory or external sample compart- ment. Polaron Equipment Ltd., 53-63 Green- hill Crescent, Watford Business Park, Watford, Hertfordshire WD1 8XG. Interface for Spectrometers A dedicated GC - IR interface is available for the makers’ 1700 Series Fourier trans- form infrared spectrometers. It enables the instruments to be connected to almost any modern gas chromatograph, giving on-the-fly capability with packed or capil- lary columns.Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinghamshire HP9 1QA. Spectrophotometer The Lambda 1A is a version of the Lambda 1 single beam ultraviolet - visible instrument and is designed for quantita- tive applications. Microprocessor con- trolled, it features 3 operating modes, 9 memory locations and integration and absorbance value, and it has a wavelength range of 190-900 nm with spectral band pass of 2 nm. The range of accessories for the Lambda product line are compatible with the Lambda 1A. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield , Buckinghamshire HP9 1QA. Spectrophotometer for Gel Scanning An integral accessory for the makers’ fast scanning DU-7 spectrophotometer pro- vides scanning facilities for tube gels, autoradiograms and thin slab gels in electrophoresis.Measurement resolution and scan speed are selectable in order to optimise results from different samples. There is a choice of slit widths for varied optical resolution and slit height can be reduced to minimise the effect of curved or misshapen gel bands. The gel scan result is shown on the video display of the DU-7 and peak positions and peak areas appear automatically by the side of the scan. Gel scan data can be stored in the memory of the spectrophotometer. There is a multi-sample kinetics accessory. Beckman Ltd. , Progress Road, Sands Industrial Estate, High Wycombe, Buck- inghamshire. Software for Spectrometers New software packages are available for the PW 1404 sequential and PW 1606 simultaneous spectrometers.These pack- ages enable the spectrometers to be used for a range of investigations not previ- ously possible with standard software. One example is the use of gamma correc- tion, which improves the accuracy of X-ray analysis of stainless steels. Pye Unicam Ltd., York Street, Cam- bridge CB1 2PX. Gel Permeation Chromatography Systems A typical system is designed around the Series 10 isocratic pump. The LC-25 refractive index and the LC-95 ultraviolet - visible detectors provide low instrumen- tal band broadening, low noise and fast detector response. Mixed bed GPC col- umns with an operating range of over 4 decades in relative molecular mass are included; they reduce analysis times to minutes rather than hours. Raw data are acquired and stored on disk using the Chromatographics 2 data system based on the Model 3600 data station.GPC5 data processing software can be used to inter- pret the stored data. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinghamshire HP9 1QA. Gel Permeation Chromatography Software Chromatochart chromatography integra- tion and control software performs rela- tive molecular mass distribution calcula- tions. Available for the Apple I1 micro- computer and soon to be launched in an IBM PC version, it enables data to be acquired and analysed from capillary and packed column gas chromatographs, HPLC systems, gel scanners, TLC densi- tometers and amino-acid analysers. Indi- vidual methods can be defined, stored and edited. Integration routines measure peak heights, widths and areas and reten- tion times.Heyden and Son Ltd., Spectrum House, Hillview Gardens, London NW8 2JQ. Software for Relative Molecular Mass Determination in Gels New software for the AMBIS 2-dimen- sional beta scanning system is available. After separation of the radiolabelled proteins by gel electrophoresis, the entire dried gel is scanned, offering an alterna- tive to the slow, trial and error process of autoradiography . Determination of un- known protein relative molecular masses is accomplished by reference to a standard graph produced by the computer from the relative molecular mass marker channel. V. A. Howe and Co. Ltd., 12-14 St. Ann’s Crescent, London SW18 2LS.ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 275 Photographic Accessory for Gel Scanner A cartridge interface is available for the Shimadzu dual wavelength CS-930 thin- layer chromatographic gel scanner.Using the integrated FACSIMILE parallel head printer, the scanner can record the profile of thin-layer chromatographic spots or gels as they appear on the plate. Record- ing can be in either a hatching or a contour mode, even on ultraviolet spots invisible to the naked eye. V. A. Howe and Co. Ltd., 12-14 St. Ann’s Crescent, London SW9 2LS. Column for Separating Permanent Gases Available in 10 m and 25 m lengths the column is 0.32 mm i.d., porous layer, open tubular, and has an inner surface coating consisting of a thin layer of finely divided Molsieve 5 A, which gives excel- lent separation of oxygen and nitrogen, The capillary column takes only a quarter of the time necessary for the same separ- tion on a packed column.The column can be combined with other capillary columns such as CP Sil5 CB in switching systems. Among the gases that can be separated are the rare gases, H2, 02, N2, CO, NO and hydrogen isotopes. The separation of CH4/CD4 is possible with a 25-m column at room temperature. Chrompack UK Ltd. , Unit 4, Indescon Court, Millharbour, London El4 9TN. Gas Chromatograph The VEGA is a compact instrument for all column types. It accepts a wide range of detectors and injectors, including the maker’s cold on-column injector. The instrument will accept the full range of the maker’s autosamplers and detectors. Two temperatures can be entered through the keyboard and retained for recall as required, for example to be activated in turn during a series of automatic analyses in conjunction with the autosampler.While one program is operating the other can be recalled and edited. The instru- ment utilises only 19 in of bench space. Erba Science (UK) Ltd., Headlands Trading Estate, Swindon, Wiltshire SN2 6JQ. Hydrocarbon Analysis The PU 4500 PNA analyser is an auto- matic gas chromatography system for hydrocarbon type analysis in petroleum fractions. Featuring the PU 4810 comput- ing integrator for automatic control and data handling, the analyser gives an accu- rate measure of the total aromatics con- tent of a sample and of the saturated paraffins and naphthenes by carbon num- ber up to CI1. Pye Unicam Ltd., York Street, Cam- bridge CB1 2PX. Soft Gel Affinity Chromatography Column The Ultraffinity-EP column enables large amounts of virtually any protein to be purified in minutes instead of hours with conventional methods.It allows a wider range of ligand-to-macromolecule inter- actions, so that everything from weakly binding proteins to strongly bound mole- cules can be isolated and even enzymes with high activity immobilised. Beckman Ltd., Progress Road, Sands Industrial Estate, High Wycombe, Buck- inghamshire. HPLC System Designed by R. P. W. Scott, the 3D HPLC system features a trifunctional detector and very high speed columns, as well as an isocratic pump and a single pen chart recorder. The TriDet detector uses a single flow cell and combines three detectors: fixed wavelength ultraviolet , fluorescence and ion conductivity. All three detection systems can be monitored simultaneously or separately and the data transmitted to recorders or integrators.The use of “Serpentine” tubing retains low peak dispersion characteristics even though relatively long lengths are used to connect the column to the flow cell. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinghamshire HP9 1QA. Fused Silica Columns Columns are available which are coated with a new chiral stationary phase. Based on L-valine - tert-butylamide, the new phase has a high maximum temperature, 220 “C isothermal and 240 “C with temper- ature programming. This allows the possi- bility of faster separations and of ana- lysing higher boiling components. The columns are particularly suited for deter- mining the optical purity of optically active drugs as well as amino acids in synthetic hydrolysates from natural sam- ples for archaeological dating by the amino acid racemisation method.They also enable quantitative amino acid determinations by enantiomer labelling to be carried out. Chrompack UK Ltd. , Unit 4, Indescon Court, Millharbour, London El4 9TN. HPLC Columns Supelcosil3.3 cm X 4.6 mm , 3 ym silica “3 X 3” fast columns have been developed for separations requiring moderate col- umn efficiency (4000 plates or less) and they can thus be used for the majority of HPLC separations. They are especially useful for running rapid gradient analyses during method development. Supelchem UK, London Road, Saw- bridgeworth, Hertfordshire CM21 9JH. Ion Chromatographs Based on the 2000i chromatograph, the 2OOOi/SP series feature a chromatography module which contains a piston pump, a manual injector valve, a column switching valve and a two-eluent selection valve.The SP series can be configured for specific applications: the System 2OOOi/SP for anion, cation and organic acids, the System 2001i/SP for carbohydrates, the Dionex 2000i ion chromatograph276 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 System 2002i/SP for the analysis of organ- ics with chromophores and/or analysis where post-column chemistry is needed for detection, and the System 2003i/SP for transition metals and silica. Dionex (UK) Ltd., Eelmoor Road, Farnborough, Hampshire GU14 7QN. HPLC Software TAMED (Totally Automated Methods Development) is a software suite that is run on the makers’ Chromatograph Con- trol Module to eliminate the trial and error process of HPLC methods develop- ment.It enables the control module to determine automatically the optimum flow-rate and solvent concentrations in order to obtain the best possible chromat- ographic resolution for a given sample. It enables both binary and ternary solvent mixtures in the isocratic mode and binary multi-step gradient separations to be opti- mised. Laboratory Data Control (UK) Ltd., Milton Roy House, High Street, Stone, Staffordshire ST15 8AR. Ion Exchange Columns Supelcosil strong anion exchange (SAX) and strong cation exchange (SCX) col- umns enable chromatographers to analyse many polar compounds in addi- tion to anions and cations. Compared with reversed-phase columns they pro- vide an alternative selectivity for analys- ing amino acids, peptides, proteins, anti- biotics, nucleotides and many other materials.They can be used without organic modifier in the mobile phase to help protect proteins from denaturation. Supelchem UK, London Road, Saw- bridgeworth, Hertfordshire CM21 9JH. Seals for Chromatography Autosampler Users A new range of seals is available for crimp caps and screw caps. There is a choice of silicone - PTFE, rubber - PTFE and silicone - PTFE - silicone construction. The seals are considerably thinner than the industry standards and so reduce needle bending problems. Chromacol Ltd., Glen Ross House, Summers Row, London N12 OLD. Total Organic Carbon Analyser An on-line version of the PHOTOchem total organic carbon analyser has been introduced. It combines the techniques of ultraviolet assisted persulphate oxidation and conductivity detection to measure organic carbon levels between 20 and 2000 p.p.b.Up to six sample streams can be connected for automatic analysis at 10-min intervals, or manually. Clandon Scientific Ltd., Lysons Ave- nue, Ash Vale, Aldershot, Hampshire GU12 5QR. Temperature Measurement The TPT-80D infrared spot temperature accessory, the Thermolink 80, which pro- vides the facility to make permanent records on charge recorders or data log- gers. Alternatively, its analogue output can be remotely linked to process control equipment, set point alarms, panel meters and voltmeters to provide a flexible pro- cess control function. AGEMA Infrared Systems Ltd., Arden House, Leighton Buzzard, Bed- fordshire LU7 7DD.Heat Flow Measurement The RC1 reaction calorimeter is designed for the measurement of heat flow in chemical reactions and physical trans- formations. It permits reaction design data to be determined automatically under conditions close to those obtaining during actual operation. Various temper- ature and dosage programmes can be con- trolled from the computer. The RC1 checks how the reactions progress under different conditions in accordance with the programme. It can be used in process development, safety investigations, trial production runs and to determine the kinetic data of reactions. Mettler Instruments AG, CH-8606 Greifensee , Switzerland. Thermomechanical Analyser The TMA 7 thermomechanical analyser is an instrument module for the maker’s 7 Series thermal analysis system.It allows dimensional and viscoelastic changes to be determined in nearly all types of sample materials. Addition of the TMA 7 to the 7 Series system means, for exam- ple, that different thermomechanical, thermogravimetric and differential- scanning calorimeter experiments can be performed simultaneously and indepen- dently of one another through a single 7500 Professional Computer. Features include automatic, computer controlled sample loading and automatic probe posi- tioning. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinnhamshire HP9 Syringe The CR-700 constant rate syringe is adjustable and delivers repeatedly iden- tical sample volumes and injection rates regardless of operator skill.Sample volume selection can be made in incre- ments as small as 0.1 p1. There are three syringes in the series, their capacities ranging from 1 to 20 pl, from 2 to 50 p1 and from 10 to 200 p1. Typically, it might be used for carbon analysis using a total organic carbon analyser. V. A. Howe and Co. Ltd., 12-14 St. Ann’s Crescent, London SW18 2LS. Preparation Set The Amica Prep-set from Hamilton con- sists of inert 50 ml polypropylene tubes, racks, screw caps, milling spheres and filter cylinders. Operations that can be carried out with the Prep-set include disintegration, dissolution, milling, sedimentation, centrifugation, incuba- tion, digestion, solid - liquid extraction, liquid - liquid extraction and filtration. V. A. Howe and Co.Ltd., 12-14 St. Ann’s Crescent, London SW18 2LS. Sample Processor System The AASP (Advanced Automated Sam- ple Processor) combines bonded phase sample preparation and automatic on-line injection and should be especially useful in handling a high volume of biological, environmental, industrial and agricultural samples. Up to 100 samples can be processed without operator attendance. It uses sorbent extraction. Compounds of interest are concentrated in specially designed cassettes, each holding 10 cart- ridges containing any of 20 different bonded silica sorbents. The samples are injected into the HPLC column from the AASP’s high-pressure cartridge chamber. The AASP features a digital display which gives the run status and error messages to prevent improper entries. It can be linked to a laboratory data management system and can work with any standard chromat- ograph.Varian Associates Ltd., 24-28 Manor Road, Walton on Thames, Surrey. Balance The AD-4 is a new version of the maker’s AD-6 electronic ultramicrobalance. Con- sisting of a separate electronic control unit and weighing chamber, it enables remote weighing to be carried out, for example in fume hoods and glove boxes. Its capacity is 3.5 g and it is sensitive to 0.1 pg. The keyboard includes the following keys: Autotare, for automatic zero and subtraction of any weight; Weigh/ Integrate, for selecting integration values from 3 to 99 s; Range, for selecting the most appropriate sensitivity; and Calib- rate, for calibration using any weight up to 1000 mg. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinnhamshire HP9 I - measurement instrument features an 1QA.1QA.ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 277 Mass Flow Meters alid Controllers The meters measure and control mass flow-rates of gases to 200 1 min-1 without the need for pressure and temperature corrections. There are nine models, meet- ing a wide ambient temperature range, with output (0-5 V d.c.) linearly propor- tional to mass flow-rate. They will main- tain pre-set mass flow to within +0.25% of full scale and are insensitive to altitude. Tylan (UK) Ltd., Unit 19, Westmead Industrial Estate, Westlea, Swindon, Wiltshire SN5 7YP. Bottle-top Dispensers The maker’s range of bottle-top dispens- ers has been extended to include three new sizes: 2-20.9 ml, 5-59 ml and 10-109 ml.The six available models offer dis- pensing capacities from 0.2 to 109 ml. They connect direct to most bottles used in the laboratory. They are autoclavable at 121 “C fully assembled. Camlab Ltd., Nuffield Road, Cam- bridge CB4 1TH. Laboratory Furnace The Ultraspeed 1700 Series can reach its maximum operating temperature of 1700 “C in only 15 min. Available in 3 sizes, 3.5, 12.0 and 28.3 1, it incorporates the means of communicating with an associated computer. The unit can be programmed and there is a continuous display of the state of the program. Lenton Thermal Designs Ltd. , 12-14 Fairfield Road, Market Harborough, Leicestershire LE16 9QQ. Centrifugal Evaporator The GyroVap has been designed to con- centrate by solvent evaporation under vacuum a wide range of materials with either controlled heating or cooling.An interlock ensures that the vacuum source operates only when the centrifuge has reached 1000 rev min-1, thus preventing bumping or foaming. A range of rotors and optional accessories is available. V. A. Howe and Co. Ltd., 12-14 St. Ann’s Crescent, London SW18 2LS. Centrifuge The J-6M/E, like the other two J-6 ref- rigerated floor-standing centrifuges, is a 6000 rev min-1 model. It has d.c. drive and features microprocessor control. Its memory can store up to 10 programs. The J-6M/E offers digital logic for speed, time and temperature settings, and a choice of acceleration and deceleration rates. It can spin a total of 20 of the makers’ rotors, including the SAG-M for blood banking and the elutriator rotor for the separation of living cells.Beckman Ltd. , Progress Road, Sands Industrial Estate, High Wycombe, Buck- inghamshire. Centrifuges Service back-up is available on the Bur- kard range of bench-top centrifuges. The Koolspin variant is a compact refrigerated unit. Temperatures of -15 “C can be reached within 30 min. The range uses microprocessor control to give repro- ducible conditions of acceleration and deceleration. Operating speeds have been raised to 20000 rev min-1, enabling the user to achieve up to 29000 g with the appropriate rotor. Safety interlocks prevent excessive speeds being reached on lower performance rotors. A full range of rotors and bucket carriers is available. FT Scientific Instruments Ltd. , Station Drive, Bredon, Tewkesbury, Gloucester- shire GL20 7HH.Centrifuge Made by MLW, the Model K80 refriger- ated and programmable centrifuge has been designed to meet BS 4402. It will spin up to 6.6 1 at 4000 rev min-1 to produce 4800g at any temperature between -10 and +40 “C. Rotor speeds can be increased to 21000 rev min-1, producing 37000 g by using a high-speed attachment. Operating programs are entered and stored in a series of plug-in modules, each saving a single program comprising speed in 100 rev min-1 steps, running time from 5 to 99 min, tempera- ture in 5 “C steps and 9 braking levels. Clandon Scientific Ltd. , Lysons Ave- nue, Ash Vale, Aldershot, Hampshire. Ultrasonic Homogeniser The Labsonic 2000 uses 4 piezoelectric crystals to produce a 20 kHz ultrasound wave, which is focused and transmitted through a shaped probe.Various probes are supplied to provide flexibility in oper- ation. There is an integrated watt meter to ensure reproducible results. Homogenisa- tion up to 15 min duration can be con- trolled by an in-built timer. FT Scientific Instruments Ltd., Station Drive, Bredon, Tewkesbury, Gloucester- shire GL20 7HH. The Turbovac 1000 turbomolecular pump features a new lubrication and bearing system which obviates the need for rou- tine re-greasing. The pump can be moun- ted in any orientation. Features include 5 options for the intake port flange and optional water or air cooling. Leybold-Heraeus Ltd., 16 Endeavour Way, Durnsford, London SWlG 8UH. Computerised Gas Analysis for IC Quality Control Based on the maker’s QMG 511 quadru- pole mass spectrometer, the IPS707 system is designed for the failure analysis of hermetically sealed IC packages and the identification of minute gas inclu- sions, or bubbles, often found in IC packaging materials, such as minerals, plastics and glass.Balzers High Vacuum Ltd., North- bridge Road, Berkhamsted, Hertford- shire HP4 1EN. X-ray and Electron Imaging An EDAX EDSCAN software package provides a means of acquiring and presenting spatially related chemical information from a sampie using a scan- ning electron microscope with attached EDAX 9100 energy dispersive analyser. It uses computer controlled microscope beam positioning to probe the specimen and collect from it X-ray and electron backscattered signals. Pye Unicam Ltd., York Street, Cam- bridge CB12PX.Literature Two application leaflets have been publi- shed on pyrolysis - gas chromatography. The first describes the practice of the technique using the maker’s instruments, especially the Model 8300 gas chromato- graph fitted with the CDS Pyroprobe 190 pyrolyser. The second gives examples of applications in analysing polymers, including man-made fibres, rubbers and plastics. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinghamshire HP9 1QA. Four “GC Application News Bulletins” are offered, all referring to the use of the liquid on-column injection technique with the maker’s Model 439 gas chromato- graph equipped with a flame-ionisation detector. The topics are: the characterisa- tion of vegetable oils by determination of triglyceride distribution, the characterisa- tion of animal fats by determining the triglyceride distribution, the characterisa- tion of human milk and butter fat tri- glycerides and the determination of the carbon number distribution, and the analysis of derivatised bile acids in blood serum.Packard Instrument Ltd. , 13-17 Church Road, Caversham, Berkshire RG4 7AA. An application report, “A Simple Gas Chromatographic System for the Quanti-278 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 tative Determination of High Concentra- tions of Benzene in Steam Cracked Naph- tha,” has been released. Packard Instrument Ltd., 13-17 Church Road, Caversham, Berkshire RG4 7AA. A 32-page brochure describes the maker’s range of columns for HPLC and GC. Each column is illustrated with applica- tion examples and technical specifica- tions.The HPLC line includes standard, microbore, high-speed and size-exclusion columns as well as a new pre-column adaptable for use as a guard or sample clean-up column. The Brochure, 5954- 0821, also lists fused-silica capillary col- umns and packed columns and phases. Hewlett-Packard Ltd., Miller House, The Ring, Bracknell, Berkshire RG12 1XN. A catalogue gives full details of a range of products for sample preparation and separation science. Included are the Bond Elut bonded silica extraction columns, the Extube range of Chem Elut and Tox Elut disposable extraction columns and a selection of HPLC columns packed with non-polar, polar and ion-exchange phases from the Sepralyte silica-based chromato- graphic sorbent range. Analytichem International, P.O. Box 158, Cottenham, Cambridge CB4 4UT. An application note describes how ion chromatography was employed to deter- mine sulphur compounds and oxalate levels in Kraft liquors. It describes the ability of ion chromatography to provide information about the ionic content of the Kraft black, green and white liquors. A typical chromatogram and 8 references are provided. Dionex (UK) Ltd., Eelmoor Road, Farnborough, Hampshire GU14 7QN. A leaflet gives information on autocalib- rate analogue gas detectors. Sensors are available for combustible gases (Model SC 110) and hydrogen sulphide (Model ST 210). To complement the sensors the TA series control modules have been introduced. These can be mixed and matched in a standard General Monitors 01 series rack to provide a system that can be integrated with traditional gas sensors, or the analogue output from the gas detector can be fed direct to a variety of control devices accepting 4-20 mA out- put. The autocalibrate analogue gas detectors have been designed to comply with BS 6060 and BS 5501. General Monitors Ireland Ltd., Queens Avenue, Hurdsfield Industrial Estate, Macclesfield, Cheshire SKlO 2BN. A brochure describes the PlOOM and P600M microprocessor based strip-chart recorders. Kent Industrial Measurements Ltd., Howard Road, Eaton Socon, St. Neots, Cambridgeshire PE19 3EU.

ISSN:0144-557X    

DOI:10.1039/AP9852200274

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

278 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Verein Deutscher lngenieure Guidelines Since 1957 the Commission on Air Pollu- tion Prevention (Kommission Reinhal- tung der Luft) of the Association of German Engineers [Verein Deutscher Ingenieure (VDI)] has been elaborating guidelines treating air pollution problems in the following five fields: the formation and reduction of emissions; transport of emissions in the atmosphere, determina- tion of stack height, dispersion models, atmospheric chemistry; effects of dust and gases on man, animals, plants and materials; measurement techniques to judge emissions and immissions, measurement planning; and processes and plants for emission reduction, dust separation techniques, bill of costs. The following titles have recently become available.VDI 2462: Part 7. Measurement of Gaseous Emissions. Measurement of the Sulphur Trioxide Concentration. Propan- 2-01 Method. Part 8. Measurement of Gaseous Emissions. Measurement of the Sulphur Dioxide Concentration. Hydrogen Peroxide - Thorin Method. VDI 2468: Part 7. Gaseous Air Pollution Measurement. Measurement of Peroxy- acetyl Nitrate. Part 8. Gaseous Air Pollu- tion Measurement. Preparation of Peroxy- acetyl Nitrate Calibration Gas. Calibra- tion of a Peroxyacetyl Nitrate Analyser. VDI 3494: Part 3. Gaseous Air Pollution Measurement. Determination of Vinyl Chloride. Automated Gas Chromato- graphic Method (A.I.R. Instruments Model 755 GC). All of the VDI loose-leaf guidelines have been combined to form the manual “Air Pollution Prevention”; they can, however, also be bought individually. Guidelines published after the end of 1982 are bilingual (German and English). They can be obtained from Beuth-Verlag GmbH, P.O. Box 1145, D 1000 Berlin 30, Federal Republic of Germany.

ISSN:0144-557X    

DOI:10.1039/AP985220278b

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 279 Publications Received Dictionary of Chemistry and Chemical Technology. GermadEnglish. Edited by H. Gross. Pp. 633. Elsevier. 1984. Price $105.75; Dfl275. ISBN 0 444 99617 6. Auger Electron Spectroscopy. Michael Thompson, Mark D. Baker, Alec Christie and Julian F. Tyson. Chem- ical Analysis Series, Volume 74. Pp. viii + 394. Wiley-Interscience. 1985. f95. ISBN 0 471 04377 X. L’Analyse de I’Eau: Eaux Naturelles, Eaux Residuaires, Eau de Mer. Seventh Edition. J . Rodier. Pp. viii + 1365. Dunod. 1985. Price Fr980. ISBN 2 04 015615 1. Mossbauer Spectroscopy Applied to Inor- ganic Chemistry, Volume 1. Edited by Gary J. Long. Modern Inor- ganic Chemistry. Pp. xviii + 667. Plenum. 1984. Price $92.50. ISBN 0 306 41647 6. Semiochemistry : Flavours and Phero- mones.Proceedings, American Chemical Society Symposium, Washington, DC, USA, August 1983. Edited by Terry E. Acree and David M. Soderlund. Pp. x + 289. Walter de Gruyter. 1985. Price DM160. ISBN 3 11 010120 3; 0 89925 008 4. Gradient Elution in Column Liquid Chro- matography. Theory and Practice. P. Jandera and J. ChurEek. Journal of Chromatography Library, Volume 31.280 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Pp. xix + 510. Elsevier. 1985. Price $90.75; Dfl245. ISBN 0 444 42124 6. The Science of Chromatography. Lectures presented at the A. J. P. Martin Honorary Symposium, Urbino , May 27-3 1, 1985. Edited by Fabrizio Bruner. Journal of Chromatography Library, Volume 32. Pp. xx + 476. Elsevier. 1985. ISBN 0 444 42443 1 (Vol. 32); 0 444 41616 1 (Series). Stripping Analysis. Principles, Instrumen- tation and Applications. Joseph Wang. Pp. viii + 160. VCH Pub- lishers. 1985. Price DM120. ISBN 0 89573 143 6 (VCH Publishers); 3 527 26192 3 (VCH Verlagsgesellschaft) . Practical Estuarine Chemistry. A Hand- book. Edited by P. C. Head. Estuarine and Brackish- Water Sciences Association Handbook. Pp. x + 337. Cambridge Uni- versity Press. 1985. Price f25; $54.50. ISBN 0 521 30165 3. Analytical Solution Calorimetry. Edited by J. Keith Grime. Chemical Analysis, Volume 79. Pp. xviii + 401. Wiley-Interscience. 1985. Price f69.40. ISBN 0 471 86942 2. A Manual of Fluorometric and Spectro- photometric Experiments. Allesia M. Gillespie, Jr. Pp. x + 151. Gordon & Breach. 1985. Price $25. ISBN 2 88124 005 4.

ISSN:0144-557X    

DOI:10.1039/AP985220279e

出版商:RSC    

年代:1985

数据来源: RSC

摘要:

280 ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 Conferences and Meetings Analyticon 85 September 17-19, 1985, London This meeting is, as usual, being run in conjunction with the Laboratory 85 exhi- bition. Organised by Scientific Symposia Ltd., it will consist of ten sessions on the following topics: “Gas Sensors: Electro- chemical and Piezoelectric”; “Laboratory Information Management Systems”; “Liquid Chromatography - Mass Spec- trometry”; “Laboratory Furniture Systems”; “Rapid Microbiological Methods”; “Flow Injection Analysis”; “Current Chromatographic Techniques”; “Biotechnology Instrumentation”; “Automation in Clinical Biochemistry”; and “Image Analysis in Biomedical Mic- roscopy.” The meeting will be held in the Commonwealth Institute, Kensington. For further information contact Scien- tific Symposia Ltd., 33/35 Bowling Green Lane, London EClR ODA.DNA Probes and Monoclonal Antibodies September 23 and 24, 1985, London These meetings will be held at the Royal Lancaster Hotel. The speakers at the DNA Probes meeting (on the 23rd) will be D. Kingsbury, M. McCrae, A. Mal- colm, L. Ratner, M. Brady and S. Gatley, while those at the Monoclonal Antibodies meeting (on the 24th) will be H. Wald- mann, G. Galfre, M. Neuberger, M. Lo, J. Martinis, J. Birch and K. Siddle. Enquiries should be addresed to Miss Helen Raquet, Oyez Scientific and Tech- nical Services Ltd., Bath House (3rd floor), 56 Holborn Viaduct, London EClA 2EX. Inductively Coupled Plasmas Autumn 1985 Applied Research Laboratories (ARL) have organised a series of seminars which will be presented by their experienced team of ICP specialists.These one-day seminars will highlight, in particular, areas of problem sample handling, the direct analysis of solid samples using ICP and on-line process control analysis. From September to December they will travel to various European cities: Paris and Lyon (France), Leverkusen, Stutt- gart and Hamburg (Federal Republic of Germany), Vicenza (Italy), London, Bristol, Birmingham, Manchester, Tees- side and Glasgow (Great Britain), Barce- lona (Spain), Stockholm and Gothenburg (Sweden), Zurich (Switzerland). In order to receive detailed information on these ICP seminars, write to ARL European Headquarters, En Vallaire , CH-1024 Ecublens, Switzerland. FACSS 85 September 29-October 4, 1985, Philadel- phia, PA, USA The twelfth annual meeting of FACSS will be held at the City Line Marriott Hotel.Among the features of the meeting are FACSS Workshops (for information contact Keith Olson, GM Research Lab- oratory, Warren, MI 48090, USA), SAS Short Courses (for information contact Robert B. Green, Code 3851, Naval Weapons Centre, China Lake, CA 93555, USA) and ACS Short Courses (for infor- mation contact the Education Division, ACS, 1155 16th Street NW, Washington, DC 20036, USA). Second European Seminar and Exhibition on Computer-aided Molecular Design October 17-18, 1985, Bade, Switzerland This meeting will be held at the European World Trade and Convention Centre. The seminars will be on Theoretical Che- mistry, Molecular Modelling, Proteins and Catalysis.ANALYTICAL PROCEEDINGS, SEPTEMBER 1985, VOL 22 281 For further information contact Miss Helen Raquet, Oyez Scientific and Tech- nical Services Ltd., Bath House (3rd Floor), 56 Holborn Viaduct, London EClA 2EX.UK Corrosion '85 November 4-6, 1985, Harrogate The conference is to be held at the Majestic and Cairn Hotels. There will be a number of papers on each of the following themes: Bacterial Corrosion; Corrosion Monitoring; Chemical Treat- ment; Cathodic Protection; Surface Pre- paration; Paints and Coatings; Materials Selection; and Corrosion Science and Research. There will also be a research poster session, technical activity meetings and plenary and keynote lectures, as well as an exhibition. For further information write to The Conference Secretary, UK Corrosion '85, Exeter House, 48 Holloway Head, Birmingham Bl 1NQ.First International Conference on Protein Engineering November 21-22, 1985, London This conference will be held at the Gloucester Hotel. The principal speakers will be G. Winter, B. Barrell, J. Walker, V. Mozhaev, L. Johnson, G. Dodson, J. Helliwell, D. White, A. Morffew, H. Morris, K. Wuthrick, A. Kossiakoff and D. Yarrow, while the various sessions will be on Genetics, Protein Structure, X-ray Crystallography, Molecular Graphics, NMR and MS Studies and Commercial Aspects. For further information contact Miss Helen Raquet, Oyez Scientific and Tech- nical Services Ltd., Bath House (3rd floor), 56 Holborn Viaduct, London EClA 2EX. Minerals Analysis December 4, 1985, London A one-day meeting on the analysis of minerals is being organised by the Special Techniques Group of the Analytical Divi- sion; it is co-sponsored by the Institution of Mining and Metallurgy.The meeting will present some of the best current practices and future trends in this impor- tant field. It will be held in the Scientific Societies Lecture Theatre in Savile Row, London, W.l, starting at 10 a.m. The topics to be covered include sampling and sample handling, flame and plasma methods, plasma mass spectrometry, X-ray fluorescence, electron microscopy and statistical methods for quality con- trol. The speakers will be drawn from universities, industry and consultancies and the following have already provision- ally agreed to take part: B. Atkin, MESA, Nottingham; D. N. Collins, War- ren Spring; A.L. Gray, University of Surrey; D. C. Johnston, BP Research, Sunbury; M. Thompson, Imperial Col- lege, London; J. N. Walsh, Kings Col- lege, London. The registration fee, which will also cover lunch, is &35 for RSC and IMM members and &45 for other delegates (bona fide students and retired members &lo). Further details are available from Richard Whitaker, Metal Box Ltd., Research and Development Division, Denchworth Road, Wantage, Oxford- shire OX12 9PB. Instrument a tion '86 March 5-6, 1986, Bristol This instrumentation exhibition will be held at the Bristol Crest Hotel. It is designed as a low cost, high quality bench show which will cover a wide range of the latest in new technology instrumentation for measurement, test and control.For further information please contact Trident International Exhibitions Ltd., 21 Plymouth Road, Tavistock, Devon PL19 8AU. SAC 8613rd BNASS July 20-26, 1986, Bristol This conference, which will be held in the University of Bristol, is organised by the Analytical Division of the Royal Society of Chemistry in conjunction with the Spectroscopy Group of the Institute of Physics. The Plenary Lectures will be given by Professor J. H. Knox (Edin- burgh), Professor M. Bonner Denton (Tuscon, AZ, USA), Professor B. V. L'Vov (Leningrad, USSR) and Professor G. Tolg (Dortmund, FRG) and the Invited Lecturers will include J. F. Alder, M. Barber, M. S. Cresser, A. R. Date, J. Goldsmith, J. G. Grasselli, D. A. Hick- man, W. Horwitz, R. D. Snook, V. Sychra, A. Thorne, A Townshend, G.Werner and T. S. West. There will also be an Association of British Spectroscopists Lecturer, Professor L. de Galan. In addi- tion to the above, contributed papers have already been offered in the following fields. Techniques: atomic absorption, fluorescence and emission spectroscopy, catalytic and kinetic methods, chromato- graphy, electroanalytical methods, enzyme techniques, flow injection methods, immunoassay, mass spectro- metry, microanalysis, molecular spectro- scopy, probe methods, radiochemistry , sample preparation, pre-concentration and separation, thermal methods, X-ray emission and other X-ray methods. Materials and Areas of Application: agricultural, atomospheric, biological and microbiological, clinical, environ- mental, food and drink, geological, indus- trial and metallurgical, pharmaceutical, plastics, rubbers and textiles, surfaces, water and effluents.Other Aspects: auto- mation and robotics, biotechnology, che- mometrics, data processing, education, historical, microbiological, clinical, envi- ronmental, food and drink, geological, industrial and metallurgical, pharmaceut- ical, plastics, rubbers and textiles, sur- faces, water and effluents, microcom- puters and microprocessors, optical fibres, quality control, sensors, the integrated laboratory. In addition there will be update courses, workshops, an exhibition and a social programme. The papers presented will include both oral contributions and posters, and some contributions will be from RSC and other Groups. Persons wishing to submit a paper discussing original, unpublished work should send in a title, followed by the names and addresses of the contributors and a 200- word abstract, a11 in double-spaced type within the boundaries of 25 X 15 cm on a single sheet of paper, to the SAC 86/3rd BNASS Scientific Programme Co- ordinator, Dr. J. D. R. Thomas, c/o Analytical Division, Royal Society of Chemistry, Burlington House, Piccadilly , London W1V OBN. For further information contact Miss P. E. Hutchinson, Secretary of the Analy- tical Division, Royal Society of Che- mistry, Burlington House, Piccadilly , London W1V OBN.

ISSN:0144-557X    

DOI:10.1039/AP985220280b

出版商:RSC    

年代:1985

数据来源: RSC