Water analysis - Analytical Chemistry (ACS Publications)

Jun 15, 1989 - Water analysis. Patrick. MacCarthy , Ronald W. Klusman , Steven W. Cowling , James A. Rice. Analytical Chemistry 1991 63 (12), 301-342 ...
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Anal. Chem. 1989, 6 1 , 95R-109R

(P19) Donahue, S.M.; Brown, C. W.; Caputo, 6.; W e l l , M. D. Anal. Chem. 1988, 60(18),1873-8. (P20) Blanke, W.; Welss, R. Gas-Wasserfach: GaslErdgas 1987, 128(8), 350-7 (Ger); Chem. Abstr. 1987, 107,179676. (P21) Grlmm, W. Industriefeuerung 1987. 42. 13-18 (Ger); Chem. Abstr. 1988, 108,170451. Meterlng and D o n l y

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(028) Pedersen, K. S.;Fredenslund, A. Chem. Eng. Sci. 1987, 42(1), 182-6. SampIIng

(Rl) Bames, W. R. R o c . Int. Sch. HydrocarbonMeas. 1987. 62nd, 172-4. (R2) De Andrade, I. R. G. 501. Tec. PETROBRAS 1988, 31(1),15-17 (Port); Chem. Abstr. 1988, 108, 189470. (R3) Sevcik, A.; Odstrcilova, V.; Vecera, S.; Hlousek, E. Plyn 1988,66(6), 174-9 (Czech); Chem. Abstr. 1988. 105,229604. (R4) Jordan, K. T.; Menzel, E. R. Proc. SPIE I n t . Soc. Opt. Eng. 1987, 737,80-4. (Sll Nakamura, M.; Iio, T. Jpn. Kokai Tokkyo Koho JP 61,219,853 86,219,8531(Cl. G01N21/41),30 Sep 1986,Appl. 85/62.397.26 Mar 1985. (S2) Markuszewski, R.; Haas, W. J., Jr.; Eckeis, D. E.; Lee, S.H. D.; Myles, K. M. Morgantown Energy Techno/. Cent. 1988, DOEIMETC-8616042, 6th 1988, 343-53. (S3) Korshak, A. A.; Burdygina, N. G. I z v . Vyssh. Uchebn. Zaved., Neft. Gaz 1988, 29(9),61-3 (Russ); Chem. Abstr. 1987, 106, 69831. (S4) McCann, P. M. Proc. Int. Sch. Hydrocarbon Meas. 1987, 62nd,

339-41. (S5)Moore, B. J.: Slgler, S. I n f . Circ.-US., Bur. Mines 1987, IC 9167,103 PP. (S6) Faber, E.; Dumke. I.; Ott, A.; Poggenburg. J. Erodei, Erdgas, Kohle 1988, 102(10),456 (Ger); Chem. Abstr. 1987, 106, 104896. 67) Baillie, L. A.; Sklnner. J. L. U.S. US 4,733,557,(Ci. 73-64.2;G01N71 loo), 29 Mar 1988,Appl. 921,919,22 Oct 1986. (S8) Shen, 0.; Llao, Y.; Zhang, 2. Chenji Xuebao 1988, 4(4), 129-30 (Ch); Chem. Abstr. 1987, 107, 25696. (S9) Scarano, E.; Russo, M. V.; Belli, R. Rass. Chim. 1985, 37(6),321-5. (S10) Kawachi, K.; Kaneko, M. Jpn. Kokai Tokkyo Koho JP 61,129,093 [86,129,093](CI. C02F3/12),17 Jun 1986, Appl. 841252,322,29 Nov 1984. (S11) Demczak, M.; Kegel, M. NaRa (Katowice, Pol.) 1988, 42(4),117-19 (Pol); Chem. Abstr. 1987, 106,20768. (S12) Mulyono. S.Lembararan Publ. Lemigas 1988, 20(2),13-18 (Indonesia); Chem. Abstr. 1987, 106, 140728. Burrle, P. H. Tech. Mess. 1988, 55(5), 194-7 (Ger); (513) Fiorisson, 0.; Chem. Abstr. 1988. 109,40404. (S14) Troeger, H. J.; Hausknecht, M. Energietchnik (Leiprig) 1986, 36(10), 373-5 (Ger); Chem. Abstr. 1987, 106. 69745. (S15) Elllott, R. A. Report 1985, GR-8510140;Order No. PB856-1028111 GAR, 39 pp; avail. NTIS. From Gov. Rep. Announce, Index ( U . S . ) 1988, 88(1),601 303. (Sl6) Stan, A. D. Mlne, Pet. Gaze 1987, 38(2),99-102 (Rom); Chem. Abstr. 1987, 107,42713. Standards

(Tl)Niedung, W. Gas-Wassetfach: GaslErdgas 1988, 129(1),9-12 (Ger); Chem. Abstr. 1988, 108,97368. (T2)Jaeschke, M. Gas-Wasserfach: GasIErdgas 1988, 129(1),30-7 (Ger); Chem. Abstr. 1988, 108,97438. (T3) Solka, B. H.; Attari, A. Report 1987,GRI-8810298;Order No. PB87185161lGAR, 96 pp; avail. NTIS. From Gov. Rep. Announce. Index ( U S ) 1987, 87(15),732 154. (T4) ASTM Standards; ASTM: Philadelphia, PA, 1988;Vol. 5.05.

Forensic Science T. A. Brettell and R. Saferstein* N e w Jersey State Police, Forensic Science Bureau, Box 7068, West Trenton, New Jersey 08628

It is the aim of this article to present a concise survey of articles appearing in publications that primarily appeal to forensic practitioners. T o accomplish this objective, we have focused our attention on the following journals: Journal of Forensic Sciences, Journal of the Forensic Science Society, Forensic Science International, Journal of the Canadian Society of Forensic Science, Analytical Toxicology, and The Microscope, as well as Chemical Abstracts Selects: Forensic Chemistry. Our survey encompasses the period from January 1987 through December 1988. Because of the normal delays in the abstraction of journal articles by Chemical Abstracts, some work covering this period will inadvertently be omitted. Hopefully these references will be included in the next biennial review.

The format selected for this survey divides coverage into three distinct areas: Drugs and Poisons, Forensic Biochemistry, and Trace Evidence. Within the scope of each of the areas, articles have been selected to describe current forensic science practices in analytical chemistry and to outline relevant forensic science research interests. To keep our discussion concise and meaningful, we have limited our survey to drugs regulated under the United States Controlled Substances Act, ethanol, and common poisons. Furthermore, to eliminate unnecessary duplication of effort, citations of articles appearing in Clinical Chemistry, the Journal of Pharmaceutical Sciences, and other pharmaceutical journals have been avoided. We believe that ample coverage of these journals is provided within the pharmaceutical and clinical chemistry 0 1989 American Chemical Society

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reviews planned for this journal. It is recommended that interested readers consult these sections in order to obtain a complete survey of the drug-abuse subject.

DRUGS AND POISONS Ethanol a n d Volatiles. Six types of evidential breath testing (EBT) machines were tested in a laboratory showing good results although different types of EBT machines showed significant differences measuring the same vapor ( I ) . The Alco-Sur was shown to be a reliable, accurate screening device when operated according to the manufactorer’s instructions ( 2 ) . Three pocket-size breath alcohol analyzers were evaluated-the Alco-Sensor 111, the Alcohol-Checker RK-1000, and the Breathalyzer PMT-1. It was concluded that the Alco-Sensor is suitable for the self-monitoring of breath alcohol levels, provided the manufacturer’s specifications are followed. The other two are unsuitable for this purpose ( 3 ) . The measurement of blood ethanol values from breath samples using the Alkomat breath analyzer may be unsuitable because of the presence of certain chemical compounds, the influence of lung functions, breath technique, and environmental temperatures ( 4 ) . Two Intoxilyzer 4011AS-A instruments, used to detect the alcohol concentrations in the breath of persons arrested for driving under the influence, were tested and found to show excellent conformity with the Beer-Lambert law (5). The accuracy and precision of breath-alcohol measurements for subjects a t random have been analyzed for those in the absorptive state (6) and the postabsorptive state (7). An opinion and discussion of the accuracy and precision of breath-alcohol measurements has been published ( 8 )as well as a review of the forensic values of ethanol determinations in blood and respiratory air (9). A statistical analysis of 1847 duplicate breath tests has been presented which showed that duplicate breath test differences do not appear to be a function of subject’s alcohol level but rather of sample provision (10). A discussion of the statistical and forensic significance of duplicate breath samples for the determination of breath alcohol measurements has been given (11). A total of 500 breath-alcohol test measurements were evaluated to determine the distribution of the third digit and the effect of truncating breath-alcohol measurements to two decimal places (12). A simple experiment has been described, suitable for a quantitative analysis course, that illustrates the chemistry of the breath alcohol test (13). Breathalyzer and blood alcohol results from drivers arrested for operating a motor vehicle while intoxicated and for related offenses were compared during a two-year period (14). Mild hypothermia, induced by experimental immersion of ten subjects in cold water, distorted the decay curve of breath ethanol of intoxicated subjects by as much as 22% while not altering overall ethanol clearance rate (15). In vitro accuracy and precision studies were conducted by using silica gel, magnesium perchlorate, and indium encapsulation breath collection tubes in conjunction with three infrared breath ethanol analyzers (16). Blood alcohol concentrations were determined by breath samples introduced into Borkenstein Breathalyzers from subjects who consumed various amounts of 40% (v/v) diluted pure ethanol during a 40-min period (17). It has been shown that elevated breath-acetone concentrations associated with prolonged fasting (36 h) are not a significant interference problem when infrared breath-alcohol analyzers are used for evidential purposes (18). The methods for the determination of ethanol in urine, breath, and saliva have been reviewed (19). Several 0.53 mm (i-d.) fused-silica open tubular columns were evaluated for the gas chromatographic determination of ethanol and other volatiles in blood by both headspace and liquid injections (20). A technique has been described for simultaneous quantification and confirmation of routine blood alcohol analysis using a single injection and dual capillary column headspace GC (21). Flow injection determination of ethanol in whole blood using immobilized enzymes has been reported with good precision and sampling frequency (22). The differences in ethanol concentrations as measured by direct injection GC, among plasma, serum and whole blood from living human subjects have been examined (23). The heart blood/femoral blood ethyl alcohol ratio has been determined for 100 cases using headspace GC-FID (24). Two sets of Toxichem controls were analyzed by GC and found to be in good agreement with Fisher’s listed assay values (2Fj). 96R

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A new colorimetric method has been described for measuring ethanol in plasma by use of a peroxidase-coupled assay system and alcohol oxidase (EC 1.1.3.13) from Pichia species (26). Blood specimens from suspected driving while intoxicated individuals and postmortem blood specimens were compared by the Abbott TDx-Radiation Energy Attenuation (REA) Ethanol Assay method and a headspace GC method (27). A simple, rapid ethanol screen based on a microdiffusion technique has been evaluated and compared to an established enzymatic procedure (Abbott TDx Ethanol Assay) (28). A case with high ethanol concentration in the heart blood determined by GC-FID and GC/MS has been described (29). The circumstances in which some drivers’ blood specimens containing added sodium fluoride deteriorated as a result of microbial contamination, accompanied by a decrease of alcohol concentration has been described (30). The comparability of ethanol concentrations in peripheral blood and saliva and the phenomenon of variation in saliva to blood concentration ratios have been reported (31). A study of the effect of hemoglobin interferences with the enzymatic alcohol analytical pack for the DuPont ACA ethanol method has been described (32). Acetone and 2-propanol concentrations in blood have been studied as markers for the acute and chronic ethanol consumption (alcoholism) (33). The effect in traffic safety of reducing the blood alcohol level in Queensland, Australia, from 0.08% to 0.05% has been discussed (34). A review with 15 references on the determination of blood ethanol concentrations in human drunk drivers has been published (35). Three cases are described where very high blood cyanide levels, estimated colorimetrically after isolation by microdiffusion, were found at postmortem but where circumstances tended to preclude cyanide poisoning and where no source could be discovered (36). An improved GC method for HCN in blood with acetonitrile as an internal standard has been developed which used GC-NPD and a packed column (37). The effects of storage conditions on cyanide concentrations in tissue samples and the cyanide distribution in five fatal cyanide poisonings were analyzed by the pyridinepyrazolone method using a Conway diffusion cell (38). Blood from a poisoning case was analyzed for carbon monoxide by GC using a modified method of Gantz (39). The quantitative analysis of carboxyhaemoglobin (HbCO) in fresh blood samples containing sulphaemoglobin (SHb) and in postmortem blood samples was investigated by using two automated spectrophotometers (40). Body fluids and tissues from the heart, urine, bile, liver, brain, and kidney from a fatal case of ethychlorvynol poisoning were analyzed by GC for ethychlorvynol (41). GC-FID methodology and tissue concentrations of chloroform are presented from autopsy evidence from a double homicide as a result of chloroform poisoning (42). Chloroform concentrations were also determined in subclavian blood from an inhalation fatal victim by headspace GC-FID and GC MS (43). Forensic toxicological analysis of tetrahydrofuran in body materials was performed routinely by GC and GC/MS (44). A reliable method to determine small amounts of fuel components, specifically gasoline and kerosine, in biological materials using two simultaneous procedures, headspace and solvent extraction methods with GC/MS, was developed (45). Samples of the food and medication from an attempted homicide were analyzed for Warfarin, the active ingredient of d-CON, using UV, GC-FID, and GC/MS (46). The effectiveness of energy dispersive X-ray fluorescence analysis has been shown by the analysis of blood and liver from a victim of mercury poisoning where mercury levels were determined along with the identification and determination of 16 toxic metals in simulated stomach contents (47). Cannabinoids. A review on the methods for the identification and quantification of cannabis constituents, including field tests based on color reactions, TLC, HPLC, GC, RIA, NMR and MS, and UV spectrophotometry has been published (48). Two overpressured layer chromatographic methods have been developed for the separation, quantification, and isolation of cannabinoids from Cannabis sativa L. (49). High resolution capillary GC-FID, GC/MS, and HPLC have been used to establish complex chemical profiles of cannabis samples of known origin (50).

FORENSIC SCIENCE

of 11-Nor-Ag-THC-COOH and none was found (70). A method for the determination of Ag-THC in whole blood that employs hexane extraction followed by identification using GC-NPD has been developed which is sensitive to 2 ng of THC/mL of blood (71). The sensitivit and specificity of serum Ag-THC and 11-nor-9-carboxy-A -THC by RIA in identifying habitual daily smokers of marijuana have been - 4' reported (72). A rapid, sensitive, and selective determination ~.r of Ag-THCin human plasma, serum, and saliva was developed with HPLC with electrochemical detection (73). A method has been described for the determination of A9-THC in the New Jersey State Police Forensic Science saliva by the use of a combination of moving-precolumn inBureau in 1976. H e has also been B m e m ber of the tacuny of the New Jersey Goverjector and glass capillary GC-ECD (74). An accidental innor's SchWi in the SCiencaS since 1985 and gestion of cannabis resin by a 2'12 year old girl is used to was appointed a member of Ihe faculty of Me National College of District discuss the clinical presentation, sequelae, and legal impliAnmey'S this past year. Or. Breneii holds memberships in the American cations of cannabis ingestion by children (75). Chemical Society. ihe American Academy 01 Forensic Sciences, the NorthMorphine a n d Related Narcotics. The reliability of eastern Association of Forensic Sciences. me MbAtlantic A~socialionof analyzing street heroin samples by headspace GC coupled with Fwensic Scientists.the Forensic Science Society. the Microchemical SocieTLC, GC, and HPLC for comparative sample analysis has ty. and the Delaware Vaiiey Chromatography Fwum. His pressmi research interests include headspaw analysis. gas chromatography, and mass specbeen discussed (76). Analytical studies on illicit heroin and trometry. its efficiency of volatilization during heroin smoking has been reported using TLC, GC, and HPLC (77). A method for the Rkhard Safmtein is Chief F01enslc Scienroutine profiling of illicit heroin samples received in casework 1161 01 the New Jersey State Poiice has been developed which depends on simple and straightLaboratory. He received B.S. and M.A. de. ' forward sample pretreatment followed by GC on a capillary nrees from lb Chv Cdiece of New Ywk in column using FID (78). A HPLC method using absorbance i963 and 1966,r i s p e c t i k y ~e received '., ratios, retention times, and a linear diode array multiwavehis Ph.D. degree in chemirlry from the City length detector, is described for the identification of diaUniversity of New York in 1970. Rior to his coming to the New Jersey State Poke in morphine in illicit heroin samples (79). Methodology has been 1970. he was employed as a forensic presented for the quantification of heroin and selected basic chemist with the Treasury Department impurities hy reversed-phase HPLC (80).The separation and (1964-1968)and S W W ~ as an anaiflicai . identification of illicit heroin samples by liquid chromatogchemist with Shell Chemical Co. raphy using an alumina and CI8 coupled column system and (1989-1970).Dr. Ssfersteh is lhe a h of ,.: ~. photodiode array detection have been described (81). An a number of technical papers covering a vaeffective TLC system for separating eight opiates and five rbty of forensic topics. He has also wrinen ' adulterants in the analysis of illicit heroin samples has been a book on the subject titled ClimimlishcJ: An Introduction lo Forensic S d l mce (PmnliMcHaii. 1990). and has edited Forensic Science Handbook. voideveloped (82). An illicit procedure for the preparation of Umes I and I 1 (Prentice-Hail. 1982, 1988).reference texts dealing with im morphine, known as "homebake', from codeine-based pharPOnant forensic science topics. H e is a coauthor of Laboratory Manual for maceutical products has been described using a procedure to Criminalislics. (Prentice-Hail, 1990). Or. Saferstein currently serves on the demethylate the codeine to produce morphine (83). Seized ednoriai b o a r e Of the Journal Of Faens* Sciences and MicrochemicalJourheroin samples from Denmark from 1981 to 1986 were nal. H e is a member of lhe American Chemical Society. the American Am'fingerprinted" to determine the changes in place of origin demy of Forensic Science. the American Microchemical Society. The Foren(84). The solid-state infrared spectral features of the (1:l) sic Science Society. the Canadian Society of Forensic Scientist. Nollheast0-6-acetylmorphine-ethyl acetate complex have been comern AssccIati~nof Fwensk SCIentists. and Mid-Atlantic Association of Forensic Scientists. pared to those of its host, 0-6-acetylmorphine base, and to its very similar analogue, 0-3,0-6-diacetylmorphine (heroin) (85). A novel application of headspace and GC/FI-IR analysis to identify the ethyl acetate complex of 0-6-acetylmorphine has also been described (86). The separation of five principal alkaloids, three minor alkaloids, meconic acid, and some unA review of marijuana metabolism, organ distribution and identified constituents in gum opium samples was achieved excretion, THC and carboxy THC detection in urine and b l d by reversed-phase HPLC (87). The optimization of the sepplasma, methods of screening for marijuana use. passive aration of seven opium alkaloids hy sub- and supercritical fluid smoking of marijuana, and tampering and adulteration of chromatography (SFC) using packed columns and carbon wine samples before analysis has been reponed (51). Methods as the primary mobile phase was studied (88). for the detertion of the marijuana metabolite, I I - N ~ ~ ~ - A ~dioxide THC-9-COOH. in urine have lieen reported that use GC MS Plasma and whole blood samples from postmortem speci( 5 2 . 5 4 , HPLC with photodiode array detertion (54, HPLC mens were analyzed for morphine with RIA and it was conwith elertrochemical detection (.55i, HPLC with UV speccluded that RIA screening of postmortem blood samples can truphotometry and elerrrnchemiral decertion (561, and TI,C be performed without prior sample pretreatment (89). A (57-591. Immunoassays cuntinur t u he a popular method of procedure has been developed for the simultaneous deterscreening urine for the detectiun oi cannabinoids. 'l'wo mination of heroin, morphine, and hydromorphone from tltioroimmunuassays were developed tor the detection of postmortem tissues by reversed-phase HPLC using electrocannabinoids in urine (601. The specificity of the rannabinoid chemical detection (90). HPLC-ECD has been used to demetnholite and phencyclidine K h l l T d.a.u. assays has heen termine morphine in blood (91,92) and codeine and morphine evdwltd ( f i l l as well ns thr EMI'I'-Cobas and TDx terhniques in human plasma (93,94). A rapid and efficient procedure for the detertion of cannahinoid- in urine from prison inmates has been described for the extraction and analysis of codeine (621. Three immunoassoyi and C C MS were used t u d r t w t and morphine in whole blood with HPLC (95). HPLC with rannahinoids in urine 163,641. The detwrion of cannabinids chemiluminescence detection has been used for the deterin urine for rhe purposc of drtermining parsive inhalation uf mination of morphine in biological fluids (96).Concentrations niarijumn smoke has heen re)iorted 165,tihi and revii*wed167). of free and conjugated morphine in blood, in 20 cases of ,. I he incidence of cannabinoids was studied in a nmsperific heroin-related deaths, have been reported (97) as well as population of pnstmortem urine qierimrns itsing FMIT and unconjugated morphine concentrations in postmortem blood HI'1.C' ( M i . L'rinunnlvses by E11IT (1.a.u. assay aiid Ahwby RIA and GC/MS (98). A simplified GC method for the rreen RIA for rannaliin(rirls and GC hlS assay tor 'I'HC-CO. rapid determination of morphine in blood has been described OH indicated that iul)stantinl amounti uf tnnrijunna-related which uses flash-heater methylation and GC-NPD (99). A metnh