er al, 1982: Mill e r & Ude n , 1983; C hristman er al, I 9 83 ), and mod el compound s (Boyce & H o rnig, I 983; Norwood er al, 1983). Levels of DCAA a nd T CAA in chlorinated tap wate rs wou ld ap pear to be similar to T HM leve ls (Uden & Miller , 1983). Th e relationship be tween a nd ha loacid and THM production ha been in vestiga ted in ex pe rim e nt s with ful vic acid. T CAA leve ls were found to be more than double those of C HCI, (Mi lle r er al, 1982) w hi ch ag rees reasonabl y we ll with the few data obtained on drinkin g waters. Analyses of c hl o rina ted South Au stra li an wat e rs, a lt houg h a t this tim e limited, confi rm that DCAA and TCAA a re present. Levels up to 200 l'g/ L T CAA have bee n d etermined and DCAA levels appear to reach this va lue in wate rs c hl orinated at norm a l rates . Dibromoacet ic acid has a lso been iden tified in one rela ti ve ly sa line water w hic h produ ces hi gh levels (up to 500 l'g/ L) o f C H Br,. In ves tigatio n of the product s of humic and ful vic acid chl orinat io n has s hown that D CAA a nd TCAA are th e major ha loaci d s formed , _however a number of hi g her ha loacid s are also for med (Chri stman er al, 1983) and these also need to be id entified and qu a ntifi ed . OTHER CHLORINATED COMPOUNDS Ev idence su ggests that a large number of co mpound s of vari ou s ot her c hemi cal classes may o cc ur in c hlorin a ted waters but at very low leve ls. R ook (1977) id e ntifi ed a number of compo und s including c hl ora l and other h a logen a ted h ydrocarbons form ed o n c hlo rination of peat extacts . On heav y chl orina tion of reser vo ir water a numb e r of com pounds including h a logenated a lco ho ls a nd aro matic compo unds were id e ntifi ed . C hloral was a lso ide ntified by C hristman er al ( 1983) a nd b y Miller & Ude n ( 1983) from c hlorina tion of humi c a nd ful vic acids . C hlora l leve ls in tap wa ter were reported to be approx imately one te nth of C HCI , level s (Uden & Miller , I 983) . C hl o rin atio n of wastewaters was reported to produce a large number of co m pounds (G laze & H ende rso n , 1975). In th e case of wastewaters w he re man y co mpound s capable of being c hl o rinated, bes ides humi c and fu lvic ac ids, ma y be present, the range of chl o rin a ted product s could be ve ry large in d eed. The prese nce of other ha lo ge na ted com pounds, a part fro m THM s a nd ha loacids in So u th Au strali a n dr inkin g water is ev ident from the c hro ma tog rams in Figure I whic h have been obtained durin g routine THM a nal yses . The compound s respo nsible for peaks m arked w ith as terisks have not been id e ntifi ed . Th ey m ay be iodinat ed THM s, ha logenated ketones or aceto nitril es as prev iou sly discussed, or th ey ma y be ot he r compo unds . C losed Loop Strippin g Ana lysis (CLSA) has been used in the State W a te r La borator y to iso late a la rge num ber of vo la til e produc ts from c hl o rin a ted reserv ior water. A wid e va riet y of po lychl orinated h ydroca rbon s (saturated and unsa turat ed) has bee n fo und , th e deg ree of chl ori nati on ex te nding to substitution b y up to fiv e c hlorin e atom s for so me co mpo unds . Thi s would partl y account for th e hi g h c hlorin e d e mand of ce rtain ~ • Ii . ., 0 NM (2 ) 7,,oi l' ~ ~ (6 ) 4 )~ B) A) ~ - • (I) • (7} (2) ~ (5) ---I . <5 l ~ r (21g1 . ::: ( 2~ (! ~ )M <':' ~'? '! J_ ~ . n~ (6) ri M (5) (10) M ~ ~ (6) ~ (8 ) l C) I • ~ D) (7) (1) ~ ~ I ~9) 1 I I (10) I M . ,r--1-,-, ~ ~r Figure 1. Some chromatograms obtained during routine THM ana lyses stora ge of extracls In freezer; (3)-CHC IJ; (4)-carbon letrachloride: (5) - CH CllBr: (6)-C HCIBrJ; (7) - impurit y from interna l standard (tetrachloroelh yle ne): (8) - 1, t , l · lrichloroac eton e: (9)-CHBrl: (10)- internal stand ard (tetrachloroethan e). (I and 2) - conlamination through Peaks mark ed • hav e nol bee n id en lified . Sample A (Solvent) B C D Concentration (µg/ L) C HCI, CCI, C H C l, Br C HCIBr, TCA C HBr, < 1 42 372 70 < 0.05 0. 50 0.80 < 0 .05 < 1 17 116 83 < 1 4 28 47 < 1 < I 4 IO < 1 < 1 1 6 waters co nta ining hi gh levels of naturally oc-. curring o rgani cs. The compou nds formed in this type o f react ion play no useful part in the di sinfection process. CHLORINATED PHENOLS It is well known that ph e nols are very im portant in re lat ion to water qualit y as c hlorinated pheno ls with very low taste and odour thres holds ma y be produced on c hlorination. Although ex pe riment s with m odel compounds for humi c a nd fulvic acids have shown that ch lo rin ated phenols may be p rod uced on c hlorination (Larson & Rockwell, 1979; Norwood et al, 1980; Boyce & H orn ig, 1983) , no ch lo rinated aromat ic compo unds were found o n chlorination of humic acid (C hri stm a n er al, 1983) and there is li tt le evi d e nce t hat c hlorin a ted phenol s occur in ch lorinated drinkin g wate rs. However a rec urring taste a nd odour proble m with the ch lori nated water supply at Mt. Gamb ier wou ld appear to be due to bromina ted p heno ls . Tribromoph e no l has been identified b y gas chromatography/ mass spectrometry and b y th e re tention tim e of it s pentafluorobenzyl d e ri vative. It s concentrat ion in the latest incid e nt was found to be 5 l'g/ L. Th e occurrence of brominated phe no ls is not surpri sing as th e co ndition s under which the wa ter is chl or in ated leads to C HBr, as th e predomi - nant THM so hypobromous acid is obv iously th e halogenatin g agent. However the precurso r and its source art unknown at thi s time but Masumoto (1982) has identifi ed phenol s in water which wou ld appear to ari se from plant material a nd these sa me phenols produce c hlorin ated phenols on c hlorinati on (Larson & Rockwell, I 979). Of particu lar interest in relation to the ch lorin ation process a re th e effluent s from pu lp and paper industries where c hlo rination is carried out for bleaching purposes. Compounds of a number of different classes have been identified. Nonpolar compound s such as C HCI, and chl orinated cyme nes, and chlorin ated pheno ls, including catechols and guaiacols have been identified (Bjorset h er al, 1979; Paas irvirta el al, 1983) . T hus effl uent s from pulp and pape r indu stri es a re poten tial ly ser iou s sources of pollu tion from ch lor inated compounds. TOTAL ORGANIC HALOGEN (TOX) The identification of a ll b yproduct s of c hlorination would requ ire len gth y and complex analytical procedures. A more genera l parameter which is a measure of the amount of ha logen incorporated into orga ni c mo lecules is the Total Orga ni c H alogen (TOX). In the analys is of water for TOX the organ ics in WATER September, /984 13