ISSN:0144-557X    

DOI:10.1039/AP98017FX033

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

397 ANALYTICAL DIVISION DIARY September, 1980 RSC ANALYTICAL DIVISION SPECIAL TECHNIQUES GROUP A meeting on REVIEW AND RECENT ADVANCES OF NMR to be held at The Read Lecture Theatre, Sherfield Building, Imperial College of Science and Technology, South Kensington, London November IZth, I980 This meeting is being held to promote a wider knowledge and acceptance of NMR by analysts for both qualitative and quantitative determinations. The speakers will include R. K. Harris, D. W. Jones, M. E. A. Cudby, P. Beynon, G. Bedford, J. Becconsall, R. Jones, R. Abraham and W. A. Thomas. The registration fee for the meeting will be f 10 for members and f 14 for non-members (coffee, lunch and tea f6 extra). For further details contact Dr. R. P. Mounce, British Gas Corporation, London Research Station, Michael Road, Fulham, London, SW6 2AD.

ISSN:0144-557X    

DOI:10.1039/AP98017BX035

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

ANPRDI 17(9) 345-398 (1980) ISSN 01 44-557X September 1980 Hon. Secretary P. G. W. Cobb Analvtical Proceedinas Proceedings of the Analytical Division of The Royal Society of Chemistry AD President L. S. Bark Hon. Treasurer J. K. Foreman Hon. Assistant Secretary D. 1. Coomber, O.B.E. Hon. Publicity and Public Relations Officer Dr. A. Townshend, Department of Chemistry, University of Hull, Hull, HU6 7RX Secretary Miss P. E. Hutchinson Editor, Analyst and Analytical Proceedings P. C. Weston Assistant Editors Mrs. J. Brew, R. W. Hazell, R. A. Young Publication of Analytical Proceedings is the responsi- bility of the Analyst Publications Committee: J. M. Ottaway (Chairman) W. H. C. Shaw H. J. Cluley D. Simpson 'P. Gray A. Townshend J. N. Miller 'P. C. Weston G. E. Penketh J. Whitehead T.6. Pierce 'Ex officio members All editorial matter should be addressed to: The Editor, Analytical Proceedings, The Royal Society of Chemistry, Burlington House, Piccadilly, London, W1 V OBN. Telephone 01 -734 9864. Telex 268001. Advertisements: Advertising Department, The Royal Society of Chemistry, Burlington House, Piccadilly, London, W1V OBN. Telephone 01 -734 9864. @ The Royal Society of Chemistry 1980 Ed itoria I The Future of Primary Journals The problems of inflation might be one of the factors that could affect the future of primary journals as we know them today. In recent years, costs of paper and printing have risen faster than the average inflation rate, which has meant that the prices charged for primary journals have tended to follow suit.For each increase in subscription rates, there is a risk of loss of subscribers; any library operating on a fixed subvention, or whose funds do not increase appropriately, must reduce its scale of pur- chases when subscriptions are increased. If, for such or other reasons a journal suffers progressive losses of subscribers, a point can ultimately be reached where further losses result in a significant increase in the unit cost (cost per copy) required to produce the journal. This increase has to be met by an increase in subscription charges, over and above any increase required to combat inflation. Hence at this point there can be a snowballing effect, with the greater increases in subscriptions risking an acceleration in losses of subscribers. Unless this trend can be reversed, the journal is doomed to become uneconomic.Happily, The Analyst and the other primary journals produced by the Royal Society of Chemistry (RSC) are viable propositions and are in no immediate risk of the type of failure outlined above. However, if inflation continues in the 1980s and 1990s as it has in the 1970s, the continued viability of currently successful primary journals cannot be taken for granted. Another relevant factor is the competition that the conventional form of primary journal may have to face from the increasing variety of ways in which information can be generated, presented and disseminated. I t was with such considerations in mind that in 1977 one of the RSC's predecessors (The Chemical Society) initiated the publication of a new form of primary journal, the Journal of Chemical Research.This journal publishes in hard copy form only the synopses of papers, 1 or 2 pages in length, thereby appreciably cutting production costs. The full texts of any or all 345WILLIAM HERAPATH : A PIONEER OF TOXICOLOGY Anal. Proc. papers are available in microfiche or miniprint form, at extra cost. This approach enables the subscriber to gain some appreciation, via the synopses, of all the papers published, and to have the full texts of those papers of particular interest to him. Moreover, this can be achieved a t lower costs than would arise with a conventional primary journal, which presents all papers in full to all subscribers regardless of their degree of interest in each paper. In its 3 years of operation, the Journal of Chemical Research has become a truly inter- national journal in that it is now a joint venture between the relevant chemical societies in the UK, France and Germany, while chemical societies in a dozen other countries have a supporting role.The fact that this journal now publishes some 300 synopses and papers per year indicates a viable concept, and it seems set fair to blaze the trail for one of the forms which primary journals might need to adopt in future. Nevertheless, consideration needs to be given to other possible future developments of primary journals and to the form that such journals might need to take in order to meet particular subject requirements. Experience has shown that while the Journal of Chemical Research is intended for the publication of synopses and papers on all branches of chemis- try, to date papers on analytical chemistry are scarcely represented.I suspect that the reluc- tance of analysts to publish in a synopsis journal such as the Journal of Chemical Research arises from two causes. One may be that analysts, despite having to deal with the multiplicity of analytical developments that have emerged in recent years, tend to be conservative in nature and could therefore be expected to prefer the traditional form of publication. A more practical reason may be that in many ana.lytica1 procedures, whether purely chemical in nature or involving complex instrumentation, minutiae of experimental con- ditions can be critically important; this may make the analyst feel that a synopsis form of publication is inhibitingly restrictive, even though the full text of his paper would also be available. If such considerations are not valid, it would be desirable for analytical chemistry to be represented in the new-style publication venture represented by the Jouvnal of Chemical Research. Analytical contributions would certainly be welcomed by the journal. However, if the above considerations are valid, it behoves analysts to give thought to what other type of analytical journal they, as readers and authors, would like to see in future, granted that the conventional form of primary journal may have a limited existence. The purpose of this Editorial is to pose this question, not to suggest answers. It is a question that analysts (and Publication Com- mittees !) should be considering now. H. J. CLULEY

ISSN:0144-557X    

DOI:10.1039/AP9801700345

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

346 WILLIAM HERAPATH : A PIONEER OF TOXICOLOGY Anal. Proc. William Herapath, 1796-1868: A Pioneer of Toxicology If to be omitted from Partington’s weighty “History of Chemistry” is the hallmark of chemical oblivion, then William Herapath has achieved it. Yet during his lifetime the courts sought his assistance in many of the causes ckZ2bres of the day, his opinions were quoted in the leading texts on toxicology, and he was frequently described as the foremost analytical and consulting chemist of the West country. William Herapath was the son of a Bristol maltster, and his first excursions into chemistry were made in connection with that trade. Finding however that the study of chemistry was more attractive than the care of his father’s business, he began to develop an analytical practice among the industrialists in the neigh- bourhood of Bristol. His eldest son William Bird Herapath, F.R.S., became a prominent toxicologist, and his younger son Thornton John Herapath was chief chemist to the Mexican and South American Smelting Company.His cousin John also left the malting trade to become a mathematician and proprietor of the well known Herapath’s Railway and Commercial Journal. The identities of the individual Herapaths are often obscured in the literature, a confusion made worse by the fact that William, John and William Bird all died in 1868.1 William was one of the founders of the Bristol Medical School in 1828, and for the next 40 years he was lecturer in chemistry and toxicology there. He was also a founder member of the Chemical Society and served on its Council from 1853 to 1856.2September, 1980 WILLIAM HERAPATH: A PIONEER OF TOXICOLOGY 347 Herapath’s first chemical communication appeared in August 1823 when, following Stromeyer’s recent discovery of cadmium in zinc compounds, he analysed flue dust from a Bristol zinc smelter., He criticised Wollaston’s proposal for separating cadmium from zinc by means of iron, suggesting instead sublimation in a tube packed with paper (having previously tried wax and oil as antioxidants).He used potassium chromate to test for zinc in the sub- limed cadmium, and minutely described the physical differences between pure and zinc- bearing cadmium. Such critical awareness of current chemical literature was to remain a characteristic of Herapath’s work.Later in 1823, for example, he was able to suggest im- provements to Dobereiner’s newly invented catalytic hydrogen lamp, gently chiding Dobereiner for a certain laxity in detail.4 His spectacular leap to fame, however, came in 1835 when he was called as an expert witness for the prosecution in the trial of Mary Ann Burdock on a charge of murdering her lodger by means of red arsenic sulphide or realgar.5 The case is important because it reveals how a skilled chemist dealt with suspected arsenic before the discovery of the classical tests of Marsh (1836), Reinsch (1841), Fleitmann (1851) and Gutzeit ( 1 879). Herapath set great store by the destruc- tion of organic matter, for which in this case he used a nitric acid - sulphuric acid mixture. He precipitated the arsenic as sulphide, reduced it in a Berzelius tube to metallic arsenic, oxidised it to As,O, (a technique used by Christison but proposed by Edward Turner in 1826), and finally converted it into Scheele’s green by addition of ammoniacal copper sulphate.For this last stage Herapath designed an ingenious spot-test. The precipitate was formed on blotting paper supported on a block of chalk; excess of copper solution was absorbed by the chalk, leaving an unequivocal green stain on the paper, which could be exhibited to a jury. In the same year Herapath appeared a t Taunton Assizes when Sophia Edney was accused of poisoning her husband with arsenic administered in fried potatoes. In this case Herapath used fused potassium nitrate to destroy the organic matter.From a very small sample (0.6 mg of elemental arsenic) he was able to present to the jury specimens of the metal, the sulphide, Scheele’s green and silver arsenite, each sealed in a glass tube on which the analyst’s name was inscribed with a diamond pencil. At the 1836 meeting of the British Association Herapath reported on the analytical methods used in these two cases, and he was able to add comments on Marsh’s recently published test.6 He recommended blank tests on the zinc to forestall forensic argument, a suggestion which, if heeded, would have saved many an expert witness from public humiliation. The most notorious case in which Herapath was retained was undoubtedly that of William Palmer of Rugeley in 1856. Palmer was accused (and ultimately convicted) of poisoning his racing associate John Parsons Cook, and among the suspected poisons were antimony and strychnine. Alfred Swaine Taylor, Professor of medical jurisprudence a t Guy’s Hospital, got into deep water during his contradictory and inconsistent evidence for the prosecution ; although he believed on medical grounds that strychnine had been administered he was unable to detect it in the submitted specimens.Hera- path, for the defence, maintained that if strychnine had been given it should have been detected ; by implication, either Taylor was incompetent and his evidence worthless or Palmer was innocent on the strychnine charge. Although roughly handled by Cockburn, the Attorney-General, who called Herapath “a thoroughgoing partisan,” it is clear that Hera- path came prepared to demonstrate experiments to the court, though he was prevented from doing this by the Lord Chief Justice.Using the H,SO, - PbO, and H,SO, - MnO, colour reac- tions of strychnine, he had studied the recovery of the alkaloid from animal carcasses in varying states of decomposition and his experimental grasp was secure. In spite of Cockburn’s strictures, the impression remains that Hera- path was defending not Palmer, but chemical analysis and the credibility of its practitioner^.^ This is confirmed by a letter that Herapath wrote to The Times following the Smethurst trial (in which, again, Taylor appeared for the prosecution) : “I consider that professional witnesses who give their opinions where the life or freedom of a man is a t stake are as much upon their trial as the prisoner.” Concerning Taylor’s misfortune with Reinsch’s test applied to a cough mixture containing potassium chlor- ate, Herapath observed : “The fact is, the whole set of operations were a bungle.Keinsch’s process is not applicable where nitrates or chlorates are present.”8 Even when positive results were obtained, he emphasised that a stain of arsenic on the sheet of copper foil was not sufficient; the metallic arsenic must still be oxidised to As,O,, and the solution of arsenious acid tested with silver nitrate, hydrogen sul- phide and copper sulphate, specimens of all five products being produced in court. Opposing counsel must have found Herapath’s evidence very difficult to shake.348 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal.Proc. In the light of this cautious approach to the identification of poisons, we must examine the claims that Herapath made for the sensitivity of his procedures. For arsenic, he insisted that 1/1000 grain (80 pg) would serve for his five- stage test, whilst for strychnine he claimed to be able to detect 1/50 000 grain (1.2 pg) a t a dilu- tion limit of 1 to 7 000. As both were essen- tially spot-test techniques, these figures are reasonable for pure substance but their validity in stomach contents or food would have been questionable. Nevertheless, Herapath’s con- temporary Henry Letheby, Medical Officer of Health for the City of London and an expert on the detection of adulteration in food, sub- stantially supported Herapath’s figures, quoting 1/20 000 grain (3 pg) for strychnine.9 Although it was the criminal cases which brought Herapath into the public eye, his chemical activities ranged very widely.He invented a continuous tanning process in which the hides, sewn into an endless belt, were passed successively through the tanning liquors and between rollers, which improved the texture of the leather. He investigated lithium salts in the excreta of the common silkworm, engaged in correspondence about the fees paid to analytical chemists for attendance a t coroners’ inquests, devised a lecture experiment to show the com- bustion of a diamond, invented an oxy-hydrogen blowpipe, designed a magnetic balance and examined the colouring matters on the cloth wrappings of an Egyptian mummy. In this connection he believed that he had explained the biblical story of Moses dissolving the golden calf.1° In 1851, a t the request of the Chief Commis- sioner of the Birmingham police, Herapath examined an Austrian cure for cholera for which great claims had been made, and in which the police were interested as a possible treatment for prison populations ; analysis revealed that the “cure” consisted of sulphuric acid (4.75y0), nitric acid (3y0), sugar (6%) and water (86.25y0).11 As a young man William Herapath had found time to engage in politics as a member of what was improbably described as the Extreme Liberal party, and at the time of his death he was senior magistrate for Bristol. The picture that emerges is that of a busy, inquisitive and resourceful chemist, passionately concerned to gain for chemical analysis the recognition that i t was so often denied.1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. References Gentleman’s Magazine, 4th series, 1868, 5 , 404; Did. Nut. Riog., 1908, 9, 615. J. Chenz. Soc., N.S., 1568, 6, xxiv. Phil. Mag., 1823, 62, 166. Phil. Mag., 1823, 62, 286. Herapath, W., Lancet, 1834-5, ( 2 ) , 276. British Association Reps., part 2, 1836, 67. Illustrated Edition of The Times report on the trial of William Palmer.. . . . .from short- hand notes taken in the Central Criminal Court, London, 1856, p. 119. Letter to The Times, August 27, 1859. Illustrated Edition of The Times report on the trial of William Palmer. . . . . . from short- hand notes taken in the Central Criminal Court, London, 1856, p. 121. Herapath, W., Phil. Mag., N.S., 1852, 3, 528. Herapath, W., Lancet, 1851, (2), 120. W. A. CAMPBELL

ISSN:0144-557X    

DOI:10.1039/AP9801700346

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

348 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. Inorganic and Organic Pollutants in the Troposphere and Natural Waters The following are summaries of eleven of the papers presented at an Interdivisional Meeting organised in conjunction with the Microchemical Methods and Electroanalytical Groups and held on September 26-28th, 1979, at the Queen’s University, Belfast. Summaries of seven of the other papers presented at the meeting will appear in a future issue. The Release of TCDD a t Seveso A. J. Howard Crenzer awd Warner L i m i t e d , 140 Buckinglzawz Palace Road, London, S W1 W 9SQ On July loth, 1976, a bursting disc on a reactor in use for the production of 2,4,5-trichloro- phenol at the Icmesa chemical plant at Seveso, about 20 km to the North of Milan, Italy, ruptured and released to the atmosphere a chemical cocktail, containing primarily sodium trichlorophenate, ethylene glycol and sodium hydroxide, and in addition as an unwanted and undesirable by-product, the highly toxic 2,3,7,8-tetrachlorodibenzo-fl-dioxin (TCDD).September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 349 The cloud resulting from the discharge drifted downwind in a S.S.E.direction. By good fortune, much of the cloud first drifted over open fields before reaching any built-up areas and centres of population. Nevertheless, deposition from the cloud occurred and both fields and buildings were contaminated. The problems posed to the authorities were unprecedented, as although there had been previous accidents involving the release of TCDD, these had been confined to enclosed premises and none had resulted in a discharge to the atmosphere and contamination of the surrounding countryside. 1.What was released from the reactor? How much TCDD was associated with the release? 2. What was the distribution of TCDD at ground level? 3. Would the contamination spread to water supplies or be carried outside the area of its original location? 4. What was an acceptable level of TCDD before normal activities in the area could be resumed ? 5. What methods were available for decontamination ? TCDD is produced as a by-product during the production of 2,4,5-trichlorophenol, which at the Icmesa factory involved the alkaline hydrolysis of 1,2,4,5-tetrachlorobenzene in the presence of ethylene glycol and sodium hydroxide at atmospheric pressure.Following the completion of the hydrolysis, the solvent, in this instance ethylene glycol, is removed by distillation at reduced pressure. If the temperature of the hydrolysate rises above about 180 "C, an exothermic reaction takes place at about 230 "C and the temperature rapidly rises to about 410 "C, with an accompanying increase in pressure and the formation of TCDD by the combination of two molecules of sodium 2,4,5-trichlorophenate. TCDD is virtually insoluble in water, only slightly soluble in fats, more soluble in hydro- carbons and most soluble in chlorinated organic solvents. It is almost immobile in soil and tends to remain close to the point of application. If sprayed on crops it does not tend to be translocated.It is not readily degraded by micro-organisms and the half-life appears to vary between 190 and 330 days. Photolysis is negligible in aqueous suspensions or in wet or dry soil, but in methanolic solution TCDD is decomposed after exposure to ultraviolet radiation or sunlight for 24 h. TCDD is not completely decomposed by heat until a temperature of 800 "C is reached. Evidence of the toxicity, teratogenic, carcinogenic and other effects of TCDD is based largely on animal experiments. The major questions facing the authorities at this time included the following: Production Process According to the Final Report of the Italian Parliamentary Commission of Inquiry (the FRIPC Report), the process took place in four stages, as follows: 1. Reaction of a mixture consisting of 1,2,4,5--tetrachlorobenzene, sodium hydroxide and ethylene glycol in molar proportions of 1: 3: 5.5 plus an unspecified amount of xylene a t a maximum temperature of 185 "C.2. Distillation of solvents under reduced pressure. 3. Acidification with hydrochloric acid. 4. Recovery and purification of 2,4,5-trichlorophenol. The batch amount was about 6000 kg and the process was timed to allow the production of one complete batch in a 24-h cycle involving three shifts. The evidence is that at 05.00 h on July loth, 1976, when distillation of solvents was pro- ceeding, the production cycle was interrupted. The reactor agitator was stopped and the reaction mixture was left to cool naturally. As it was a Saturday, there was no shift due to take over at this time.Some time later in the morning the temperature, instead of falling, began to rise again. There is no evidence cited in the FRIPC report that the normal maxi- mum reaction temperature of 185 "C for the first stage was exceeded, and apparently the reactor contents had cooled naturally to a lower temperature. The question of what caused the rise in temperature to the exothermic zone remains. Efforts to reproduce this in the laboratory were reported to be unsuccessful.Anal. Proc. At 12.37 h, a bursting disc rated at about 3.5 atm and fitted to the top of the reflux column ruptured. I t appears that the function of the bursting disc was to protect the equipment in the event of a faulty control of air pressure used to transfer the sodium trichlorophenate from the reactor to another vessel for acidification. This accounts for the bursting disc being vented to the outside atmosphere through a short stack.350 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS Analytical Procedures and Results The immediate problem confronting the local authorities when the presence of TCDD was confirmed on July 14th, 1976, was to delineate the contaminated area and to take steps to safeguard the population from further contamination. Evidence of the distribution of the contamination began to accumulate from the examina- tion of leaves, grass, soil and wipe samples from solid surfaces. The first definition of the most heavily contaminated area was made on July 24th, 1976, on the basis of analytical results and animal mortalities. By July 26th 225 people had been evacuated from the most heavily contaminated area.As more results accumulated the zone was gradually extended and by the end of August Zone A, as it was called, covered 108 hectares and the number of people evacuated totalled over 730. Further analytical results from areas at greater distances from the point of discharge showed lower concentrations of TCDD, and this led to the first definition of Zone B. In this area evacuation was not proposed, but children under the age of 12 were removed during daylight hours, as were women in the first 3 months of pregnancy. There were also rigorous controls on food and water supplies. In addition, the authorities defined a zone of “respect,” Zone R, which was a buffer zone between areas contaminated and areas considered to be unaffected by TCDD.Zone R consisted of 1430 hectares. Obviously this definition of contaminated areas remained tentative until further samples had been analysed. Fortunately, as the result of earlier industrial accidents, realisation that herbicides such as 2,4,5-trichlorophenoxyacetic acid might contain significant traces of TCDD and the massive use of these herbicides as defoliants in the Vietnam war, analytical procedures for the determination of very small amounts of TCDD already existed. By using gas chroma- tography and capillary columns combined with mass spectrometry (GC - MS) it had been found possible, under the most favourable conditions, to determine as little as 5 pg of TCDD. The first results obtained from soil, vegetation and wipe samples produced highly variable results.However, by mobilising the resources of laboratories in Milan and introducing trained personnel and a rigid sampling routine, more consistent and reliable results were obtained. Firstly, the high values found on vegetation, particularly trees, indicated that a substantial part of the contamination had been deposited on upstanding material. The second factor was the low incidence and level of TCDD contamination found inside buildings. This was accounted for by the fact that the discharge occurred on a Saturday, when most factories, workshops, schools and other public buildings were closed. In addition, as was customary because of the heat, most houses had almost all their windows shuttered. Thirdly, there was no evidence of contamination of well water and other drinking water supplies with either TCDD or the more water-soluble sodium 2,4,5-trichlorophenate. Apparently there was little penetration of the contamination in the soil. Soil samples were obtained by removing the surface vegetation and taking cores 6.5 cm in diameter and 7 cm deep.Three cores were collected a t each sampling point; two were combined for TCDD determination and the third retained as a reference sample. The results were expressed in micrograms per square metre. The main problem was the clean-up of the samples before presentation to the gas chromato- graph, and this involved solvent extraction and column chromatography. The efficiency of recovery of TCDD was checked by spiking uncontaminated soil with known amounts of TCDD.I t was found that when TCDD levels were 0.01 pg per 500 g of soil or more the recovery averaged 86%. When the soil concentration was as low as 0.005 pg per 500 g the recovery decreased to 667&. All results were corrected for these recovery values, the lower factor being applied when the total TCDD content did not exceed 9 pg. Zone B consisted of 269.4 hectares. These results established three important factors.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 35 1 Within 6 months of the accident the number of samples of all kinds collected and analysed for TCDD by the GC - MS method amounted to several thousands and it reflects great credit on all concerned that such high standards were maintained. Level of Contamination and Acceptable Limits It was at about this time that Cremer and Warner were retained as consultants by the Lombardy regional authority to advise on decontamination procedures.At that time, the exact amount of TCDD emitted was still in doubt, as was the area over which significant amounts had been deposited. It was therefore decided to attempt to model the incident as a check on the information then available and hopefully to provide additional information on the dispersion of TCDD. In general, the model confirmed most of the assumptions made about the incident and gave reassurance that high levels of contamination would not be expected further afield. There were, however, very high levels of TCDD measured close to the source (up to 20000 pg m-2), which were not reflected in the model calculations.This would be explained by the emission of larger droplets or particles as the exit velocity decreased towards the end of the discharge. The general agreement over the remainder of the area tended to confirm that a total emission of about 2 kg of TCDD was of the right order. For further details of the modelling technique, readers are referred to a paper presented to the Royal Meteorological Society by P. J. Comer. One of the most difficult problems facing the authorities was the definition of an acceptable level of contamination so that decontamination procedures could be reviewed and developed in the light of this level. Although there was a considerable volume of data on the toxicity of TCDD, this was mainly based on animal experiments. Clearly it was an extremely toxic material, the LD,, for male guinea pigs being about 5 pg kg-l.There was also a considerable amount of information arising from previous industrial accidents with TCDD on the effects on humans, but unfortu- nately most of this was unquantitative. The Medico-Epidemiological Commission examining this problem ultimately concluded that a tolerance limit of 5 pg m-2 for the soil provided a very large safety margin. Indepen- dently, the consultants arrived at a similar figure when asked to consider criteria for redefining the boundaries of Zone B. For the interior of buildings where contact was more likely to be prolonged, the Commission recommended a value of 0.1 pg m-2, and for ground in the imme- diate vicinity of schools, public buildings and work places a limit of 0.75 pg m-2 was adopted.The adoption of these tolerance limits made possible the development of a plan for the systematic decontamination and rehabilitation of Zones A and B. Decontamination At the time of the accident the weather was hot and dry and most of the fields were covered with thick vegetative growth standing 0.5-1 m tall. From the first analytical results it seemed likely that the heaviest contamination remained deposited on the vegetation. It was suggested that spraying the soil with stabilising resin emulsions might seal the contamina- tion to the vegetation and bare earth and that the contamination could be removed by cutting and collecting vegetation. Unfortunately, permission to proceed was not immediately obtainable and the dry weather ended abruptly in a series of violent thunderstorms and heavy rain.The contamination was thereby transferred from the vegetation to the soil and subse- quent decontamination rendered more difficult. Of the decontamination procedures available, incineration, photolysis and microbiological degradation were given serious consideration. After a study of the conditions required for destruction of TCDD by incineration, Cremer and Warner concluded that it was possible to design a suitable incinerator and therefore recommended the installation of such an incinerator for the destruction of contaminated combustible materials such as vegetation, rabbit hutches, chicken houses and sheds, and materials used for decontamination such as swabs, vacuum cleaner contents and protective clothing.In the event, however, local feelings against an incinerator reached such a pitch that it became politically impossible to adopt this method. Photolysis required the addition of a solvent and a hydrogen donor, and this was tried in a352 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. field experiment spraying of herbage with a mixture of olive oil and cyclohexane. However, in spite of positive indications of TCDD reduction, the method was not adopted as a period of heavy rain began in autumn. Although a review of the literature indicated the possibility of TCDD degradation by soil micro-organisms, the lengthy time involved in proving this method precluded it from inclusion in the decontamination plan for residential areas. Hence the general concept of decontamination was limited to physical removal of contamin- ated materials and vegetation from the lesser to the more contaminated areas and the stock- piling of these until a decision could be made about their ultimate disposal.The interiors of buildings and houses were decontaminated by a combination of vacuum cleaning and washing down with detergents . All operations within the boundary of Zone A had to be carried out under the strictest control of access and procedures similar to those used in handling radioactive materials were adopted. A main stockpile for contaminated material was set up in Zone A and materials were stored under conditions that would prevent re-dispersion and public access.I t was also necessary to prevent the spread of contamination by the movements of rats and other animals. The immediate objectives of the decontamination programme, as approved by the Technico- Scientific Commission in Rome, were (a) to dispose of any “high spots’’ of TCDD contamina- tion in Zone B and (b) to complete the decontamination of the residential area in Zones A6 and A7 in order to permit the displaced occupants to return to their homes as soon as possible. It was decided that in open fields a TCDD level of less than 15 pg m-2 would not be dis- turbed, but that access would be restricted by fencing. Above that level the top 10 crn of soil would be scraped off and removed to the stockpile in Zone A. In private gardens the topsoil would be removed to a depth of 10 cm wherever the surface concentration exceeded 5 pg m-2.Vegetation from gardens was collected in plastic sacks and further enclosed in plastic silos at the long-term storage site. The most highly contaminated zones were closed to all unauthorised access by the erection of a tall fence of corrugated GRP sheets. Decontamination of the exteriors of properties was carried out with a combination of high-intensity vacuum cleaning and high-pressure water jets. Another problem which had to be dealt with was the disposal of the approximately 40000 rabbits, chickens and other domestic animals that had been destroyed by the veterinary services. The carcases had been deposited in about 700 large plastic containers in concen- trated sodium hydroxide solution.These containers were transported to the Icmesa factory and placed in concrete decantation tanks, which were then covered with 1 m of soil. In the long term, the decontamination of the Icmesa works and houses in Zone A2, the replacement of topsoil and the ultimate destruction of TCDD in the stockpiles of contaminated materials has still to be tackled. The history of previous accidents is not particularly en- couraging in this respect as whole factories have had to be demolished and in some instances embedded in concrete and dumped in the sea. Nevertheless, by late 1977 most of the householders evacuated from Zones A6 and A7 were able to return to their houses and in March 1978 a report issued by the Department of Derma- tology of the University of Milan was able to conclude that the incidence of chloracne in the contaminated areas had decreased and that the condition of patients was improving.All decontamination work was checked by GC - MS examination of samples. I thank the partners of Cremer and Warner for making it possible for me to present this paper and my colleagues who have assisted me in its preparation. Photochemical Production of Ozone in the Lower Troposphere over Northern Ireland W. D. McGrath Department of Chemistvy, David Keir Buildin.g, The Queen’s University of Belfast, Belfast, B T 9 5AG, Northern Ireland Ozone is a minor constituent of the normal unpolluted lower atmosphere, or troposphere. The classical and currently held theory of tropospheric ozone postulates its formation in the strato-September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 353 phere, injection into the troposphere by mass transport and its final destruction at the ground.he mechanism of photochemical ozone production in regions of high NO, pollution combined with high insolation, such as pertains in Los Angeles, is now well understood; under such conditions values of ozone concentration in excess of 100 p.p.b. (parts per lo9) have been measured. Recently, however, abnormally high concentrations have been reported in rural areas in the South of England and Ireland as well as in Northern Eur0pe.l It has been sug- gested that this could be due to long-range transport in certain instances. The purpose of the measurements described here was to look for evidence for direct photochemical production of ozone in the Belfast area and possible long-range transport effects, Experimental Ambient ozone concentrations in the air were made continuously during the period 1 April- 31 August, 1979.These were carried out at a height of 50 m above sea level at a site in South Belfast, well removed from industrial pollution. The technique used was that of gas-phase chemiluminescence. Two instruments were employed, one utilising the reaction between nitric oxide and ozone and the other that between ethylene and ozone. Both instruments were calibrated against standard ozone mixtures, made up from pure ozone prepared in the labora- tory. The small amount of light emitted from the reaction cell when ambient air was mixed with either nitric oxide or ethylene was optically chopped and focused on to a photomultiplier tube (Hammamatsu 456). The resultant 250-Hz signal was averaged using a boxcar inte- grator (PAR) and displayed on a continuously running chart recorder.The over-all time constants for full signal were 10 s for the NO - 0, system and 1-50 s with the C2H, - 0, system. Both detection systems had a lower limit of sensitivity of 1 p.p.b. Continuous measurements were also made of the UV-B solar radiation (using a commercial radiometer), wind speed and direction, temperature , relative humidity and barometric pressure. Recorded data were put on to punched cards and stored on magnetic tape for processing on a computer (ICL 1906). Results The complete results of this study will be combined with others relating to different parts of the UK and will be published elsewhere.The following have been selected to illustrate two general points of interest. The highest ozone concentrations measured during the period occurred during April, peaks of 102, 105 and 103 p.p.b. being recorded on the 8th, 29th and 30th of the month, respectively (mean hourly concentration averages). This effect (of high early Spring values) has been observed by several other workers in different parts of the world and is consistent with the classical theory of tropospheric ozone. The interrelation of UV-B intensity, temperature and relative humidity with ozone con- centration is illustrated in Fig. 1, for a typical day exhibiting fairly high total insolation. It can be seen that the ozone concentration follows the UV-B intensity, with a definite time lag, as it does the temperature profile.The relative humidity shows a drop between about 1000 and 2200 h, but when temperature variation is taken into consideration the effective real concentration of water vapour has not changed appreciably. Periodic measurements of ambient hydrocarbon concentrations, using gas-chromatographic detection techniques, showed no abnormally high values. The principal component, naturally occurring methane, remained constant during the period of measurements at 1.2 & 0.1 p.p.m. Laboratory experiments were also carried out using simulated atmospheric gas samples , irradiated with a filtered high-pressure xenon arc lamp. In these experiments the light intensity and wavelength characteristics were selected to correspond to those due to solar radiation at ground level on a cloudless day at peak insolation.The relative concentrations of water vapour and methane were varied over a 10: 1 range of the average obtainable in the Belfast area. These experiments showed conclusively that under conditions where both methane and water vapour were present ozone was synthesised, a steady-state concentration of ozone being established within about 30 min after initiation of irradiation. The important fact to emerge from this is that maximum ozone levels are associated with an Fig. 2 illustrates the dependence of ambient ozone concentration on wind direction.354 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS AfiaL. Proc. easterly wind. This is indicative of a possible long range transport of ozone from the British mainland.- lj + 80.0 2 .- c-' 4 60.0 2 40.0 * 20.0 c E 0 a, 3.0 2 2.5 m e 2.0 1.5 > 1.0 3 0.5 r .- ?! 40 1 Y m I I I I 1 - ( I I I I I U 0 2 4 6 8 10 12 14 16 18 20 22 - aJ Time/h 20 18 16 14 12 10 s Ic' 8 6 4 2 0 NE E I SE S ENE ESE SSE SSW Wind direction Fig. 2. Plot of number of days with ozone concentra- tion 2 80 p.p.b. expressed as a percentage (f) of the total number of days with wind in Fig. 1. Plot of data for Friday, 18th May, 1979. a given direction. In Fig. 3 we have evidence of the so-called "Sunday effect".2 The tendency towards high Statistical analysis of our ozone concentration measurements showed that we could express ozone levels at week-end periods is again explicable in terms of long-range transport, the ambient ozone concentration by either of the expressions where (RH) is the relative humidity, (UVB) is the intensity of solar radiation in the UVB region expressed in absolute terms as W cm-2, (T/K) is the absolute temperature, [H,0) is the absolute concentration of water in molecules ~ m - ~ and /Il, P2, P3 and p4 are constants; for equation (I), p1 = 7.1379, p2 = -0.5464, p3 = 0.3459 and p4 = -19.7027 (correlation coefficient = 0.8002, no.of records used= 168); and for equation (2), = 7.7017, p2 = -1.8799, P3 = 0.2668 and P4 = 21.5676 (correlation coefficient = 0.8447, no. of records used = 168). Discussion We believe that photochemical processes must be extremely important, if not decisive in some instances, in determining the normal tropospheric ozone content, and that the participa- tion of NO, is not essential for atmospheric ozone synthesis, unless there is no ozone at all present initially.In the latter instance NO, would be required to initiate the process by photodissociation to NO + 0.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 355 We propose that an atmospherically important process for tropospheric ozone production involves the following sequence, which will be operative either in a non-polluted rural situation or in an urban area affected by hydrocarbon pollution : 0, + hv -+ 0, + O(lD) OH + CH, -+ CH, + H,O .. O(lD) + H,O +- 20H . . .. .. . . CH3 + 0, + M -+ CH302S + M CH302z + OH 3 CH,O, + H,O (unimolecular decomposition) . . (M will be mostly 0, or N,;J indicates vibrational excitation) .. CH,O, -+ CH,O + 0 O + O , + M + O , f + M .. .. 03f + hv -+ 0, + O(lD). . 0 , f + M - + 0 3 + M .. . . .. . . .. .. .. .. .. .. .. .. .. .. .. . . . . .. .. .. .. .. .. .. . . .. .. . . Three points are worth emphasising in the above scheme: (a) the central role of tlle O(lD) atom, ( b ) reactions (7) and (8) which lead to odd oxygen without the necessity of invoking NO, and (c) the production of vibrationally excited ozone in the recombination reaction (9). From experiments carried out here we have been able to show that 031 produced in reaction (9), the atmospheric process responsible for ozone formation, absorbs at longer wavelengths than 100 90 80 70 60 8 k. 50 40 30 20 10 n Sun. Mon. Tue. Wed. Thu.Fri. Sat. 1.00~ 10-7 G [03i < 1.20x 10-7. 4.oox 10-8 G [031 <6.oox 10-8. 8.00~ G LO31 < 1 . 0 0 ~ 2 . 0 0 ~ < LO3] <4.00x 0 6 . 0 0 ~ < [O,] <8.OOx lo@. 0.00 < [o,] < 2.00 x Fig. 3. Number of hourly readings in specific concentration ranges repre- sented as percentages (f) of total number of readings for each weekday.356 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. ground-state ozone and that the quantum yield for O(lD) production in the wavelength range 310-330 nm is considerably enhanced. This means that the importance of O(lD) reactions in the lower troposphere [particularly reaction (4)] may well be considerably underestimated in current modelling schemes. Our laboratory experiments also indicate that the reaction sequence (7) + (8) is extremely efficient in producing ozone, proceeding at gas kinetic rate at room temperature.This is the first time that methylene peroxide has been proposed as an important atmospheric species, although its role in ozonolysis reactions has been recognised for several years. References 1. 2. Cox, R. A., Eggleton, A. E. J., Derwent, R. G., Lovelock, J. E., and Pack, D. H., Nature (London) Graedel, T. E., Farrow, L. A., and Weber, T. A., Environ. Sci. Technol., 197'7, 11, 520. 1975, 255, 118. Recycling Carbon Dioxide from Fossil Fuel Combustion Eleanor M. Bennett, Brian R. Eggins," Joanne McNeill and E. Anne McMullan School of Physical Science, Ulster Polytechnic, Newtownabbey, Co. Antrim, BT37 OQB, Northern Ireland Pollution by Carbon Dioxide and the Carbon Economy Clearly, when a number of people respire in an enclosed space such as a room, submarine or space capsule, the resulting stuffiness is due to pollution by carbon dioxide.The remedy for the first is easy, but for the last two special carbon dioxide absorption provisions have to be made. An effect that is more insidious is that caused by the huge and increasing combustion of fossil fuels. The result is an exponential increase in the carbon dioxide concentration in the atmosphere, which has been recorded for over 100 years.1 The result of this increase is to produce a "greenhouse effect," causing an increase in the earth's temperature. It is predicted that by 2000 A.D. the mean temperature of the earth will have increased by 0.5 "C, which could cause some melting of the polar ice-caps, hence raising the mean sea level by 25 cm. By 2070 A.D.the temperature rise would be 7 "C, resulting in a rise of sea level of 7 ml-with catastrophic results for low-lying cities such as Belfast, London and New York. The consumption of fossil fuels needs also to be seen in the context of the ecological carbon cycle. To some extent this consumption is putting the cycle out of balance. Our present economy relies very heavily on organic compounds derived from fossil fuels. As these are used up and hence become more expensive, our carbon economy is thrown into disarray, as is shown by the present problems of the synthetic fibre industry in Northern Ireland. We need not just means of halting the pollution effects of carbon dioxide, but also new sources of carbon compounds.It can be scrubbed out by absorption in aqueous alkali or aqueous carbonate to form hydrogen carbonate. The carbon dioxide can be regenerated by heating the hydrogen carbonate or by electrolytic oxidation. Removal of carbon dioxide from chimney gases is easy. Electrolytic Reduction of Carbon Dioxide A better way is to recycle the carbon dioxide to form a fuel (methanol) or other organic intermediates. The simplest route on paper for the reduction of carbon dioxide is electrochemical reduction via formic acid and formaldehyde to methanol-a very useful organic fuel (energy st o re) which can power an internal combustion engine or a fuel cell. * To whom correspondence should be addressed.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 357 +2f?- +2e- +2e- t 2 e - .- - CO, t HC02H c CH20 f CH30H e CH, + 2H+ + 2H+ +2H+ +2H+ +H2O +H2O AGO/kJ mol-1 +38.6 +11.6 +36.7 +113.8 E*/V 3s. N.H.E. -0.20 -0.06 -0.19 -0.59 The reduction of carbon dioxide to formic acid is easy and quantitative. However, despite the apparently favourable thermodynamics, AGO = 11.6 k J mol-l, the high activation energy (over-potential) for the reduction of formic acid to formaldehyde makes it unfavourable com- pared with hydrogen evolution. Appropriate electrocatalysts may improve the situation. Recent studies with tin2 and semiconductor3 electrodes are promising. The initial reduction of carbon dioxide molecules gives the carbon dioxide radical anion^.^ The fate of these depends on the electrode, solvent, electrolyte and pH.Three routes are observed : CO + C0,2- (disproportionation)5s6 7 / + e - H+ CO, c CO,; --+ HC0,- + HC0,H (pr~tonation)~ \ coo- \ 0 I (dimerisation)8 CO, The third route to oxalate occurs in dimethylformamides or aqueous alkali containing tetra- alkylammonium salts. Two groups of workers have found that iiz aqueous tetramethylam- monium hydroxide carbon dioxide is reduced to malic acid (on mercury)gJO or to glycollic acid (on lead) , g 9 1 1 although others?, could not repeat these results. Results We used a glassy carbon electrode to study solutions of carbon dioxide in aqueous 0.1 mol dm-3 tetramethylammonium chloride adjusted to a pH in the range 8-10 with tetramethyl- ammonium hydroxide. Both cyclic voltammetry and rotating disc electrode voltammetry (Fig. 1) showed two waves of equal height whose products corresponded to one-electron waves with respect to carbon dioxide.The current functions of the cyclic voltammograms decreased 0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6 -1.8 -2.0 Potential /Vvs. S.C.E. Fig. 1. Rotating disc voltammograms of carbon dioxide on glassy carbon at pH 10. A, 40; B, 30; C, 20; and D, 10 rev s-l.358 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Pvoc. with increasing sweep rate, indicating kinetic control. On the shorter time scale of the rotat- ing disc electrode, the waves appeared mass transport controlled. Controlled-potential electrolysis of similar solutions at about pH 9 and on the first wave (-0.9 V) produced oxalate, unless the hydroxide concentration was too high (0.5 mol dm-3), in which event mainly formate resulted.We have also shown that oxalate itself gives a reduction wave at -1.7 V and that glyoxylate is reduced on mercury at - 1.1 V, both at pH 9. Similar experiments on the second wave (-1.7 \’) gave glyoxylate. Discussion It is well known that oxalic acid can be reduced to glyoxylic acid,l3 but usually in acidic solution. The thermodynamically favoured glyoxylic acid hydrate, (HO),CHCO,H, must dis- courage further reduction. Clearly Bewick and Greener’slO 3 l1 and Wolf and Rollin’sQ condi- tions allowed the reduction to proceed further. I t is also reported in the literature that glycollic acid can be further reduced to either methanol14 or succinic acid.l5 All these observations can be rationalised according to the following scheme : + e - + 2e- + 2e- CO, f CO,.---t C0,- ~~z CH(OH), + CHO x+ CHOH --+ 2CH30H f c0,- I 1 c0,- C0,- I c0,- I \ I ‘\ 3.C0,- c0,- c0,- b I I CHOH-CH, - - ->CH, i I I 2Hf CHOH CHOH CH, I c0,- I c0,- I co, Although the analysed total carbonate plus carbon dioxide content of our solutions was about 1 x lo-, mol dm-3, the electrochemical data indicate an effective free carbon dioxide concen- tration of 10-4-10-6 mol dm-3 between pH 8 and 10. Further, as the free carbon dioxide is electrolysed, the dehydration of carbonic acid is relatively slow,16 giving rise to the kinetically controlled process. k , I< k - , HC03- + Hf t-- H,C03 ;& CO, + H,O If K , > k1, then d[HCO,-]/dt = Kk, [HC03-] [H+]. earlier workers.These equilibrium and kinetic effects do not appear to have been taken into account by Conclusion In view of the difficulty of reducing formate, the reduction of carbon dioxide via oxalate looks more promising, especially as a possible route to methanol as well as other interesting compounds exists. However, because of the low initial concentration of free carbon dioxide and slow dehydration of carbonic acid, it might be better to reduce carbon dioxide to oxalate in dimethylformamides followed by reduction of oxalic acid in aqueous media.13 Support for this work from the Chemical Society is gratefully acknowledged. References 1. 2. 3. Bockris, J. O’M., and Nagy, Z., “Electrochemistry for Ecologists,” Plenum, New York, 1974. Russell, P. G., Kovac, X., Srinivasan, S., and Steinberg, ill., .J.Electrochem. SOC., 1977, 124, 1329. Halmann, M., Nature (London), 1978, 275, 115. 4. Aylmer-Kelly, A. W. B., Bewick, A., Cantrill, P. R., and Tuxford, A. &I., Faraday Discuss., 1974, 56, 96.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 359 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Roberts, J. L., and Sawyer, D. T., J . Electroanal. Chem., 1965, 9, 1. Sawyer, D. T., and Haynes, L. V., Anal. Chem., 1967, 39, 332. Ryu, J., Anderson, T. N., and Eyring, H., J . Phys. Chem., 1972, 76, 3278. Tysee, D. A., Wagenknecht, J. H., Baizer, M. M., and Chruma, J . L., Tetrahedron Lett., 1972, 4809. Wolf, F., and Rollin, J., 2. Chem., 1977, 17, 337. Bewick, A., and Greener, E. P., Tetrahedron Lett., 1969, 4623.Bewick, A., and Greener, E. P., Tetrahedron Lett., 1970, 391. Kaiser, von U., and Heitz, E., Ber. Bunsenges. Phys. Chem., 1973, 77, 818 Pickett, D. J.. and Yap, K. S., J . Appl. Electrochern., 1974, 4, 17. Baur, E., 2. Elektrochem., 1937, 43, 821. Sontag, W., 2. Elektrochem., 1924, 30, 333. Kern, D. M., J . Chem. Educ., 1960, 37, 14. Enrichment Factors as an Indication of Air Pollution Source C. McDonald* and H. J. Duncan Agricultural Chemistry, Department of Chemistry, University of Glasgow, Glasgow, G12 8QQ A heavily industrialised area such as Glasgow with a diverse and gradually changing industrial pattern is a suitable site for the study of atmospheric levels of trace elements. About 22 ele- ments were detected and analysed in Glasgow’s atmosphere over a 2-year peri0d.l The results compared favourably with other centres throughout the world.The intention on this occasion is to concentrate on one particular aspect of the work, viz., the relative enrichment factors of the elements measured.2 An aerosol reference material enrichment factor, E ( X ) , is defined as concn. X aerosol concn. X reference E ( X ) = concn. R aerosol concn. R reference I where concn. X aerosol and concn. X reference are the concentrations of element X in the aerosol and reference material, respectively. Similarly, concn. R aerosol and concn. R reference are the concentrations of the normalising element in the aerosol and reference material, respectively . In the present study, enrichment factors were calculated using soil and crustal rock as reference materials.The soil and crustal rock levels employed were those of Bowen3 and were a Scottish average. Three studies were carried out in Glasgow: 1. One site (University) was monitored over a 13-month period. Samples were collected on Millipore filter-paper using the sampler recommended by Warren Spring Laboratory at a rate of 30 m3 per 48 h. This was found to prevent clogging of, or pressure drop across, the filter. A volume of 30 m3 of air was required for the accurate measurement of the selected elements by instrumental neutron-activation analysis followed by y-ray spectroscopy. About 156 samples were collected and analysed for 17 elements. Enrichment factors normalised to Fe were calculated on the yearly average and are illustrated (Table I) together with those for Lii3ge in Belgium.2 From the Glasgow figures it can be seen that there are two classes of elements-Fe through to Cs with enrichment factors close to soil proportions, and Sb through to Ag, which have enhanced enrichment factors. Lu and Yb are only moderately enriched and do not readily fall into either class. These results are in reasonable agreement with those reported for Li6ge.2 using Sc as the normalising element, found that Zn, Se, Sb and Pb were enriched by several orders of magnitude and La, Fe, Hf and Th had ratios close to soil proportions, i.e., a similar pattern to Glasgow.This is not to say that those elements with low enrichment factors did indeed arise from soil or rock. In fact, in the Lii3ge study it was estimated that between 70 and 98% of the masses of the elements were from local pollution.One explanation of this anomaly (soil proportions but not soil derived) was given by Rahn,2 who suggested that the elements were due to the presence of fly ash in the atmosphere of cities from fuel burning and other related activities. Three aerosol samples were collected per week. In another study, Rancitelli et * Present address : Public Analyst’s Department, Strathclyde Regional Council, Glasgow, G3.360 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. TABLE I ENRICHMENT FACTORS FOR ELEMENTS IN THE ATMOSPHERES OF GLASGOW AND LII?GE Element Fe* .. .. .. sc* .. . . .. La* . . .. .. Mn* .. .. .. Na* .. .. .. Th* .. .. . . Cr* . . .. . . co* . . .. .. Hft .. . . . . cs* . . .... Lut .. .. . . Ybt . . .. . . Sbt .. .. . . Zn* . . .. . . Br* . . .. .. Se* . . . . .. Ag* . . .. .. * Based on soil. t Based on rock. Glasgow 1 2 3 4 7 8 11 13 13 19 52 56 118 822 1706 2 133 3 490 Li&ge 2.9 1.2 3.8 5.1 1.2 - - 5.8 20 - - - 2 500 2 100 2 200 4 300 910 Rahn suggested that there exist two distinct inorganic fractions in coal, one of which is the rock fraction consisting of Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Zn, Th, La and Ce, which was confirmed by Mason.5 This mineral fraction was deposited at the same time as the original organic material. The second fraction, consisting of V, Co, I, Se, As and Sb, is not present in the mineral fraction and was probably precipitated from ground water by absorption or chemical reaction as the coal was being formed.As can be seen in Table 11, most of the elements in the first fraction are those which are closest to soil or rock proportions and this fly ash is an alternative source of large amounts of material found in cities that has rock proportions : rock particles released nearly unchanged by the pollution source. A further explanation of the enrichment of the volatile elements (Se, Sb and Br) is that these elements are volatilised during combustion and condense preferentially on to the smallest particles, which have a longer residence time in the atmosphere than the larger fly ash particles. TABLE I1 ENRICHMENT FACTORS FOR METALS IN GLASGOW'S ATMOSPHERE The exception is Zn, which has additional industrial sources. Site No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Fe 1 1 1 1 1 1 1 1 1 1 1 1 1 1 A1 2 4 3 5 4 5 6 2 3 2 2 4 3 5 Mn 4 4 8 5 2 3 7 3 4 5 2 5 5 3 Cr 12 17 15 9 11 8 20 15 10 8 6 5 9 14 Zn Ni 337 76 219 181 126 323 123 232 134 222 227 293 233 146 243 61 335 87 427 80 205 43 147 52 439 171 232 146 c u 135 42 4 133 83 14 363 39 2 5 26 23 78 405 Pb 880 1440 2 730 1790 910 1570 1830 520 1330 700 820 270 1080 940 Cd 11 050 10 890 12 360 7 930 34 290 1920 13 990 5 060 3 700 3 150 2 460 1710 3 630 29 180 2.In the second study in Glasgow,6 14 sites in different areas of the city were studied. Samples were collected using the apparatcs described above with the sampling time increased to 1 week, giving a sample volume of 45 m3. A slower throughput of air was necessary to pre- vent clogging of the filter-paper. Samples were collected at a height of 20-30 m above ground level.Each site was monitored for 1 month, giving four samples per site.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 361 The samples were analysed by atomic-absorption spectroscopy using a heated graphite furnace after dissolution of the samples in acid. Enrichment factors were calculated as before and averaged for each site. The results (Table 111) again demonstrate the uniformity of the enrichment factors for Al, Mn and (Fe) throughout the city and, to a lesser extent, for Cr and Zn also. These elements are again those found in the inorganic fraction of coal. As mentioned above, Zn is also in this group but has additional industrial sources that tend to raise the enrichment factor for this element.In at least four instances for Cu the enrichment factor is close to soil proportions and in a further six samples the enrichment factors are below 100. Ni tends to have higher values with only six samples below 100 and none below 50. It is likely, therefore, that Ni is derived mainly from pollution sources other than coal, but Cu on the other hand is mainly from fly ash. Pb and Cd as would be expected are highly enriched compared with soil. TABLE I11 ENRICHMENT FACTORS FOR METALS IN GLASGOW’S ATMOSPHERE ON EACH STAGE Stage Size rangelpm Fe A1 Mn Cr Zn Ni c u Pb Cd - - - - - - - - I 1 6.3-1 7 .O 2 2.0-6.3 1 3 1 9 759 22 74 1426 1358 3 0.7-2.0 1 2 1 8 380 28 76 2132 754 4 0.43-0.7 1 2 1 7 8980 372 71 7604 8390 5 (0.43 1 - 1 1 16 363 136 41 4904 2511 3. In the third study,’ the particle size distribution of atmospheric particulates and the distribution of elements thereon was investigated at one site (University).A cascade impactor was employed, which divided each sample into five size ranges. Sampling at the quoted rate of 17.5 1 min-l necessitated a 15-day sampling period in order to collect sufficient material on each stage for analysis, Atomic-absorption spectroscopy was again used for the analysis described above, and the enrichment factors were calculated, Once again (Table 111) the enrichment factors for Fe, Al, Mn and Cr are uniform and close to soil ratios. Ni is close to soil ratios down to 0.43 pm, after which it increases dramatically. This would indicate that Ni has additional industrial sources. High-temperature processes favour the formation of small particles.Cd, Pb and Zn are all more enriched in the small particle range, suggesting industrial sources. The enhanced enrichment factor for Pb in the smallest particle size range is also consistent with the emission of the element from automobile exhausts. Conclusions Based on enrichment factors there is strong evidence to support the fly ash source of atmos- pheric particulates in Glasgow, with elements falling into two main classes : (a) those produced from the burning of fossil fuel and (b) those having additional industrial sources. One of us (C. McD.) gratefully acknowledges receipt of a Science Research Council post- We are grateful to the Glasgow Weather Centre for access to meteoro- graduate studentship. logical data.1. 2. 3. 4. 5. 6. 7. References McDonald, C., and Duncan, H. J., Atmos. Environ., 1979, 13, 413. Rahn, K. A., “Study of National Air Pollution by Combustion Progress Report,” Service de Chimie Bowen, H. J . M., “Trace Elements in Biochemistry,” Academic Press, New York, 1966. Rancitelli, L. A., Cooper, J. A., and Perkins, R. W., Comp. Stud. Food Environ. Contam. Proc. Symp., Mason, B., “Principles of Geochemistry,” Third Edition, John Wiley, New York. 1966. McDonald, C., and Duncan, H. J., J . Environ. Sci. Health, 1978, A13, 687. McDonald, C . , and Duncan, H. J., Atmos. Environ., 1979, 13, 977. Medicale, Toxicologie et Hygiene, University of Libge, 1972. 1974, 431,362 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. Monitoring of Asbestos in Ambient Environs P.G. Byrne Analytical Chemistry Defiartment, Institute for Industrial Research and Standards, Ballymun Road, Dublin, Ireland Asbestos is a term used to describe a number of hydrated silicates that occur naturally in fibrous form. The four most common forms are: chrysotile, often called white asbestos; crocidolite, often called blue asbestos ; amosite, often called brown asbestos; and anthophyllite, often called grey asbestos. Further details are shown in Table I. TABLE I DETAILS OF THE COMMON FORMS OF ASBESTOS Type Shape Origin Chrysotile . . .. . . Long and curly Canada Crocidolite . . . . . . Straight and rigid South Africa Amosite . . .. . . Similar but South Africa Russia Finland World wide Anthophyllite . . .. Actinolite and tremolite .. Comments 95% of all asbestos products Voluntarily not used in England since 1970 Used in laggings and insulations Rarely found Not processed industrially TABLE I1 DETAILS OF SOME ASBESTOS PRODUCTS USED IN INDUSTRY Product Asbestos sheets . . .. . . . . . . . . Heat insulation . . . . . . .. . . .. Sprayed insulation (this practice is now discontinued) . . Brake linings . . .. . . .. . . . . Textiles (fire curtains, etc.) . . .. . . . . Some floor coverings . . .. . . . . . . Some moulded lagging sections . . . . . . . . Moulded silicate or magnesia . . .. . . . . Old lagging . . . . .. . . . . . . . . Type and approximate asbestos content 12-15~0 Chrysotile 25-40y0 Amosite 55% Crocidolite, amosite or chrysotile 35-60% Chrysotile 85-10070 Chrysotile 5-10y0 Chrysotile up to 55% Amosite up to 15% Amosite Anything could be present Because of its great heat resisting properties asbestos has been used by industry in a wide variety of applications, some of which are shown in Table 11.Unfortunately, it is now known that people who inhale asbestos dust in their work may develop such serious diseases as asbestosis, lung cancer and cancer of the abdominal cavity lining. It has also been demon- strated that people who are only indirectly exposed to asbestos sources may also develop malignancies of the same type. Table 111 gives typical exposure levels when working with asbestos products. To protect the workforce, regulations were brought specifying the follow- ing emission limits : Crocidolite (blue asbestos) 0.2 fibres per millilitre All other forms 2.0 fibres per millilitre A fibre was defined as a particle whose length was greater than 5 pm, whose diameter was smaller than 3 pm and having a length to diameter ratio of greater than 3 to 1.There is no agreed level or regulation for exposure rates outside the factory environs but several years ago a level of 1000 ng m-3 was set as a limit by a planning authority. This limit was a couple of orders of magnitude more stringent than the in-factory regulations and this paper deals with the method that was developed to monitor asbestos at such low concentrations.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 363 TABLE I11 TYPICAL EXPOSURE LEVELS WHEN WORKING WITH ASBESTOS PRODUCTS Industrial operations Levels of fibre content/ fibres per cubic centimetre Asbestos cement #voduds- Hand sawing .. . . .. . . . . .. 2-4 Machine sawing . . . . .. . . . . .. 10-20 Machine sawing plus ventilation . . .. . . (2 Drilling . . . . .. .. .. . . .. 2-10 Drilling and finishing . . .. .. . . .. 2-10 Asbestos insulation boavds- Brake linings- De-riveting . . .. . . .. . . .. 1-3 L aggings- Demolition and removal of sprayed coatings, dry . . 20-150 thorough soaking . . .. . . . . . . 1-5 Demolition and removal of sprayed coatings, after Textiles- Cutting and sewing cloth . . . . .. .. ( 2 Table IV shows a review of some of the techniques used in the identification and quantifica- tion of asbestos. It was soon apparent that only electron microscopes would be capable of detecting asbestos at the nanogram per cubic metre range. Some preliminary work on the scanning electron microscope (SEM) showed that while this instrument was capable of detect- ing minute fibres, there was often some difficulty in recognising the fibre among the rest of the debris present. The SEM does have the advantage of examining the entire filter-paper with its fibres as received and some work is still being done in this direction but it was felt that, for the particular problem in hand, the transmission electron microscope (TEM) was most suited.After discussion with workers in England, Holland and the United States1-6 a method, the scheme of which is shown in Fig. 1, was developed. TABLE IV TECHNIQUES USED IN THE IDENTIFICATION AND QUANTIFICATION OF ASBESTOS Two fibres per cubic centimetre may be considered as very approximately lo5 ng m-3.Qualitative1 Technique quantitative Polarising light microscopy . . Qualitative Phase contrast light micro- SCOPY . . . . . . Quantative X-ray diffraction . . . . Either Infra-red spectroscopy . . Either SEMIEPMA .. .. . . Either TEM, Electron Diffraction (EPMA) . . .. . . Either Limit of detection In theory, 1 fibre In practice, about 0.05 fibres per cubic centimetre the filter-paper About 10 p g on Probably in the milligram range Nanogram per cubic metre range About 1 ng m-3 Comments Used for routine identification of asbestos Used for routine monitoring near point sources of emission (in factory environs) Could be developed as a fast screening technique ; gives no information on fibre size Used mainly as qualitative tool or, if quantitatively, for bulk sample analysis Difficulties may be experienced in resolving the asbestos fibres from the other debris present Method favoured by most laboratories analysing a t the nanogram per cubic metre level Some of these stages will now be considered in more detail.The large volume of air is obtained by sampling at about 60 1 min-l over a 24-h period. The amount of dust and other debris collected in this period makes the filter appear anything from light grey to black, depending on the location. A special cutting tool is used to provide reproducible quarter segments of each filter sample. This allows additional segments for re-check analysis either at the I.I.R.S. or at another out- side test house; 10% of all samples taken are checked by a second analyst.364 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS Anal.PYOC. In the low-temperature ashing stage, the power is kept to a minimum to minimise any losses during this operation. In addition, the disposable glass phials chosen have restricted necks, thus helping to prevent loss. The oven itself has five sample ports and this number of samples can be run simultaneously. This stage is usually performed on an overnight basis, thus allowing time for other duties. Representative section (%I of filter taken Volume sampled 80-100 m3 of air on 47 mm 0.8 pm filters The mass of asbestos is calculated from volume measurements and also t Low-temperature ashed (70 "C) overnight 10 ml of filtered Long period in ultrasonic bath (25 ml) I I I .1 0-pl aliquot is transferred to 4 carbon-coated 200-mesh TEM grids 1 I J + Five square openings from each grid chosen a t random .t The asbestos fibrils in the above 20 openings are examined a t a mag. of approx. 20000~. The length and diameter of each are noted u, 100 +-I 0 0 z 0 100 200 300 400 Time/m in Fibre breakdown with sonification. Fig. 2. Fig. 1. Flow diagram of asbestos analysis. After ashing, which removes the filter and all other organic matter, only a minute residue remains. To this is added 5 ml of filtered distilled de-ionised water and the glass phials are placed in a rack in a high-powered untrasonic bath. This stage is also performed on an over- night basis or for at least 6 h. Fig. 2 shows that during this period all the fibres present will be reduced to fibrils of ultimate minimum diameter of about 340 A.It must be noted that this operation destroys the original size and shape of a fibre but does provide more fibrils available for counting and thus improves the over-all sensitivity and reproducibility of the method. The samples are then made up to a fixed volume.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 365 Preparation for TEM work first begins by putting a very thin (200 A) coating of carbon on 200-mesh TEM grids. A lo-$ aliquot of solution is then placed on each grid and allowed to dry. This stage is repeated in quadruple for each sample in order to maximise homogeneity. The grids are examined at a magnification of between 4000 and 20000 times. The chrysotile asbestos (the only form expected) is recognised by its rather unique morphology and, if neces- sary, by electron diffraction.The lengths and diameters of the fibrils are noted and quantita- tive results are obtained by converting volumes into masses or more conveniently from a calibration graph prepared using previously prepared standards. The calibration graph of average number of fibres per grid opening vemm nanograms of chrysotile on the grid is a straight line passing through the origin. To improve the counting strategy, 5 square openings from each grid are examined. The total number of fibrils for the twenty openings examined are noted and the average is obtained. The amount of chrysotile on the grid and thus on the original filter can be calculated from the graph and the answer is expressed in nanograms per cubic metre.The limit of detection of this method is estimated to be less than 1 ng m-3 but for routine reporting purposes a limit is set an order of magnitude above this. It can be appreciated that owing to inherent difficulties reproducibility, especially at low concentrations, will be poor and at best is estimated to be about rJr 50%. The technique is being continually reviewed and current research is concentrated on possible losses during the ashing stage and on the feasibility of fibril counting from electron micrographs. The latter would have the dual advantages of providing permanent records and minimising time spent on the electron microscope. This means a minimum of about 4 h TEM work per sample.References 1. 2. Rohl, A. N.. and Langer, A. M., Environ. Health Perspect., 1974, 9, 95. Henry, W. M., Heffelfinger, R. E., Melton, C. W., and Kiefer, D. L., “Development of a Rapid Survey Method of Sampling and Analysis for Asbestos in Ambient Air,” NTIS publication APTD-0965 of contract CPA 22-69-110, Batelle, 1972. Zumwalde, R. D., and Dement, J. D., “Review and Evaluation of Analytical Methods for Environ- mental Studies Fibrous Particulate Exposures,” N.I.O.S.H., Cincinnati, personal communication, not for publication, January 1977. 3. 4. 5. 6. Rickards, A. L., Anal. Chem., 1973, 45, 809. “Electron Microscope Measurement of Airborne Asbestos Concentrations-A Provisional Methodology Beanian, D. R., and File, D. M., “The Quantitative Determination of Asbestos Fibre Concentrations,” Manual,” EPA Technology Series EPA-600/2-77-178, August 1977.Don Chemicals, personal communication. Current Activities and Future Priorities in Air and Water Pollution Research W. S. Clough Directorate General of Research, Department of the Environment, 2 Marsham Street, London, S. W.l The Problem The extent of pollution of air and water in the UK was illustrated by reference to relevant examples of statistics on levels and trends in concentrations over a period of about 20 years. Much of the data presented were taken from the “Digest of Environmental Pollution Statistics 1978” (HM Stationery Office, London), which is produced by the Department of the Environ- ment (DOE) and updated annually. The data on air pollution show, in general, a decreasing trend in concentrations ; sulphur dioxide, particles and other pollutants derived from coal burning show the most noteworthy reductions.The decrease can be ascribed mainly to the implementation of the Clean Air Acts and the change over to alternative fuels, although the climate over recent years and the high-stack policy applied to power stations may also have contributed to the decline. Other pollutants, such as hydrocarbons, nitrogen oxides, ozone, carbon monoxide and lead, which are produced from the combustion of all fossil fuels and/or from the internal combustion engine, have not shown the same decreasing trend. There has been a decreasing trend in the general pollution of rivers although the sometimes rapid progress of earlier years has tended to slow as the relatively easy problems are solved and the more difficult areas, usually in highly industrialised stretches, remain.Pollution levels in the Thames demonstrate a continuing “success story” in clean-up, but there are other examples366 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. where specific pollutants such as phosphate and nitrate showed rising trends to the extent that remedial action was instigated to ensure that quality standards for water abstraction were not exceeded. Regulation The release of pollutants into the environment and the concentration of pollutants in particu- lar areas (such as air, drinking water and marine waters) is controlled by means which range from the strict legislation of UK and EEC law to the less formally defined, but sometimes equally effective, force of international opinion.Brief descriptions were given of the develop- ment and implementation of legislation using as examples the UK Control of Pollution Act 1974 and the EEC Directive on the Disposal of Toxic Substances in the Aqueous Environment. The role of international bodies such as the WHO and OECD was also outlined. DOE Research The requirement for a programme of research on pollution in the DOE follows logically from the existence of the problem and the Department’s policy responsibilities which span all aspects of pollution of the general environment. The programme is “Applied Research” in the Rothschild sense and is organised on the customer/contractor basis. It is addressed to pro- viding answers to specific problems raised within the Department, but it contains a consider- able element of long-term programmes which are pursued at Research Establishments that have become centres of expertise and advice to the Department.Funding for the programme is provided by DOE and is almost totally used to support extra-mural contracts. The majority of these are placed with four major contractors, vix., the Natural Environment Research Council, the Water Research Centre, the Atomic Energy Research Establishment (Hanvell) and the Warren Spring Laboratory. Remaining contracts are widely spread between other establishments, including Universities, Technical Colleges and industry. Responsibility (and funding) for “pure” research on pollution (as opposed to the applied programme above) lies with the NERC and the Science Research Council.Under the general policy that “the polluter pays,’’ the solution to specific/localised problems is the responsibility of the polluter and research on the amelioration of localised or industry-specific effects does not figure in the DOE programme. DOE Research Organisation DOE Policy Directorates have responsibilities for given sectors of the Department’s over-all function and are customers for research. The Directorate General of Research (DGR) has, as one of its functions, the responsibility to provide an over-all research programme to meet both the immediate and longer term needs of the Department. The research programme is defined with the assistance of the relevant Policy Directorates and with the benefit of the views of the major contractors. The internal machinery for establishing priorities for research funding was outlined and, in particular, the sub-division of the programme into subject areas and the rela- tive effort in each area was described (see Table I).Project A . . .. B . . . . c . . . . D . . .. E .. . . F .. . . G . . . . H .. . . k * - .. . . . . L . . .. TABLE I SUBJECT AREAS AND BIDS FOR FUNDING x 1000 (1979/80) a t Subject area Sept. 1978 prices Coastal Management 561 Estuarine and Marine Pollution 524 Water Resources 1053 Freshwater Pollution 537 Water Quality and Health 632 Cross Sectoral Items 612 Solid Waste Management 1431 Air Pollution 1629 Noise 242 Environmental Radioactivity 166 Total 7 930 Sewage Disposal 544September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 367 The management of the research programme is the responsibility of DGR and a DOE Nominated Officer is appointed for each contract, whose duty is to supervise progress accord- ing to the terms of contract.In most areas review groups are formed consisting of customer, contractor, DGR and other representatives to report on progress and advise on the develop- ment of the work. Programme Content A general review was given of the projects in progress under the general headings in Table I and two items of work (the study of the oxidation of sulphur dioxide in the ambient atmosphere and the uptake/retention by humans of lead from motor vehicle exhausts) were described in more detail. Future Trends In the part of the programme deaIing with air pollution, the Department is currently reviewing its effort on monitoring with a view to tailoring the measurements to meet specific objectives.These include (a) the requirement for data to provide evidence of compliance with agreed pollution limits (e.g., to meet current and potential UK and EEC legislation), ( b ) exposure data for use in studies of effects of air pollution on health, vegetation and artefacts, (c) data input required for modelling studies and (d) continuing information on trends in air concent rat ions. There is a continuing requirement to increase knowledge of the effects of both air and water pollution, i.e., dose - effect relationships, and increased emphasis on these aspects is likely in the immediate future.In the research programme on water the study of health effects of pollutants, especially “new” chemicals which are often present in very small concentrations, will be expanded, The study of techniques to prevent water pollution and clean-up polluted supplies, i.e., to meet established standards, will be regarded as more the responsibility of the water industry. Water Quality Surveillance in a Highly Re-used River D. C. Hinge Thames Water, Lea Division, The Grange, Crossbrook Street, Waltham Cross, Hertfordshire, EN8 8LX The River Lee and its tributaries drain approximately 1300 square kilometres to the north of London, including north and east Hertfordshire and ten London Boroughs to the north of the Thames. For over 300 years, this river system has been used as a source of drinking water for part of the population of London.Within the last 100 years, there has been a considerable increase in population in London and the Home Counties, particularly with the development of new towns, which has led to a steady increase in the volume of sewage effluent discharged into the river system upstream of water supply intakes. Today, the proportion of sewage effluent in the river system averages 25% on an annual basis but, under summer flow conditions, can rise to as high as 75% by volume at the water supply intakes. Although the primary use of the river is for water supply, the high population makes many other demands, including agriculture, horticulture, industrial cooling water and a wide range of amenity and recreational uses.As well as the known pollution entering the river as sewage effluent, the river is also susceptible to incidental pollution. Given the backing of strong pollution control legislation, which dates back over 100 years, this intensive use of a river demands detailed water quality surveillance work. Water Quality Surveillance The current programmes of water quality surveillance largely derive from the Rivers (Prevention of Pollution) Acts of 1951 and 1961 and involve chemical and biological moni- toring of the river system. Today, the laboratory analyses about 7000 samples per year and employs 19 staff of various disciplines for analysis and interpretation.368 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. Sampling For chemical analysis,l sampling techniques depend on the constituents on which informa- tion is required.For standard pollution control constituents such as ammonia and BOD, ordinary bucket and bottle techniques are adequate, provided that representativeness within the cross-section of the river is determined beforehand. For other constituents, particularly trace organic materials, it is necessary to use direct sampling using acid-washed bottles and, in some instances, filtration, preservation and concentration on-site may be necessary. More intensive studies of the river system for specific constituents require the use of auto- matic recording instruments or automatic samplers. Since 1968,293 a programme of continuous monitoring of river quality at five strategic points has been developed and this is now reaching the stage where useful statistics on river quality can be derived.Sampling for the invertebrate life on the bed of the river provides information on the past history of river quality. This is done at 60 points in the river twice a year and either riffle sampling or grab sampling is used as the basic technique. In addition, information on fish populations is gradually being accumulated and here either mark/recapture or successive capture techniques are used. Analysis The chemical analysis of river water has followed the same general trend that there has been in analytical chemistry over the past two decades, namely, a shift towards more instru- mentation coupled with a lowering of the concentration range in which there is interest.The basis of the routine methods used are contained in the Department of the Environment’s “Green”4 and “Blue” books, which provide a good mechanism for regular updating of analytical methods in this field of work. The main brunt of chemical analysis is borne by two automatic analysers coupled with a data processor. This system minimises clerical effort in calculating results from charts, etc., and providing information on analytical quality control. In analysing the increasingly wide range of organic constituents that may have significance in the context of re-use, there are many problems in extraction, formulation and detection, bearing in mind that one is dealing not only with water samples but also with river muds and biological materials. The results are currently being entered into a water quality archive data base from which summary information on water quality for various purposes can be generated.River Water Quality River Classification The main thrust of interpretation work over the past few years has been in the develop- ment of a river water quality classification system based not only on chemical and biological criteria but on general environmental conditions as well. This classification has led to the introduction of the 95 percentile concept and, on the basis of the statistics of 3 years’ data (1975-1978), rivers have been classified. On the River Lee, all rivers above water supply intakes are in Class 2 or better. This system is now being used for performance monitoring and for planning purposes, whereby the future requirements for effluent standards can be derived.Effects of Re-use Table I shows the changes that take place in a number of constituents between the point at which water is supplied to the population in the north of the area through to the point where the treated waste water from that population is discharged and thence diluted in the river before reaching the river abstraction points. As an example of the effect of re-use, studies on nitrate concentrations in the river system have been carried out over the last few years. These studies have identified the need to reduce the concentration of nitrate in nitrified sewage effluent. This has now been achieved ~perationally.~ Studies continue on the influence of land run-off and whether this will require some further action.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS TABLE I EFFECT OF RE-USE 369 Parameter Carbonate hardness/mg I-’.. Non-carbonate hardnesslmg 1- Ammoniacal nitrogenlmg 1-I Nitrate-nitrogenlmg 1-1 . . Calciumlmg 1-1 . . . . Magnesiumlmg 1-1 . . .. Sodiumlmg I-’ . . .. Potassiumlmg 1-1 . . .. Sulphate/mg 1-1 . . . . Chloridelmg 1-1 . . .. Fluoride/mg 1-1 . . . . Phosphate/mg 1-1 . . .. Silicalmg 1-I . . . . .. TOC/mg 1-1 of C . . .. Syndetslmg 1-1 . . . . Boron/mg I-’ .. .. E . coli cells per 100 ml . . .. -1 . . . . .. .. . . . . .. .. .. .. .. .. .. .. .. .. Supplied water 263 48 0 4.6 119 3.8 10 1.9 26 21 0 0.1 16 Trace 0 0 Absent Sewage effluent 244 74 0.1 20.6 7.4 115 109 19 81 109 0.3 7.8 8.1 0.2 0.9 22 50 x lo2 River abstraction 252 81 0.1 8.4 6.6 8.1 122 49 83 57 0.3 1.5 7.0 0.2 0.3 12 2 x 102 The Future The highly re-used River Lee provides a good catchment to study all possible influences on the use of the system beyond the 50 or so constituents which are normally covered.The system known as catchment quality control6 has been instigated and this has provided information on the usage of chemicals in the area and their possible concentrations in the river. This information is being followed by selected analysis and, at the moment, substances such as pentachlorophenol, EDTA and photographic chemicals are proving to have some significance. It is intended that these studies, together with the continued vigilance of pollution control officers, will continue in order to maintain the River Lee as a fit source of water for the population of London.Conclusion Water quality surveillance in the River Lee involves the integration of many scientific disciplines so that good management of the river basin provides water that is, at any time, satisfactory to the uses demanded by the public. References 1. 2. 3. 4. 5. Hinge, D. C., Chem. Ind. (London), 1973, 727. Toms, R. G., Hinge, D. C., and Austin, J. L., J . Inst. Water Pollut. Control, 1973, 1, 20. Hinge, D. C., Paper presented a t WRC Symposium on Practical Aspects of Water Quality Monitoring Systems, December 1977. Department of the Environment, “Analysis of Raw, Potable and Waste Waters,” HM Stationery Office, London, 1972. Hawkins, J. E., Collinson, B., and Stott, D. A., “Proceedings of International Symposium on Treat- ment of Combined (Urban and Industrial) Waste Waters, University of Libge,” Volume lB, pp.1/25-6/25. Wood, L. B., and Richardson, M. L., Paper presented a t IAWPR Workshop, Vienna, September 1979. 6. Pollution of Lough Neagh : A Multi-disciplinary Approach R. B. Wood Limnology Laboratory, New University of Ulster, I’raad Point, Druunenagh, Magherafelt, County Dewy, Northern Ireland Pollution was chosen as the theme for this conference to bring many sub-disciplines of chemistry together and my main purpose is to widen our horizons still further, by taking one local example of pollution and showing how a very wide range of disciplines, among them natural and social sciences, history and politics, need to be brought to bear on an environ- mental problem.Anal.Proc. 370 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS Nature of Lough Neagh’s Problems In 1967 a spectacular accumulation of algae in Lough Neagh clogged water filters, killed fish (especially eels held in keep-boxes before marketing) and stank. The lough, over 350 km2 in area, sustains Europe’s largest eel fishery, has a very important run of salmon through it via the river Lower Bann to the spawning rivers, should be able to supply perhaps 200 million gallons a day drinking water if properly regulated and has significant amenity value especially sailing and wildfowl conservation. Detailed studies began on determining the seasonal succession of algael because several species are involved, each with its own ecological foibles of nutrition, temperature, respiration, photosynthesis, buoyancy, susceptibility to grazing and disease, etc.Early work2 included study of nitrogen fixation by Aphanizomenonflos aquae (which occupies a similar niche to the 1967 bloom) and its ability to by-pass normal nitrogenous nutritional constraints. The results showed that if phosphate were in excess, and if competitors such as Oscillatoria agardhii were themselves reduced by grazing or parasitism, Aphanizomenon could thus come to dominance. Jewson’s3-6 work on photosynthesis required for its full understanding very detailed analysis of the optics of Lough Neagh, penetration of light and spectral shifts with depth, photosynthetic efficiency, competition between algae and peat colour for light, the balance between day length and the light/dark parts of the water column that permits photosynthesis to exceed respiration and net growth to occur, and the response of algal cells to being circulated from full sunlight to virtual darkness in a few seconds.’ Our list of disciplines already includes the physics of radiation, physiology and biochemistry, taxonomy, meteorology and hydro- mechanics.Foy et aL8 have studied in greater detail the growth of blue - green algae in the laboratory using controlled day length, light and temperature, and Gibsong-ll has published elegant work on respiration and the carbohydrate content of algae in the field, all to the same broad end: why do the algae perform the way they do in Lough Neagh? The origin of the excess of phosphate that sets an upper limit to the algal crop12 is highly germane.Very painstaking studies of phosphorus budgets have been undertaken since the first rough field and desk estimates were made.13-17 These budgets not only involve very large numbers of precise chemical analyses but also require studies of climate and the hydro- metry of rivers, the distribution of people and farm animals, farming practice and human habits, soil chemistry, the efficiency of sewage works and septic tanks as well as the mathematical skills to regress and project intelligently into areas where complete study is impossible .149* Phosphorus as the culprit was broadly accepted in 1971 by the then Minister responsiblelg but much more work on sources, and the differential utilisation of species of phosphorus by algae, was carried out and helped lead to the acceptance that sewage-borne phosphorus is the largest single contributor and the most susceptible to remedy.Acceptance has involved seemingly endless meetings between biologists, chemists, engineers, administrators and politicians, and this aspect of a multi-disciplinary approach to environmental problem solving must be stressed, for without diplomatic advocacy the most brilliantly derived data may be useless; without some sympathetic listening to others trained in quite different disciplines and patterns of thinking, even advocacy in the Marshall Hall class may not lead to justice. The immediate task was to find why algae grow so well in Lough Neagh. From the debates implied above a second tier of questions arise.1. 2. 3. Is an occasional algal bloom such a problem? Would the lough recover if phosphate were restricted or has it always been like that? Can and should we afford it ? If it will recover, how soon and to what state should we aspire? Secondary Effects of Excessive Algal Growths One example of this is given in Fig. 1 where the oxygen conditions in Lough Neagh over several years are shown. Notwithstanding the exposed, shallow nature of the lough (no mountains to protect it from the Atlantic winds, mean depth only 8.6 m) the biomass ofSeetember, 1980 37 1 algae is such that, in its respiration and decomposition, great demands are put on the oxygen content of the waters, which wind-stirring barely keeps topped up. Extensive periods below saturation persist and a few days of calm weather are enough for severe depletion to occur, as shown by some of the rapidly plunging troughs.Gibson, Wood, Jewson and Rippey in so far unpublished work on sediment and microbial respiration have all concluded that bottom waters could go from full to 50% saturation in 3 4 d of flat calm weather and in microzones just above the sediment surface much sooner than that. Even apparently good oxygen conditions (as in Fig. 2) may mask at depth local problems, which are of two kinds. Chemically reducing conditions permit massive release of algal nutrients from the enriched muds (see Fig. a), which may further stimulate algal growth. Stevens and Gibsonz0 have described the field situation while Rippeyzl has analysed in some detail the chemical fractions and the complex of chemical reactions and back reactions involving ligand exchange mechanisms that operate. POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS J F M A M J J A S O N D s 100 120 100 60 130 s 100 8 70 120 100 s 50 5 0 t l I I I I I , ' , I , , , J F M A M J J A S O N D Fig.1 . Mean percentage oxygen saturation in L. Neagh (Skaddy Station), 1970-1976. Mean values are compensated for lesser volumes of water with increasing depth. Arrows on 1975 and 1976 indicate the full depth profiles shown in Fig. 2 . On a more biological level even transient anoxia has a major influence on bottom fauna, on fish feeding and on the success of eggs on the fish breeding grounds. Carter's excellent st~dies~~-25 of Lough Neagh chironomids (themselves notorious as nuisance swarms resulting ultimately from the excessive growth of algae) have shown how, over the past few years, pollution intolerant species are gradually becoming restricted to inshore areas and replaced in deeper water by, for example, Chironomus anthracinus and Chironomus plumosus, well known as indications of extreme eutrophication.There is ample evidence that the pollan. for example, (Lough Neagh white fish) now exists in much lower n ~ m b e r s ~ ~ ~ ~ ~ than it did 60-70 years ago, as shown by archival search.28 The less desirable perch now almost dominates the l o ~ g h , ~ ~ resident and migratory salmonids must be at considerable risk if the wind does not blow hard once a week, and even the tolerant eel cannot be considered safe.Problems of water abstraction are touched on under Cost below.372 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. NHB/pg 1-l Si/pg I-’ 0 900 0 0.3 1.2 I I 1 1 1 1 - 0 2 % 0 2 % Plpg I-’ 0 100 0 100 0 300 10 lD 2202 = 98% CO2 = 71% 17 July, 1975 1T17rm;r I l l 1 0 500 FeIpg 1-l Fig. 2. Vertical distribution of O,, Fe, P, NH,, pIi and Si in L. Neagh during two calm periods. Original State of Lough Neagh and Chances of Recovery Recovery is always difficult to predict because loughs, like people, are all different but the literature shows many lakes that have responded to reduced phosphorus input, e.g., Lake Wa~hington,~~ Lake N ~ r r v i k e n , ~ ~ Lake and only a few have not, and these, e.g., Lake Trummen, have special problems such as excessive silting up requiring dredging first.Cer- tainly, palaeolimnological studies clearly show that deterioration of Lough Neagh began only 80 years or so ago. Palaeolimnology is itself a multi-disciplinary science, in which sediment cores are analysed for the fossil and other evidence they contain. Older material is over-layed by newer (though sometimes disturbed) material and it is often possible to reconstruct the ecology of a lough and its catchment back through millenia. It requires minor engineering skill to take the undisturbed cores of lough sediments, and dating expertise involving measure- ments of carbon-14, geomagnetic declination, susceptibility and coercivity, lead-210 and caesium-137 (not to mention an appreciation of cold-war politics which influenced the timing of the production of caesium-137 from nuclear bomb fall-out), the changing inputs of pollen grains reflecting the introduction of exotic species such as flax, or the clearing of the natural woodlands, whose dating is known from historical r e ~ e a r c h ~ ~ ? ~ ~ or the 1941/42 plough-up of grass and sowing of cereals.With cores accurately dated, microfossils of diatom frustules, head capsules of chironomid larvae and carapaces of cladocerans after careful identification and counting can give clear evidence of the qualitative and quantitative changes in the flora and fauna in past years. Battarbee35 and Carter36 have shown how, after thousands of years of stable conditions in which Lough Neagh would be described as mildly niesotrophic, changes toward much more eutrophic species coupled with vastly increased numbers began about 1900 AD. A very much simplified picture of the quantitative changes they have described is shown in Fig.3. There is much more and detailed evidence, particularly chemical, which the sediments contain giving information on soil conditions, erosion, heavy metals and phosphate input, redox conditions at the mud - water interface and stable algal pigments of which space prevents rehearsal. One reassuring feature of Fig. 3 is that the timing of the upturn in Lough Neagh’s eutrophication is nicely consistent with the introduction of piped water and sewage around the turn of the century (shown by more archive work) and the post-war appearance of detergent phosphorus. Contemporary nutrient budget work had already pointed to sewage.Clearly, the natural state of the lough to which we must hope to revert is mesotrophic as in the late 19th Century when it produced perhaps only 10% of the present diatom crops and 3% of the midge swarms, yet sustained thriving pollan and other fisheries. Phosphate removal at major sewage works (technically straightforward and standard Many aspects of this work are referred to in Battarbee.35September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 373 practice in many countries) is the obvious first step, perhaps reducing by 50% the present loading of orthophosphate and is now stated as government policy. With this have gone directives about the siting of septic tanks, where possible to encourage phosphate adsorption by soils rather than direct discharge into streams, the storage and spreading of slurry from intensive animal rearing, the use of fertilisers in reafforestation of peatlands, and the use of phosphate-poor detergents, e.g., in the milk processing industry. 1400 1600 1800 2000 A.D.3. The arosslv simplified changes in palaeo-iroductivity *of L. Neagh as shown by the influx of (a) diatoms and (b) midge head capsules to the sediments in recent centuries. (After B a t t a r b ~ e ~ ~ and CarteP). cost Marshalling economic arguments in favour of environmental conservation is not easy, because the most difficult of all sciences comes into play, animal (human) behaviour. What is the value of a pair of great crested grebe? Why do politicians act the way they do? Although the true figures for phosphate removal are hard to come by, estimates have come down from around E20 million (suggested by one man who didn’t want to have it done) to around E0.2 million capital with somewhat higher recurrent costs.These do not seem vast sums when set against an eel fishery currently supporting some 500 families in a very depressed area, or when set against the cost of filtering Lough Neagh water before supply. A 9-month study of Caster Bay water works showed a good correlation between algal crops and filter problems, and that some 6.5% of output was lost amounting to approximately 220 million gallons of water. At about 50 pence per 1000 gallons (the real, not charged, cost), the lost output was &llOOOO per annum, even ignoring the high capital investment in mechanical scrapers now found necessary.The Dunore Point works almost certainly suffers from the same scale of problem but is three times larger in design. It could be that much of the annual running cost of phosphate removal is already being spent without any of the extra benefits to fish or amenity. Although it would be wrong to conclude that phosphate removal would do away with the need for all filtration, at least something should go into the credit b a1 ance . Multi-disciplinary Philosophy The work described has ranged over dozens of notionally discrete, natural and social scientific disciplines and I have tried to show how each has played a part in developing a story with a serious practical end-point as well as contributing to basic ecology.Although not obvious from the superficial treatment given here, each has been pursued with a rigour374 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. appropriate to the specialist (and specialist papers have resulted). No grand synthesis can ever be properly based on wide-ranging dabbling and those who advocate the role of integrated science must beware lest breadth becomes synonymous with superficiality. Equally, the day of the omniscient natural philosopher has passed but what environmental science badly needs are those with enough wide vision to see how different experts can contribute and how those skills can be made to harmonise. Clearly, similar integrating thoughts were with the Chemical Society in convening this meeting. Much of the work described here was carried out by students and colleagues in the University. Their co-operation and stimulation is gratefully acknowledged as is the research funding from many bodies including the Department of the Environment (NI), NERC, Department of Fisheries, Dublin, The Fishmongers’ Company of the City of London, The Hon. the Irish Society, Antrim County Council, British Enkalon and the Department of Agriculture (NI). It is also a continuing pleasure to record the splendid co-operation which exists between my laboratory and the FBIU (Department of Agriculture, NI), some of whose excellent work is inadequately reviewed above. 1. 2. 3. 4. 5. 6. 7. 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. 33. 34. 35. 36. References Gibson, C. E., Wood, R. B., Dickson, E. L., and Jewson, D. H., Mitt. Int. Ver. Limnol., 1971, 19, Riddols, A., DPhil Thesis, New University of Ulster, 1974. Jewson, D. H., Int. Revue Ges. Hydrobiol. Hydrogr., 1975, 60, 759. Jewson, D. H., Freshwater Biol., 1976, 6, 551. Jewson, D. H., Proc. R . Tr. Acad., Sect. B., 1977, 77, 87. Jewson, D. H., Oikos, 1977, 28, 74. Jewson, D. H., and Wood, R. B., Verh. Int. Vev. Limnol., 1975, 19, 1037. Foy. R. H., Gibson, C. E., and Smith, R. V., Br. Phycol. J . , 1976, 11, 151. Gibson, C. E., J . Ecol., 1975, 63, 867. Gibson, C. E., J . Ecol., 1978, 66, 97. Gibson, C. E., Verh. I’nt. Ver. Theor. Angew. LimnoZ., 1978, 20, 630. Parr, M. P., and Smith, R. V., Water Res., 1976, 10, 1151. Wood, R. B., and Gibson, C. E., Water Res., 1973, 7, 173. Smith, R. V., Tech. Bull. Minist. Agric. Fish Fd., London, 1975, No. 32, p. 315. Smith, R. V., Water Res., 1977, 11, 453. Alexander, G. C., and Stevens, R. J., Water Res., 1976, 10, 757. Stevens, R. J., and Smith, R. V., Water Res., 1978, 12, 823. Stewart, D. A., PhD Thesis, Queen’s University of Belfast, 1975. Hansard (N. Ireland), 2nd June 1971. “Lough Neagh (algal blooms),” Statement by R. Bradford, Minister of Development, p. 787. Stevens, R. J., and Gibson, C. E., i n Golterman, H. L., Editor, “Interactions Between Sediments and Freshwater,” SIL/UNESCO Symposium, Junk/Pudoc, 1976, p. 343. Rippey, B., i n Gotterman, H. L., Editor, “Interactions Between Sediments and Freshwaters,” SIL/ UNESCO Symposium, Junk/Pudoc, 1976, p. 348. Carter, C. E., Ir. Nut. J . , 1975, 18, 245. Carter, C. E., Oikos, 1976, 27, 346. Carter, C. E., i n “Holarctic Ecology,” Volume 3, in the prcss. Carter, C. E., Acta Univ. Cavol., in the press. Wilson, J., DPhil Thesis, New University of Ulster, 1979. Dabrowski, K., personal communication. Keegan, T. A. J., BA Thesis, New University of Ulster, 1978. Rogers, J ., unpublished work. Edmondson, W. T., “The Present Condition of Lake Washington,” Verh. Int. V w . Limnol., 1972, Ahlgren, I., i n Golterman, H. L., Editor, “Interactions Between Sediments and Freshwaters,” Thomas, E. A., and Wildi, P., “The Effects of Storage on Water Quality,” WRC Symposium, 1975, McCracken, E. M., Ulster J . Archaeol., 1947, 10, 15. McCracken, E. M., “The Irish Woods Since Tudor Times. David and Charles. Newton Abbot, 1971. Battarbee, R. W., Phil. Trans. R. SOC. London, Ser. B., 1978, 281, 303. Carter, C. E., Freskwatev Biol., 1977, 7, 415. 146. 18, 284. SIL/UNESCO Symposium, Junk/Pudoc, 1976, p. 372. Water Research Centre, Medmenham, Oxfordshire, 1975, p. 343. Their Distribution and Exploration,”

ISSN:0144-557X    

DOI:10.1039/AP9801700348

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

September, 1980 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS 375 Different Forms of Phosphorus in Freshwater R. J. Stevens Department of Agriculture, Freshwater Biological Investigation Unit, Greenmount Road, Muckamore, Antrim, BT41 4PX, Northern Ireland Phosphorus Chemistry in Freshwater Phosphorus has been identified as a key factor governing the growth of algae in Lough Neagh. Like carbon, phosphorus can exist in freshwater in a vast number and variety of molecular structures. The dominant phosphorus compounds will contain phosphorus with a co- ordination number of 4. Chief among these are the phosphates, in which phosphorus exists in oxidation state +5. Compounds containing the phosphorus-carbon bond have been identified in biological systems. Such compounds could persist in freshwater because of the stability of the bond, but they are thought to be insignificant quantitatively compared with phosphate-containing compounds.Some phosphate properties governing the different forms of phosphorus likely to exist in freshwater are (i) condensation reactions resulting in esters and polyphosphates, (ii) precipitation reactions forming low-solubility compounds, (iii) adsorption on to surfaces of clay minerals and hydrous metal oxides and (iv) soluble complex formation with transition and alkaline earth metals. Phosphorus Analyses in Freshwater The analytical procedures are based on the reaction of orthophosphate with molybdate in acidic solution to give molybdophosphoric acid, which, when reduced, forms molybdenum blue. Murphy and Riley’s method1 using antimony as catalyst and ascorbic acid as reducing agent is widely accepted.The concentration of all forms of phosphorus (total phosphorus) is determined by an acid-persulphate digestion of the unfiltered sample prior to the analysis for orthophosphate. Total phosphorus can be divided into two main components, soluble and particulate, by filtration of the sample through a membrane filter, conventionally with 0.45pm pore size. The concentration of all forms of soluble phosphorus (total soluble phosphorus) is determined by an acid-persulphate digestion of the filtered sample prior to the analysis for orthophosphate. The concentration of phosphorus determined by direct analysis of the filtered sample for orthophosphate is called soluble reactive phosphorus. Soluble reactive phosphorus concentrations may be greater than true orthophosphate con- centrations because the acidic conditions of the test may hydrolyse labile esters and poly- phosphates, disintegrate metal - orthophosphate complexes or dissolve colloidal hydrous metal oxides containing adsorbed orthophosphate. Experimental evidence that soluble reactive phosphorus was greater than orthophosphate by about 20% was obtained by comparison with an enzymatic orthophosphate method.2 Soluble unreactive phosphorus is the difference between total soluble and soluble reactive phosphorus analyses.I t represents phosphorus compounds capable of passing through the membrane filter and requiring digestion in acid-persulphate to convert them into orthophosphate.The particulate phosphorus concentration can be obtained by the difference between the total and total soluble deter- minations, or by direct analysis of the material retained on the membrane filter. The relative amounts of soluble reactive phosphorus, soluble unreactive phosphorus and particulate phosphorus in the major river inputs to Lough Neagh are about SO%, 15% and 35%, respectively. It is known that algae can use orthophosphate for growth, and algal available phosphorus in freshwater is often regarded as being equivalent to soluble reactive phosphorus. The chemical nature and availability to algae of the soluble unreactive and particulate phosphxus fractions are largely unknown. Evidence has been obtained for the existence of inositol phosphates in the soluble unreactive f r a ~ t i o n .~ , ~ The quantitative identification of components in the soluble unreactive and particulate phosphorus fractions is being investi- gated in this laboratory. Soluble Unreactive Phosphorus The concentrations of soluble unreactive phosphorus in the river inputs to Lough Neagh As these concentrations are too low for any direct identification are typically 10-20 pg 1-l.Anal. PYOC. of specific phosphorus compounds, a concentration step was developed. Evaporation, freeze-drying, ultrafiltration and adsorption - precipitation as methods of concentration were evaluated. A simple adsorption - precipitation technique was chosen using lanthanum as the coagulant, resulting in a concentration factor of at least 100 for soluble unreactive phosphorus.The soluble unreactive phosphorus concentrates were then subjected to gel filtration chromatography after selection of a suitable gel (Sephadex G-50), column (90 x 3.2 cm) and buffer (sodium tetraborate). Soluble unreactive phosphorus eluted at the void volume, indicating compounds with relative molecular mass > 10000, and together with soluble reactive phosphorus, indicating compounds with a relative molecular mass of about 1000. Similar observations have been made by gel filtration and anion-exchange chromato- graphy of freshwater without pre-concentration of soluble unreactive pho~phorus.~.~ Starting the concentration procedure with 10 1 of freshwater results in about 20pg of soluble un- reactive phosphorus eluting from the gel filtration column as the high relative molecular mass component.Attempts are now being made to process 100-1 batches of freshwater, perform gel filtration on a preparative scale and use a volatile buffer, so that soluble unreactive phosphorus fractions may be isolated in sufficient amounts to be able to perform more separation and identification techniques. Techniques such as mass spectrometry, gas chromatography of phosphate derivatives combined with mass spectrometry and 31P nuclear magnetic resonance spectroscopy could be useful. 376 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Particulate Phosphorus Possible components of the particulate phosphorus fraction are sand, silt, coarse clay, medium and fine clay aggregates, algae, bacteria, zooplankton, organic debris and hydrous metal oxides with adsorbed orthophosphate, organic phosphates or polyphosphates.The hydrous iron( 111) oxide - orthophosphate component of particulate phosphorus is being investigated at present. Iron(II1) exists in freshwaters at pH 7-8 as hydrous iron(II1) oxide, on to which orthophosphate can be complexed and/or adsorbed. This hydrous oxide should be readily soluble in acid. Particulate phosphorus retained on a membrane filter was treated with sulphuric acid of similar concentration to that used in the soluble reactive phosphorus test. The orthophosphate and iron( 111) solubilised were then determined. There was a positive relationship between the amount of orthophosphate and the amount of iron(II1) solubilised for a range of river water samples.In the 76 samples analysed, acid- soluble orthophosphate accounted for 49% of the particulate phosphorus fraction. Acid- and alkali-soluble concentrates from particulate phosphorus are also being subjected to gel filtration studies in the same way as for soluble unreactive phosphorus concentrates. Organic phosphorus compounds that exist in the particulate phosphorus fraction because of association with particulate material may be identifiable. References 1. 2. 3. 4. 5. 6. Murphy, J., and Riley, J. P., Anal. Chim. Acta. 1956, 27, 31. Stevens, R. J., Water Res., 1979, 13, 763. Eisenreich, S. J., and Armstrong, D. E., Environ. Sci. Technol., 1977, 11, 497. Herbes, S. E., Allen, H. E., and Mancy, K. H., Science, 1975, 187, 432. Peters, R. H., J . Fish. Res. Board Can., 1978, 35, 315.Francko, D. A., and Heath, R. T., Limnol. Oceanogr., 1979, 24, 463. Reduction of Nutrient Input to Lough Neagh by Phosphorus Removal at Sewage Treatment Works A. V. Gray Water Quality Branch, Industrial Science Division, Department of Commerce, 5-1 1 Verner Street, Belfast, Northern Ireland The addition of extra nutrient to a lake can result in excessive algal blooms. A gradual enrichment of Lough Neagh has been taking place since 1900, due mainly to the advent of the water closet and changing agricultural practices involving the widespread use of artificialSeptember, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 377 fertilisers. Fish life suffered, domestic and industrial water supplies were affected and the amenity value of the shoreline deteriorated.Published methods of controlling eutrophication1 include harvesting weed and/or algae, using fish as grazers, addition of copper sulphate or herbicides, flow diversion or dilution and lake modification. The Wood and Gibson report2 indicated that phosphorus was the limiting nutrient in Lough Neagh and estimated that 80% of the total phosphorus load entering it had originated from the major treatment works. Subsequent measurement by the Water Quality Branch (WQB) of the phosphorus load discharged from the major sewage treatment works3 revealed that the figure was only about 40% of the total. The remainder originates from agricultural run-off, land drainage, the rural population and rainfall.4 In 1967, massive blooms of Anabaena pas-aqua occurred.Chemical precipitation at source has also been employed. Phosphorus in Sewage The water-borne phosphorus entering a sewage treatment works comes from three main sources. The domestic contribution is split between the phosphorus originating from detergents and that of human origin from excreta. The third source is the industrial contri- bution. In Northern Ireland the detergents contribute about 45-50y0 of the total amount of phosphorus in sewage and industry is responsible for 15-20~0. The remainder is of human origin. The results of a survey5 of a Northern Ireland housing estate suggest that the domestic contribution may be lower than in the remainder of the UK. Untreated sewage contains a mixture of phosphorus compounds, including dissolved ortho- phosphate, dissolved and particulate organic phosphate, inorganic condensed phosphates and particulate inorganic phosphates, either precipitated or absorbed on to other solids.During the normal treatment stages at a sewage works, some of the particulate phosphorus will be biologically degraded and inorganic condensed phosphates will be hydrolysed to dissolved orthosphosphate. Detergent formulations include polyphosphates as builders and water conditioners, typically sodium tripolyphosphate (STPP) , Na,P,O,,. Human excreta contains various organic phosphates in addition to orthophosphate.6 Phosphorus Reduction at Sewage Treatment Works Some of the phosphorus present in sewage is removed during the normal treatment pro- cesses. Removals of 5-15y0 have been recorded at the primary sedimentation stage.’ During biological purification at the secondary treatment stage, phosphorus is required for normal cell growth, the amount being normally limited by the carbon requirements.Up to 20% reductions have been recorded at a normal activated sludge stage,s while 15% reductions at most were reported across a biological filter.g Enhanced phosphorus reductions have been obtained at some activated sludge works by modifiying the normal mode of operation, This “luxury uptake” process has received considerable attention in South Africa,lo-12 where consistent phosphorus removals of 85% have been claimed. Other physical methods for phosphorus removal include ion exchange, reverse osmosis, electrodialysis and adsorption using soil spreading1 As the control of biological processes for phosphorus removal is not straightforward and physical methods are generally economically prohibitive, most phosphorus reduction plants normally employ chemical addition.Chemical Methods The addition of a single chemical coagulant, or in some instances a mixture, normally results in the precipitation of soluble phosphates and coagulation of other species present, followed by particle agglomeration and subsequent settlement in the existing sedimentation tanks. The chemical solids so produced may have settlement characteristics inferior to the normal sewage solids and the existing sedimentation tanks may be somewhat ineffective in solid - liquid separation. Mechanical flocculation is often employed as a means of over- coming this problem by increasing the frequency of particle collision and causing larger378 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal.Proc. aggregates to form, usually of increased density. Sometimes polyelectrolytes are added to improve floc aggregation further. A subsequent filtration stage may be employed to produce very small phosphorus residuals. Coagulants may be added at one of three different points in the normal sewage treatment process, viz., pre-primary, post-primary and post-secondary (or tertiary). Normally the chemical employed is a salt of calcium (most commonly lime), iron [as the iron(I1) or iron(II1) chloride or sulphate] or aluminium (as the sulphate, chlorohydrate or aluminate). Iron(I1) sulphate and lime have been dosed together on occasions.Development Work in Northern Ireland Conventional Dosing Taking account of local circumstances, the former Water Pollution Research Laboratory (WRRL), now the Water Research Centre (WRC), suggested that lime should be added as the coagulant at the tertiary treatment stage to effect a reduction in the phosphorus content of the sewage. Laboratory experiments were then undertaken by WQB to establish dose rates, floc settlement characteristics and size of flocculation tank required in order that a pilot-scale plant could be constructed. The results of the laboratory experiments indicated that the higher the alkalinity of the sewage, the greater is the amount of lime required to attain the same degree of phosphorus removal. Further, the process appeared to be pH dependent.By employing filtration lower lime doses could be used, with less sludge pro- duced (Fig. 1). 0 10 20 30 a? 2 6 40 E 50 3 60 z t? 70 L 80 30 1 m 6 20 $ --. - 0 a, 0, U 10 3j 90 100 8 9 10 1 1 12 PH Fig. 1. Percentage of phosphorus removed and increase in sludge volume with increase in pH. The initial pilot-plant investigations were carried out using pH-controlled dosing followed by flocculation, sedimentation and filtration to achieve phosphorus reduction. The results were encouraging, about a 75% phosphorus removal being achieved after settlement alone, and greater than 85% by subsequent pass'age through an Immedium filter (Fig. 2). Split-effluent Dosing This method involves splitting the sewage into two unequal portions, adding the total lime dose to the smaller volume and mixing for a certain period, then blending with the remainder of the sewage and finally mixing for a further period.The benefits of the split-effluent process are that phosphorus removals similar to those normally produced by the conventional process can be achieved using smaller amounts of coagulant, and the concomitant reduction in the pH of the final effluent reduces neutralisation costs (Fig. 3). At roughly the same time a coagulant was produced by the Industrial Science Division from local bauxite deposits. It was found to have a potential for removing phosphorus from sewage effluents. Consequently, laboratory investigations were carried out on severalSeptember, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS c ! - B /-- \ ......D . . , , . ,.: , , , , ,. , ,, , , , , ,., , , ,, ,, , . , . ... ....... . . . . .... . . .. . .._. . . . .. .. .. .. . ... . ..... 1 I 379 12 24 12 24 12 Wed. Thur. Fri. Fig. 2. Results for Rallymena pilot plant. A, Un- treated; B, after settlement; C, Immedium filtered; and D, 0.45-pm filter. coagulants. The final costings which the Department of the Environment produced showed clearly that the split-effluent lime process should be implemented at biological filtration plants. At activated sludge works dosing with iron(I1) sulphate to the mixed liquor stage was the most beneficial and economic process. 4 .o t I m -. - E 3.0 0 r Q L a - B 2.0 + m 3 - 0 $ a 1 .o 0 100 200 300 400 Lime dose/mg I-' Ca(OHh Fig. 3. Addition of lime to sewage: comparison of methods.Sample PF 112. Alkalinity, 99 mg 1-l: Split, 200 : 800. Phosphorus concentrations : settled, conventional (B), split effluent (C) ; filtered ( < 1 pm), conventional (F), split effluent (E). Sludge volumes: conventional (A) ; split effluent (D). WQB then carried out laboratory work to establish the necessary design parameters for The optimum ratio for flow Minimum mixing times of 2 min were required at large-scale implementation of the split-effluent lime process. separation was found to be about 1 : 4.380 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. Proc. both the first and second stages of the process if goDd phosphorus removals were to be achieved with sedimentation alone. Thz initial results were encouraging, and 75% phosphorus removals were achieved using a 1:4 effluent split and a lime dose of 220 mg 1-1 of Ca(OH), (Fig.4). Floc shear was critical on the second stage mixing. Modifications were then made to the existing pilot plant. Q m 2.0 c 0 I - Average = 3.56 mg % removal = 84.55 I- After sedimentation L--J Average = 0.25 mg I-' P I I I I I I-' P '. '. t Average = 0.55 mg I-' P U nf i I tered 24 24 24 24 Sat. 15.5.76 Sun. 16.5.76 Mon. 17.5.76 Tue. 18.5.76 Fig. 4. Pilot-plant phosphorus concentrations. Run PPE. Dose, 240 mg 1-l of Ca(OH),. Split, 19:81. Sludge production at the pilot plant was found to be about 0.6-0.7% of the total treated volume, compared with about 1.5% found in the laboratory work. The concentrations of solids in the sludge produced varied between 48 and 61 kg m-3 (4.8-6.1y0 solids).The pilot plant was then further modified to enable it to treat the total flow at the works. During periods of smooth operation excellent phosphorus removals of greater than 90% could be achieved (Fig. 5). 24 12 24 12 24 12 24 12 24 12.4.78 13.4.78 14.4.78 15.4.78 Fig. 5 . Full-scale plant phosphorus concentrations. Dose, Solid lines, unfiltered; broken line, filtered. 220 mg 1-1 of &(OH),. Iron(I1) Sulphate Dosing A full-scale phosphorus reduction plant capable of dosing iron( 11) sulphate was constructed at the Ballynacor sewage treatment works at about the same time as the full-scale split- effluent lime plant was built at the Ballymena works. Owing mainly to shortages of staff, WQB were not able to operate this plant concurrently with work at the Ballymena works.September, 1980 POLLUTANTS IN THE TROPOSPHERE AND NATURAL WATERS 381 The plant at the Ballynacor works consists of a debagging area and a feed hopper with a screw dry feeder leading into solution make-up storage tanks.These lead to a break- pressure tank, which is piped directly to the metering pumps. Control instrumentation has been installed to provide for automatic flow related dosing. Typical dose rates envisaged were 6-16 mg 1-1 of Fe. It was expected that effluent total residual phosphorus concentration of 1-1.5 mg 1-1 would be achieved. Recent Developments During the period of running the split-effluent lime process, bulk supply of lime from local producers ceased. The very significant increased costs of imported lime plus the potential availability of the locally produced alumino-ferric liquor have recently led to a re-appraisal of the choice of coagulant for phosphorus reduction. In the long term the capital and operational costs of using lime in the split-effluent process could be considerably greater than for dosing the alumino-ferric liquor.The Department of the Environment therefore requested WQB to carry out a feasibility study on the use of this coagulant added to crude sewage as a means of phosphorus reduction. The initial results indicate that dosing with the alumino-ferric liquor at three different rates depending on the time of day could be a viable alternative to the processes previously envisaged for phosphorus reduction at sewage treatment works in the Lough Neagh catchment. Full-scale trials are about to commence, the results of which will be used in deciding future management policy.References 1. 2. 3. 4. 5. 6. 7. Porcella, D. B., and Bishop, A. B., “Comprehensive Management of Phosphorus Water Pollution,” Ann Arbor Science Publishers, Ann Arbor, Mich., 1975. Wood, R. B., and Gibson, C. E., Water Res., 1973, 7, 173. Wilson, J. A., “Contribution of Point Sources Especially Domestic Sewage,” Lake Pollution Eutro- Smith, R. V., “Lough Neagh Investigations,” Eutrophication of Lakes and Reservoirs, Symposium Alexander, G. A., and Stevens, R. J., Water Res., 1976, 10, 757. Thorpe, W. V., Bray, H. G., and Jamej, S. P., “Biochemistry for Medical Students,” Churchill, Edinburgh, 1964, p. 515. Jenkins, D., and Menar, A. B., “The Fate of Phosphorus in Sewage Treatment Process, Part I, Primary Sedimentation and Activated Sludge,” SERL Report No.67-6, University of California, Berkeley, 1967. Jenkins, D., and Menar, A. B., “The Fate of Phosphorus in Sewage Treatment Processes, Part 11, Mechanism of Enhanced Phosphate Removal by Activated Sludge,” SERL Report No. 68-6, University of California, Berkeley, 1968. Vollenweider, R. A,, 1968, “Scientific Fundamentals of the Eutrophication of Lakes and Flowing Waters, with Particular Reference to Nitrogen and Phosphorus as Factors in Eutrophication,” Report to OECD, Paris, DAS/CSI/SS, 27, 1. phication Control, Seminar of the National Science Council, Killarney, 1977. of the Institution of Public Health Engineers, 1976. 8. 9. 10. 11. 12. Barnard, J.L., Water Res., 1975, 9, 485. Barnard, J. L., “Nutrient Removal in Biological Systems,” J . I m t . Water Pollut. Control, 1975, 74, Barnard, J. L., Water S.Afr., 19’76, 2, 136. 143. Determination of Polynuclear Aromatic Hydrocarbons in Water N. T. Crosby and D. C. Hunt Depavtment of Industry, Laboratory of the Government Chemist, Cornwall House, Stamford Street, London, SE1 9NQ Polynuclear aromatic hydrocarbons (PAHs) are fused-ring compounds formed during the pyrolysis or incomplete combustion of organic matter. Benzo [alpyrene (3,4-benzpyrene) is probably the best known and most extensively studied member of this family of compounds following its identification as a carcin0gen.l About 200 closely related PAH compounds have now been identified but not all are carcinogenic.These compounds are only very slightly soluble in water, their volatility is low and the absence of polar groups results in little reactivity apart from intense characteristic fluorescence emission spectra. Hence there is a real need to develop reliable analytical methods that can identify and discriminate382 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS Anal. PYOC. between a large number of individual compounds likely to be present in a wide variety of substrates only at extremely low levels. Other sources of PAHs include vehicle exhaust emissions and industrial effluents so that the compounds are found widely distributed through- out the environment. PAHs may, therefore, occur in water supplies as a result of pollution by industrial effluents, run-off from tarred or asphalted roads or by leaching from soil or from atmospheric fall-out.The potential danger to human health of these compounds was recognised in 1971 by the World Health Organization (WHO). In their International Standards for Drinking Water2 they recommended that amounts of six representative compounds (fluoranthene, 3,4- benzfluoranthene, 1 1 ,12-benzfluoranthene, 3,4-benzpyrene, 1,12-benzperylene and indeno- [1,2,3-cd]pyrene) should not, in general, exceed 0.2 pg 1-1 in potable waters. Higher con- centrations would be indicative of pollution and insufficient treatment. A similar standard has been proposed by the Council of the European Economic Community.3 Whilst the literature contains numerous papers on the determination of many different PAHs in a wide variety of substrates, few have dealt specifically with the separation and measurement of the six compounds recommended by WHO.Borneff and Kunte4 have described a two- dimensional thin-layer chromatographic method, following extraction of the sample with cyclohexane, which has a detection limit of about 2-3 ng 1-1 for each individual PAH. However, the potential of high-performance liquid chromatography coupled with fluorescence detection for this type of work has been investigated, initially for the determina- tion of residual amounts of PAHs in foods. The available column packing materials were unsatisfactory for the separation of these compounds and, hence, a new chemically bonded stationary phase, phthalimidopropyltrichlorosilane (PPS) , was prepared and evaluated.This particular material was selected bearing in mind both the structure of PAH compounds with their aromatic ring systems as well as the known selective extraction properties of dimethylformamide. The preparation of the new material has been described by Hunt eta1.536 Separations using the PPS column can be achieved that are not possible with other packing materials, e.g., octadecylsilane (ODs), and with both columns useful changes in retention times are observed that can be used to confirm the identity of unknown compounds. The PPS column can be used in both normal- and reversed-phase modes, the order of elution of the six compounds being different from that obtained on the ODS column. Of particular interest is the change in retention time of benzo [alpyrene and the fact that benzo[k]fluoranthene and perylene are separated on the PPS column but not on the ODS column.Many of the problems encountered in the analysis of different samples for PAHs arise from the difficulty of separating the compounds from the sample matrix. For example, we were asked to determine benzo[a]pyrene in samples of smoke produced during the burning of stubble. The smoke samples were collected on impactor filters and particles of soot were obviously present as well. In developing a method activated charcoal was used as a test substrate to check the recovery of PAH compounds from the filter media. Simple extrac- tion using a variety of solvents gave unacceptably low recoveries. Hence, the Soxhlet apparatus over a 7-h period was used.Recoveries of benzo[a]pyrene with four different solvents are shown in Table I. Clearly, benzene is far superior to other solvents for this particular substrate and yet other solvents are often used when particulate matter is known to be present. Superficially, water should be one of the easiest substrates for analysis as PAHs are only very slightly soluble in aqueous systems. However, at the low concentrations encountered TABLE I RECOVERY OF BENZO [a]PYRENE FROM ACTIVATED CHARCOAL USING A SOXHLET APPARATUS Recovery, yo v- 7 Solvent Range Mean Benzene . . . . . . 80-100 87 Cyclohexane .. .. 5-6 5.6 Dichloromethane . . .. 4720 8.6 Acetone . . .. .. 8-17 14September, 1980 POLLUTANTS I N THE TROPOSPHERE AND NATURAL WATERS 383 adsorption on to glass surfaces and sediment (if present) may cause difficulties for the analyst.In our work we have taken samples of River Thames water at Waterloo Bridge for analysis in the belief that other surface waters of drinking water quality would give fewer problems. Methods of analysis are generally checked by the addition of known amounts of the deter- minant to the sample, followed by analysis to check on recoveries. In this instance, the poor solubility of PAHs in water makes this operation difficult and the compounds are usually added in an organic solvent (often the same solvent used in the subsequent extraction stage). Clearly, this does not adequately reflect the real-life sampling situation. We attempted to “spike” tap water with PAHs dissolved in methanol. After shaking, the sample was filtered through a membrane filter and 60-80y0 of the PAHs were recovered.However, after standing overnight before extraction and analysis, only 45-60Y0 of the original amounts of PAHs were recovered, suggesting that adsorption on to the walls of the glass bottle was taking place. Direct extraction of the water sample and bottle using isooctane gave recoveries of SO-SO% even after the sample had been left to stand for 3 days before extraction. This is shown in Table 11. If, however, the solvent was added to the bottle before taking the sample, increased recoveries in the range 75-95y0 were obtained. Hence, we recommend that some of the extraction solvent be added to each sample bottle before sampling the water for analysis.TABLE 11 EFFECT OF PRIOR ADDITION OF SOLVENT TO SAMPLE BOTTLE Unspiked/ng 1-1 A r \ Compound No solvent With solvent Fluoranthene . . .. . . 10.2 15.3 Benzo[b]fluoranthene . . . . 0.7 1.3 Benzo[k]fluoranthene . . . I 0.2 0.3 Benzo[a]pyrene . . .. . * 1.8 4.2 Tndeno[1,2,3-cd]pyrene . . . . ND* ND* Benzo[ghi]perylene . . .. 2.4 4.4 Spiked e R G no solvent, yo solvent, yo 69 74 66 83 71 81 81 96 60 88 59 82 * Not detected. The effect of filtration is shown in Table 111. A sample of raw River Thames water was sampled both with and without filtration and both with and without addition of solvent prior to sampling the water. Enhanced recoveries of PAH compounds were obtained for both unfiltered and filtered samples through prior addition of solvent. Using the Perkin- Elmer 3000 detector, picogram amounts of PAHs can be measured, giving a detection limit in favourable circumstances as low as 0.01 ng 1-1 in water. TABLE I11 EFFECT OF FILTRATION AND SAMPLING ON PAHs IN RIVER THAMES WATER PAH compounds/ng 1-1 Filtered Unfiltered f A \ Compound e W - b o solvent hWith solvent ’ Fluoranthene . . .. . . 10.2 15.3 540 667 Benzo;blfluoranthene . . .. 0.7 1.3 85 99 Benzo[k]fluoranthene . . . . 0.2 0.3 17 20 Renzo:a]pvrene . . . . .. 1.8 4.2 294 430 IndenoC1,2,3-cd]pyrene . . .. ND* ND* ND* ND* Benzo[ghi]perylene . . .. 2.9 4.4 500 541 * Not detectxl References 1. Cook, J. W., Hieger, I., Kennaway, E. L., and Mayneord, W. V., Proc. R. SOC., London, Ser. B, 1932, 111, 455.384 EQUIPMENT NEWS Anal. Proc. 2. 3. 4. 5. 6. World Health Organization, “International Standards for Drinking Water,” WHO, Geneva, 1971. Council Directive 75/440/EEC, Off. J . Eur. Commun., L.194, 25 July 1975, p. 29. BornefT, J., and Kunte, H., Arch. Hyg. Bakterzol., 1969, 153, 220. Hunt, D. C., Wild, P. J., and Crosby, N. T., J . Chrornatogr., 1977, 130, 320. Hunt, D. C., Wild, P. J., and Crosby, N. T., Water Res., 1978, 12, 643.

ISSN:0144-557X    

DOI:10.1039/AP9801700375

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

384 EQUIPMENT NEWS Anal. Proc. Equipment News Liquid Chromatogram Column Packer A new column packer for high-performance liquid chromatograms operates up to a pressure of 9000 lb in-2, which is sufficient to pack all 5 mm i.d. analytical and 8 mm i.d. preparative columns. The volume per stroke is 2.35 ml and the maximum flow-rate is about 300 ml min-l. There are reservoirs for two packing solvents. The column is fitted with a safety screen, enab- ling the column to be reversed safely under the high pressure. Insert 542 on the Reader Enquiry Service form for further information. Columns for Liquid Chromatography The Shodex S800 series is composed of a range of columns suitable for use with water-soluble polymers and organic materials, e.g., bio- chemicals, foods, drugs and complex industrial wastes, The packing is designed to operate with an aqueous mobile phase.Perkin-Elmer Ltd. Insert 543 on the Reader Enquiry Service form for further information. Shandon Southern Products. Open Tubular Columns Columns for open tube chromatography are now available in natural quartz and fused silica. Both materials produce inert columns, with the former slightly more acidic. Both are more robust than glass columns. Perkin-Elmer Ltd. Insert 544 on the Reader Enquiry Service form for further information. Spectrophotometer The Micro Match is equipped with a diffraction grating and 16-channel silicon detector designed for high wavelength accuracy and long stability. A micro-processor and video unit are incorpor- ated in the standard array, with graph plotter, graphical video display and line printer available as optional additions. Three different colour difference equations can be set up a t any one time, e.g., illuminents D65 (artificial daylight) and A (tungsten) plus two others. Instrumental Colour Systems.Insert 545 on the Reader Enquiry Service form for further information. Atomic-absorption Spectrophotometer The SB 900, a compact, high-performance basic spectrophotometer, contains a novel spray chamber - burner design. Versatility can be achieved by adding accessories, such as simul- taneous background correction, a vapour generator, a printing calculator and dual lamp supplies. Guaranteed detection limits are arsenic 0.4 p.p.m., magnesium 0.000 2 p.p.m., copper 0.003 p.p.ni. and potassium 0.003 p.p.m.EDT Research. Insert 546 on the Reader Enquiry Service form for further information. Injector for Gas Chromatographs The injector is designed specifically for use with the Sigma series of gas chromatographs, employ- ing glass, metal, fused silica and natural quartz open tubular columns, as well as packed columns. It can be fitted to any Sigma instrument with a heated injection block and will perform split, normal splitless and “Grob” type splitless injec- tions. Perkin-Elmer Ltd. Insert 547 on the Reader Enquiry Service form for further information. Quartz Capillary Columns Columns made in fused vitreous silica are now available with a choice of FFAP, Carbowax 20R1, OV-101 and OV-17 stationary phases. With an internal diameter of 0.2 mm and lengths of 25 and 50 m, the tubes have an external coating of polymeric material enabling them to withstand temperatures up to 300 “C.Scientific Glass Engineering (UK) Ltd. Insert 548 on the Reader Enquiry Service form for further information. Capillary Column Aid ,4 magnetic label with a wipe-clean surface which will adhere to a metal surface of a gas chromatograph is available free of charge. Insert 549 on the Reader Enquiry Service form for further information. Erba Science (UK) Ltd.384 EQUIPMENT NEWS Anal. Proc. Equipment News Liquid Chromatogram Column Packer A new column packer for high-performance liquid chromatograms operates up to a pressure of 9000 lb in-2, which is sufficient to pack all 5 mm i.d. analytical and 8 mm i.d. preparative columns. The volume per stroke is 2.35 ml and the maximum flow-rate is about 300 ml min-l.There are reservoirs for two packing solvents. The column is fitted with a safety screen, enab- ling the column to be reversed safely under the high pressure. Insert 542 on the Reader Enquiry Service form for further information. Columns for Liquid Chromatography The Shodex S800 series is composed of a range of columns suitable for use with water-soluble polymers and organic materials, e.g., bio- chemicals, foods, drugs and complex industrial wastes, The packing is designed to operate with an aqueous mobile phase. Perkin-Elmer Ltd. Insert 543 on the Reader Enquiry Service form for further information. Shandon Southern Products. Open Tubular Columns Columns for open tube chromatography are now available in natural quartz and fused silica. Both materials produce inert columns, with the former slightly more acidic. Both are more robust than glass columns.Perkin-Elmer Ltd. Insert 544 on the Reader Enquiry Service form for further information. Spectrophotometer The Micro Match is equipped with a diffraction grating and 16-channel silicon detector designed for high wavelength accuracy and long stability. A micro-processor and video unit are incorpor- ated in the standard array, with graph plotter, graphical video display and line printer available as optional additions. Three different colour difference equations can be set up a t any one time, e.g., illuminents D65 (artificial daylight) and A (tungsten) plus two others. Instrumental Colour Systems. Insert 545 on the Reader Enquiry Service form for further information.Atomic-absorption Spectrophotometer The SB 900, a compact, high-performance basic spectrophotometer, contains a novel spray chamber - burner design. Versatility can be achieved by adding accessories, such as simul- taneous background correction, a vapour generator, a printing calculator and dual lamp supplies. Guaranteed detection limits are arsenic 0.4 p.p.m., magnesium 0.000 2 p.p.m., copper 0.003 p.p.ni. and potassium 0.003 p.p.m. EDT Research. Insert 546 on the Reader Enquiry Service form for further information. Injector for Gas Chromatographs The injector is designed specifically for use with the Sigma series of gas chromatographs, employ- ing glass, metal, fused silica and natural quartz open tubular columns, as well as packed columns.It can be fitted to any Sigma instrument with a heated injection block and will perform split, normal splitless and “Grob” type splitless injec- tions. Perkin-Elmer Ltd. Insert 547 on the Reader Enquiry Service form for further information. Quartz Capillary Columns Columns made in fused vitreous silica are now available with a choice of FFAP, Carbowax 20R1, OV-101 and OV-17 stationary phases. With an internal diameter of 0.2 mm and lengths of 25 and 50 m, the tubes have an external coating of polymeric material enabling them to withstand temperatures up to 300 “C. Scientific Glass Engineering (UK) Ltd. Insert 548 on the Reader Enquiry Service form for further information. Capillary Column Aid ,4 magnetic label with a wipe-clean surface which will adhere to a metal surface of a gas chromatograph is available free of charge.Insert 549 on the Reader Enquiry Service form for further information. Erba Science (UK) Ltd.384 EQUIPMENT NEWS Anal. Proc. Equipment News Liquid Chromatogram Column Packer A new column packer for high-performance liquid chromatograms operates up to a pressure of 9000 lb in-2, which is sufficient to pack all 5 mm i.d. analytical and 8 mm i.d. preparative columns. The volume per stroke is 2.35 ml and the maximum flow-rate is about 300 ml min-l. There are reservoirs for two packing solvents. The column is fitted with a safety screen, enab- ling the column to be reversed safely under the high pressure. Insert 542 on the Reader Enquiry Service form for further information.Columns for Liquid Chromatography The Shodex S800 series is composed of a range of columns suitable for use with water-soluble polymers and organic materials, e.g., bio- chemicals, foods, drugs and complex industrial wastes, The packing is designed to operate with an aqueous mobile phase. Perkin-Elmer Ltd. Insert 543 on the Reader Enquiry Service form for further information. Shandon Southern Products. Open Tubular Columns Columns for open tube chromatography are now available in natural quartz and fused silica. Both materials produce inert columns, with the former slightly more acidic. Both are more robust than glass columns. Perkin-Elmer Ltd. Insert 544 on the Reader Enquiry Service form for further information. Spectrophotometer The Micro Match is equipped with a diffraction grating and 16-channel silicon detector designed for high wavelength accuracy and long stability.A micro-processor and video unit are incorpor- ated in the standard array, with graph plotter, graphical video display and line printer available as optional additions. Three different colour difference equations can be set up a t any one time, e.g., illuminents D65 (artificial daylight) and A (tungsten) plus two others. Instrumental Colour Systems. Insert 545 on the Reader Enquiry Service form for further information. Atomic-absorption Spectrophotometer The SB 900, a compact, high-performance basic spectrophotometer, contains a novel spray chamber - burner design. Versatility can be achieved by adding accessories, such as simul- taneous background correction, a vapour generator, a printing calculator and dual lamp supplies.Guaranteed detection limits are arsenic 0.4 p.p.m., magnesium 0.000 2 p.p.m., copper 0.003 p.p.ni. and potassium 0.003 p.p.m. EDT Research. Insert 546 on the Reader Enquiry Service form for further information. Injector for Gas Chromatographs The injector is designed specifically for use with the Sigma series of gas chromatographs, employ- ing glass, metal, fused silica and natural quartz open tubular columns, as well as packed columns. It can be fitted to any Sigma instrument with a heated injection block and will perform split, normal splitless and “Grob” type splitless injec- tions. Perkin-Elmer Ltd. Insert 547 on the Reader Enquiry Service form for further information. Quartz Capillary Columns Columns made in fused vitreous silica are now available with a choice of FFAP, Carbowax 20R1, OV-101 and OV-17 stationary phases.With an internal diameter of 0.2 mm and lengths of 25 and 50 m, the tubes have an external coating of polymeric material enabling them to withstand temperatures up to 300 “C. Scientific Glass Engineering (UK) Ltd. Insert 548 on the Reader Enquiry Service form for further information. Capillary Column Aid ,4 magnetic label with a wipe-clean surface which will adhere to a metal surface of a gas chromatograph is available free of charge. Insert 549 on the Reader Enquiry Service form for further information. Erba Science (UK) Ltd.Septembey, 1980 EQUIPMENT NEWS 387 Hydrogen Sensor A hydrogen sensor with a detection limit of 0.5% by volume for hydrogen in air is available to monitor the conditions inside a gas-chromato- graph oven.As the explosive limit of hydrogen is 4% by volume, this sensor ensures safe operating conditions to enable hydrogen to be used as carrier gas, which is particularly useful in surface-coated, open tubular column, high- resolution gas chromatography. Insert 550 on the Reader Enquiry Service form for further information. Erba Science (UK) Ltd. Gas Chromatograph - Infrared Interface System An all-nickel interface system consisting of a nickel-plated injector port and thermal con- ductivity detector, all nickel valves and tubing and either glass or nickel columns, is available to extend the application of this technique to the analysis of unstable compounds, e.g., diacetyl- morphine.Bio-Rad Laboratories. Insert 551 on the Reader Enquiry Service form for further information. Recording Infrared Spectrophotometers The 680 Series of ratio recording infrared spectrophotometers use microprocessors to calculate sample transmittance or absorbance and to control instrument operation. Models 681, 682 and 683 scan down to 600, 400 and 200 cm-l. The ratio recording accuracy is better than 0.2% transmittance. The instruments are compatible with the Perkin-Elmer infrared data station. Perkin-Elmer Ltd. Insert 552 on the Reader Enquiry Service form for further information. Memory Meters The range of Datastore memory meters are battery operated instruments with 256, 512 or 1 024 readings capacity. They can record events occurring in less than 0.5 s or a t long intervals, and replay them a t a more convenient speed.The interval between recording events and replaying information is variable between 100 ps and 5 h. Waldon Precision Apparatus Ltd. Insert 553 on the Reader Enquiry Service form for further information. Chromatography Data Stations The Sigma 10B/2 data station can support data collections from two chromatographs, whilst the Sigma 10B/4 can operate with four chromato- graphs. Both include magnetic-tape cassettes for data storage and retrieval and an RS 232C communications port. When used with the AS-100 liquid sampler both can provide fully automated control via a binary-coded decimal reader and BASIC 11. Perkin-Elmer Ltd. Insert 554 on the Reader Enquiry Service form for further information.Spinning NMR Probe The FX 60QS, a 6O-MHz nuclear magnetic resonance spectrometer fitted with the “magic angle” probe is designed for use on solid samples, to detect carbon-13 nuclei. The high-speed spinning and cross polarisation of this “magic angle” system overcomes the usual line broaden- ing effect with solid samples. Insert 555 on the Reader Enquiry Service form for further information. Portable pH Meter The PHM 80 portable pH meter is battery oper- ated with a 4-digit display of pH or mV, with a resolution of 0.01 pH or 1 mV units. Insert 556 on the Reader Enquiry Service form for further information. JEOL (UK) Ltd. Radiometer A/S. Luminescence Detector The Pico-lite is designed to detect luminescence produced in biological or chemical reactions by any of the different recommended techniques.It can also be applied to the developing field of luminescence immunoassay (LIA) . It incorpor- ates a sample changer for six samples, with temperature controls, a hard-copy printer and output for external recording devices. Packard Instrument Ltd. Insert 557 on the Reader Enquiry Service form for further information. Digital Thermometer The portable D700 digital thermometer has a range of -50 to 199.9 “C with a resolution of 0.1 “C or of 0-700 “C with a resolution of 1.0 “C. Channel Electronics (Sussex) Ltd. Insert 558 on the Reader Enquiry Service form for further information. Particle Size Analyser The Cilas, Type 715, Granulometer with an ultrasonic generator and agitator ensures homo- geneity of the sample.About 1 g of the powder dispersed in 500 ml of liquid circulates continu- ously through a glass cell. The analyser gives a 16-point, 1-192 ,urn printout and displays an updated curve of the distribution. Specfield Ltd. Insert 559 on the Reader Enquiry Service form for further information.PUBLICATIONS RECEIVED Anal. Proc. Level Controller An infrared level controller, the Series 83, oper- ates on the change of refraction occurring when the conical tip of a quartz-light conductor is im- mersed in a liquid. When in the gas phase, infrared light passes through the light conductor and is reflected back by the conical tip. When the conductor is immersed in liquid, the refrac- tion at the tip disperses the infrared light in the liquid. An accuracy of &-1 mm is claimed, independent of the size of the vessel. Three types of sensor are available to cope with different liquids.Kent Industrial Measurements Ltd. Insert 560 on the Reader Enquiry Service form for further information. Colony Counter A colony counter will accept any Petri dish up to 124 mm diameter and operates by merely depressing the Petri dish. A Wolffhuegel counting graticule, a protective dish well liner and a 90 mm adapter ring are included. A full view magnifier ( x 2) is an available access- ory. Gallenkamp Ltd. Insert 561 on the Reader Enquiry Service form for further information, Laboratory Freeze Drier A small benchtop freeze drier provides rapid drying by the very short vapour path length from the drying vessel to the condenser. Con- struction is all in glass - stainless steel. Borolabs Ltd. Insert 562 on the Reader Enquiry Service form for further information. Disposable Separating Funnels The Schleicher and Schull 597 is a silicone im- pregnated filter-paper which gives rapid and complete separation of aqueous and water immiscible solvents. The funnels are pervious only to the organic phase, being equally applic- able with solvents with higher or lower specific gravities than the aqueous phase. The phase separation fails only if a stable emulsion forms or if the surface tension of the aqueous phase is significantly diminished. Anderman & Co. Ltd. Insert 563 on the Reader Enquiry Service form for further information.

ISSN:0144-557X    

DOI:10.1039/AP9801700384

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

388 PUBLICATIONS RECEIVED Anal. Proc. Publications Received Analysis of Airborne Pollutants in Working Atmospheres : The Welding and Surface Coatings Industries. Janet Moreton and N. ,4. R. Falla. Analytical Sciences Monographs, No. 7. Pp. viii + 184. The Chemical Society. 1980. Price L l Z ; $32 (RSC Members L9). ISBN 0 85186 860 6. Part I, The Welding Industry, covers emission and types of particulate and gaseous pollutants, sampling of workshop atmospheres and the analysis of fumes and pollutant gases. Part 11, The Surface Coatings Industry, covers the origin of airborne pollutants and the collection and analysis of gaseous and particulate atmos- pheric pollutants. A final chapter discusses future trends in both industries, and the introduction to the book includes a useful summary of government regulations and maxi- mum recommended concentrations of airborne pollutants in the UK, USA and elsewhere.Absorption Spectra in the Infrared Region. Volume 5. Edited by L. LAng. Pp. 319. Akadkmiai Kiad6. 1980. Price $25. ISBN 963 05 0187 2 (series); 963 05 1768 X (Vol. 5 ) . This is the fifth volume of the series, which presents the infrared spectra of selected organic compounds over the range of 400-4000 cm-l, together with full details of samples and experimental conditions. The empirical formula, relative molecular mass and melting- point of each substance are also given. Chemistry : The Working Science. George Moriber. Pp. xii + 532. Van Xostrand Rheinhold. 1980. Price L14.20. ISBX 0 442 24852 0. This book introduces students to the world of chemistry, the sources, production and uses of chemicals.It presents chemistry as both a body of scientific knowledge and a field of practical endeavour that strives to improve our material well-being. An Infrared Spectroscopy Atlas for the Coatings Industry. The Infrared Spectroscopy Committee of the Chicago Society for Coatings Technology. Pp. xii + 896. Philadelphia: Federation of Societies for Coatings Technology. 1980. Price $75 (members of the Federation of Societies for Coatings Technology) ; $100 (non- members). ISBN 0 934010 00 5 . This book is an indexed compilation of 1433 infrared spectra of materials commonly utilised388 PUBLICATIONS RECEIVED Anal. Proc. Publications Received Analysis of Airborne Pollutants in Working Atmospheres : The Welding and Surface Coatings Industries.Janet Moreton and N. ,4. R. Falla. Analytical Sciences Monographs, No. 7. Pp. viii + 184. The Chemical Society. 1980. Price L l Z ; $32 (RSC Members L9). ISBN 0 85186 860 6. Part I, The Welding Industry, covers emission and types of particulate and gaseous pollutants, sampling of workshop atmospheres and the analysis of fumes and pollutant gases. Part 11, The Surface Coatings Industry, covers the origin of airborne pollutants and the collection and analysis of gaseous and particulate atmos- pheric pollutants. A final chapter discusses future trends in both industries, and the introduction to the book includes a useful summary of government regulations and maxi- mum recommended concentrations of airborne pollutants in the UK, USA and elsewhere. Absorption Spectra in the Infrared Region.Volume 5. Edited by L. LAng. Pp. 319. Akadkmiai Kiad6. 1980. Price $25. ISBN 963 05 0187 2 (series); 963 05 1768 X (Vol. 5 ) . This is the fifth volume of the series, which presents the infrared spectra of selected organic compounds over the range of 400-4000 cm-l, together with full details of samples and experimental conditions. The empirical formula, relative molecular mass and melting- point of each substance are also given. Chemistry : The Working Science. George Moriber. Pp. xii + 532. Van Xostrand Rheinhold. 1980. Price L14.20. ISBX 0 442 24852 0. This book introduces students to the world of chemistry, the sources, production and uses of chemicals. It presents chemistry as both a body of scientific knowledge and a field of practical endeavour that strives to improve our material well-being. An Infrared Spectroscopy Atlas for the Coatings Industry.The Infrared Spectroscopy Committee of the Chicago Society for Coatings Technology. Pp. xii + 896. Philadelphia: Federation of Societies for Coatings Technology. 1980. Price $75 (members of the Federation of Societies for Coatings Technology) ; $100 (non- members). ISBN 0 934010 00 5 . This book is an indexed compilation of 1433 infrared spectra of materials commonly utilised390 PUBLICATIONS RECEIVED Anal. Proc. in the coatings industry. Spectra include typical examples of polymers, monomers, solvents and organic and inorganic pigments, as well as common additives used in the coatings industry.This publication also contains chapters covering the theory of infrared spectroscopy, qualitative and quantitative analysis, instrumentation, accessories for infra- red spectrophotometers, selected applications and an extensive bibliography. Analytical Atomic Absorption Spectro- scopy. Selected Methods. Jon C. Van Loon. Pp. xii + 337. Academic Press. 1980. Price ,519.60. ISBN 0 12 714050 6. This book was conceived to appeal to the practising analyst. Theory is presented in a descriptive, non-rigorous fashion. Citations have been kept to a minimum to improve the flow of material and to avoid the impression that the reading of these references is essential. The procedures were selected with a view to their reliability. Emphasis was placed on choosing thoroughly tested methods, preferably ones that were evaluated by using standard reference samples or inter-laboratory com- parison. The chapters include General Principles, the Analysis of Waters, Geological Materials, Organic Samples, Metals and Alloys, Air Samples, Petroleum and Petroleum Products, Industrial Samples, Determination of Metal Compounds and Expected New Developments in Atomic Spectroscopy.In addition to the conventional chapters, a short section has been presented on elemental speciation using atomic-absorption spectro- scopy, which is crucial to the solution of environmental, biological and health related problems. Analyse Qualitative Rapide des Cations et des Anions. Fourth Edition. G. Charlot. Pp. vii + 96. Dunod. 1980. ISBN 2 04 010857 2. Professor Charlot describes a qualitative analyti- cal method adopted in numerous laboratories, in which each element is characterised in the presence of others without separation or with only minimum separation.The reactants, organic solvents, complex formation, effect of pH, etc., are considered. The method, which is particularly suitable for semi-micro work, is rapid and allows one element to be studied independently of the others present in a few minutes. Generally, only one drop of sample solution is required, and the reactions involved are simple to carry out. The book is divided into two sections (Cations and Anions), with a further breakdown into procedures for indi- vidual elements and species. General College Chemistry. Sixth Edition. Charles W. Keenan, Donald C. Kleinfelter and Jesse H.Wood. Harper International Edition. Pp. xvi + 880. Harper and Row. 1980. Price i7.50. ISBN 0 06 043615 8. This book provides a general introduction for undergraduate chemists. Auger Electron Spectroscopy. A Biblio- graphy: 1925-1975. Compiled by Donald T. Hawkins. Pp. viii + 11-297. IFI/Plenum. 1977. Price $54. ISBN 0 306 65168 8. This volume provides a list of references pertinent to Auger surface analysis for use as an aid for locating specific references, in researching a particular topic or when con- sidering various aspects of instrumentation or data analysis. The Particle Atlas. Second Edition. Vol- ume VI. Electron Optical Atlas and Techniques. Edited by Walter C. McCrone. Pp. ii + 1457- 1703. Ann Arbor Science Publishers, 1980. Price L50.Volume VI of the Particle Atlas attempts to detail the advances in particle identification by electron optical methods since 1972, when Volume I11 was written. The advances since then include particle manipulation techniques, the identification of smaller and smaller particles and specialised applications, e.g., asbestos. The electron optical characterisation of 41 2 new substances brings the total coverage for these volumes to 1022 substances. Many of the new particles are described by TEM and SAED, as well as SEM and EDXRA. ISBN 0 250 40196 1. Radioelement Analysis : Progress and Problems. Proceedings of the Twenty- Third Conference on Analytical Chemistry in Energy Technology. Edited by W. S. Lyon. Pp. xii -t 424. Ann Arbor Science Publishers. 1980. Price L16.50.ISBN 0 250 40343 9. “Radioelement Analysis : Progress and Prob- lems” was selected as the subject for the 1979 conference on Analytical Chemistry in Energy Technology because of the growing interest in radioelement analysis, spurred by concerns of environmental questions and management prob- lems concerning waste. Although much pro-390 PUBLICATIONS RECEIVED Anal. Proc. in the coatings industry. Spectra include typical examples of polymers, monomers, solvents and organic and inorganic pigments, as well as common additives used in the coatings industry. This publication also contains chapters covering the theory of infrared spectroscopy, qualitative and quantitative analysis, instrumentation, accessories for infra- red spectrophotometers, selected applications and an extensive bibliography.Analytical Atomic Absorption Spectro- scopy. Selected Methods. Jon C. Van Loon. Pp. xii + 337. Academic Press. 1980. Price ,519.60. ISBN 0 12 714050 6. This book was conceived to appeal to the practising analyst. Theory is presented in a descriptive, non-rigorous fashion. Citations have been kept to a minimum to improve the flow of material and to avoid the impression that the reading of these references is essential. The procedures were selected with a view to their reliability. Emphasis was placed on choosing thoroughly tested methods, preferably ones that were evaluated by using standard reference samples or inter-laboratory com- parison. The chapters include General Principles, the Analysis of Waters, Geological Materials, Organic Samples, Metals and Alloys, Air Samples, Petroleum and Petroleum Products, Industrial Samples, Determination of Metal Compounds and Expected New Developments in Atomic Spectroscopy.In addition to the conventional chapters, a short section has been presented on elemental speciation using atomic-absorption spectro- scopy, which is crucial to the solution of environmental, biological and health related problems. Analyse Qualitative Rapide des Cations et des Anions. Fourth Edition. G. Charlot. Pp. vii + 96. Dunod. 1980. ISBN 2 04 010857 2. Professor Charlot describes a qualitative analyti- cal method adopted in numerous laboratories, in which each element is characterised in the presence of others without separation or with only minimum separation. The reactants, organic solvents, complex formation, effect of pH, etc., are considered.The method, which is particularly suitable for semi-micro work, is rapid and allows one element to be studied independently of the others present in a few minutes. Generally, only one drop of sample solution is required, and the reactions involved are simple to carry out. The book is divided into two sections (Cations and Anions), with a further breakdown into procedures for indi- vidual elements and species. General College Chemistry. Sixth Edition. Charles W. Keenan, Donald C. Kleinfelter and Jesse H. Wood. Harper International Edition. Pp. xvi + 880. Harper and Row. 1980. Price i7.50. ISBN 0 06 043615 8. This book provides a general introduction for undergraduate chemists. Auger Electron Spectroscopy. A Biblio- graphy: 1925-1975.Compiled by Donald T. Hawkins. Pp. viii + 11-297. IFI/Plenum. 1977. Price $54. ISBN 0 306 65168 8. This volume provides a list of references pertinent to Auger surface analysis for use as an aid for locating specific references, in researching a particular topic or when con- sidering various aspects of instrumentation or data analysis. The Particle Atlas. Second Edition. Vol- ume VI. Electron Optical Atlas and Techniques. Edited by Walter C. McCrone. Pp. ii + 1457- 1703. Ann Arbor Science Publishers, 1980. Price L50. Volume VI of the Particle Atlas attempts to detail the advances in particle identification by electron optical methods since 1972, when Volume I11 was written. The advances since then include particle manipulation techniques, the identification of smaller and smaller particles and specialised applications, e.g., asbestos.The electron optical characterisation of 41 2 new substances brings the total coverage for these volumes to 1022 substances. Many of the new particles are described by TEM and SAED, as well as SEM and EDXRA. ISBN 0 250 40196 1. Radioelement Analysis : Progress and Problems. Proceedings of the Twenty- Third Conference on Analytical Chemistry in Energy Technology. Edited by W. S. Lyon. Pp. xii -t 424. Ann Arbor Science Publishers. 1980. Price L16.50. ISBN 0 250 40343 9. “Radioelement Analysis : Progress and Prob- lems” was selected as the subject for the 1979 conference on Analytical Chemistry in Energy Technology because of the growing interest in radioelement analysis, spurred by concerns of environmental questions and management prob- lems concerning waste. Although much pro-392 NEW BRITISH STANDARDS gress had been made, significant problems were as yet unsolved. This book presents the Proceedings of the Conference, including the Plenary Lecture “A Special Radioelement Problem : ORNL Assist- ance to Three Mile Island in Handling Contamin- ated Air and Water.” The sections included are Radiochemical Separations and Measure- ments, Radiochemical Determinations and Measurements, Gamma Spectrometry and Activation Analysis, Environmental Analysis, On-line Monitoring and Facilities, Mass Spectro- metry and Quality Assurance and Standards. Anal. PYOC.

ISSN:0144-557X    

DOI:10.1039/AP9801700388

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

392 NEW BRITISH STANDARDS Anal. PYOC. Erratum AUGUST (1980) ISSUE, p. 300. In the article on Fred Ibbotson, the caption to Fig. 2 should begin R-L instead of L-R.

ISSN:0144-557X    

DOI:10.1039/AP980170392b

出版商:RSC    

年代:1980

数据来源: RSC

摘要:

COURSES 393 September, 1980 Courses Particle Size Analysis September 22-26, 1980, Bradford This Course is to be organised by The Institution of Chemical Engineers and held at the School of Powder Technology of the University of Brad- ford. It is intended for particle size analysts and is aimed at providing participants with an understanding of basic principles and the application of these principles to real problems. The Course has been arranged so that the first and last days are optional. The lecturers giving the Course are Dr. T. Allen, Dr. D. I. Ellis, Dr. L. Svarovsky, Dr. N. G. Stanley-Wood, Dr. D. Blackford and Mr. P. J. Bridger. General enquiries about this Course should be addressed to Dr. T. Allen, School of Powder Technology, University of Bradford, Bradford, West Yorkshire, BD7 1DP.Modern Electrophoretic Techniques September 22-23 and 25-26, 1980, Leeds and London These 2-day courses are organised by LKB Instruments Ltd. and will be held at the Multi-Discipline Laboratories, School of Medi- cine, New Medical School, University of Leeds, Leeds, LS2 9 JT and the Department of Botany, Birkbeck College, Malet Street, London, WClE 7HX, respectively. The Programme will be as follows. Day 1. Workshop. This will include lectures and practical laboratory work on the theory and practice of analytical electrofocusing in polyacrylamide gel, iso- electric focusing in agarose and preparative isoelectric focusing in columns and by the flat- bed granulated gel technique. A theoretical and practical treatment of immunoelectro- phoretic techniques will also be covered.Day 2. Morning. Workshop. Continuing with the experiments in preparative isoelectric focusing and immunoelectrophoresis and lec- tures by invited speakers, it is to conclude with an evaluation of results. Day 2. After- noon. Seminar. Isotachophoresis is the most significant electrophoretic separation technique to emerge in recent years. Instrumentation application areas, where LKB Tachophors are already being used, are in the field of clinical chemistry (research and industry). Specific analysis areas include: organic acids (in food and in body fluids); peptides (uraemic toxins, purity control) ; proteins (both routine and research studies) ; metabolites (nucleotides, purines, etc.) ; antibiotics ; binding studies (interactions).A registration fee of L48.00 plus L7.20 VAT (z.e., currently 15% or the rate ruling at the time of payment) (Total L55.20) to cover buffet lunch and other overheads will be required from those participating in the Workshop. There will be no charge for those attending the Seminar only, although registration is essential for both. Please forward payment with regis- tration. The number of participants to the Workshop will be strictly limited to 24. The ITP seminar on the afternoon of day 2 will be an open session where proof of registration will be required upon entry. Detailed programmes will be sent to all delegates on registration. Registration forms are available from Miss S. Todd, Research Division, LKB Instruments Ltd., 232 Adding- ton Road, Selsdon, South Croydon, Surrey, CR2 8YD.394 ANALYTICAL PROCEEDINGS Anal.Proc. Analytical Sciences Monographs No. 2 The Chemical Analysis of Water: General Principles and Techniques by A. L. Wilson The volume covers all stages of the complete analytical process including: deciding on the analytical information required; sampling, including place, time and frequency, as well as devices and techniques; the analysis proper and the reporting of results, their statistical treatment, and the factors involved in the choice of analytical methods (including on-line and automatic methods) for particular purposes; and data handling. Hardcover 196pp 8%‘’ x 6;” f7.50 ($16.50) RSC Members f5.75 0 85990 502 0 No. 3 Pyrolysis-Gas Chromatography by R. W. May, E. F. Pearson and D. Scothern Many papers have been published, particularly over the past decade, on aspects of pyrolysis-gas chromatography. A large number of different types of apparatus have been used, on a wide range of samples.This monograph attempts to present the available knowledge in a form useful to the practising analyst, helping in the choice of an appropriate method and in the avoidance of the more common pitfalls in this, perhaps deceptively, simple technique. Hardcover 117pp 8%” x 6” 0 85186 767 7 f 7.20 ($1 5.75) RSC Members f 5.50 No. 4 Elect rot hermal elements, and areas of application of the first of these two techniques, electrothermal atomization. Hardcover 135pp 8%” x 5e” 0 85186 777 4 f6.75 ($14.75) RSC Members f5.00 No. 5 Dithizone by H. M. N. H. Irving The author of this monograph, who has been closely associated with the development of analytical techniques using this reagent for many years, and who has made extensive investigations into the properties of its complexes, has gathered together a body of historical and technical data that will be of interest to many practising analytical chemists.Hardcover 112pp 8%” x 55” 0 85186 787 1 f7.25 ($16.00) RSC Members f5.50 Atomisation for Atomic Orders: No. 6 lsoenzyme Analysis Edited by D. W. Moss This monograph attempts to draw together the most important experimental techniques which have resulted from the modern recognition that enzymes frequently exist in multiple molecular forms. This monograph also indicates the advantages and limitations in isoenzyme studies of these modern experiments.Brief Contents : Multiple Forms of Enzymes; Separation of Multiple Forms of Enzymes; Selective Inactivation of Multiple Forms of Enzymes; lmmunochemistry of Multiple Forms of Enzymes; Catalytic Differences between Multiple Forms of Enzymes, Methods of Obtaining Structural Information, Selection of Methods of Analysis. Hardcover 171 pp 8%” x 55” 0 85186 800 2 f9.00 ($22.00) RSC Members f6.75 Absorption Spectrometry by C. W. Fuller Since the introduction of atomic absorption spectrometry as an analytical technique, by Walsh, in 1953, the use of alternative atomization sources to the flame has been explored. At the present time the two most successful alternatives appear to be the electrothermal atomizer and the inductively-coupled plasma. In this book an attempt has been made to provide the author’s views on the historical development, commercial design features, theory, practical considerations, analytical parameters of the RSC Members should send their orders to: The Membership Officer, The Royal Society of Chemistry, 30 Russell Square, London WCIB 5DT All other orders should be sent to: The Royal Society of Chemistry, Distribution Centre, Blackhorse Road, Letchworth, Herts. SG6 1 HN The Royal Society of Chemistry

ISSN:0144-557X    

DOI:10.1039/AP9801700393

出版商:RSC    

年代:1980

数据来源: RSC