Survey of volatile halogenated organics (VHO) in Italy

Wat. Res. Vol. 20, No. 8, pp. 959-963, 1986 Printed in Great Britain

0043-1354/86 $3.00+0.00 Pergamon Journals Ltd

SURVEY OF VOLATILE HALOGENATED ORGANICS (VHO) IN ITALY LEVELS OF VHO IN D R I N K I N G WATERS, S U R F A C E W A T E R S A N D SWIMMING POOLS G. AGGAZZOTTI and G. PREDIERI Istituto di Igiene, Universitfi degli Studi di Modena, Via G. Campi, 28741100 Modena, Italia (Received November 1984)

Almtract--A survey undertaken in Italy (Emilia-Romagna region) has shown that Volatile Halogenated Organics (VHO) are present in many water samples; analysis has been performed by static head-space gas chromatographic technique. In drinking water samples low levels of pollution have become evident before any treatment, while after chlorination with sodium hypochlorite, or chlorine as a gas, VHO have appeared, almost exclusivelyas trihalomethanes (THM), sometimes at fairly high levels (max = 41.8 ~g l-t). Surface water samples have been collected every other month in one year, and have shown different levels of contamination; in most cases VHO (mainly chlorinated solvents) appeared just as traces, seldom at high concentration (max = 263/lg 1-t ). Swimmingpool samples have shown the high levelsof contamination (max = 177.4#g I 1), mainly due to THM, as a consequence of chlorination with sodium hypochlorite. As a matter of fact, it has become evident that VHO pollution is wide-spread in every kind of water; while contamination of surface waters can only involve environmental and aquatic life, contamination especially of drinking waters, and also of swimming pool waters must be controlled as it can directly act on human health. Key words--Volatile Halogenated Organics, trihalomethanes, drinking water, surface water, swimming

pool water, Italy

INTRODUCTION The presence of Volatile Halogenated Organics (VHO) in waters continues to be the subject of much public concern and active research since the discovery by Rook (1974, 1975, 1977) that small amounts of these compounds, mainly trihalomethanes (THM), are produced during chlorination of natural waters containing high amounts of organic substances. Till now many surveys have been performed all over the world in order to monitor local situations (Symons et al., 1975; Sonnenborg and Bohn, 1978; Montiel, 1980; Norin and Renberg, 1980; Schreiber, 1981; Chambon et al., 1983). In 1980, in Italy, the National Health Department funded ten University Hygiene Institutes (Modena University Institute was included) to research into drinking water conditions as regards VHO presence (Cremisini et al., 1983a,b; Giannico et al., 1983). These studies have shown a generally favourable situation, on the whole; however, two special conditions became evident in some cases. First, VHO presence (mainly trichloroethylene) appeared in some natural ground waters, coming from deep wells, as a consequence of infiltrations from industrial waste-waters (Giovanardi, 1979; Gilli et al., 1979; Ziglio and Giovanardi, 1981).

Second, THM production became evident in samples of drinking waters after treatments with chlorine (C12) or sodium hypochlorite (NaC10); just small quantities appeared after treatment with chlorine dioxide (C102). We presume that THM presence does not depend on hypochlorite quality; as a matter of fact, we have tested many samples of commercially produced hypochlorite with negative results. The same waters appeared free from THM when analysed before any disinfection treatment; in raw waters the level of organic matter, measured by oxidation with hot potassium permanganate, fluctuated between 0.3 and 2.1 mg 1-~ 02 (Gilli et al., 1979; Dardanelli et al., 1980; Olivo et al., 1981; Del Prete and Amodio, 1982; Sarritzu et al., 1983; Grosso et al., 1984). Researches on surface waters in Italy have shown very different results from each other (Gilli et al., 1979; Sanna et al., 1979; Dardanelli et al., 1980; Sarritzu et al., 1983; Castello et al., 1983; Aggazzotti and Predieri, 1984; Kanitz et al., 1984). Other research has been performed on swimming pool waters, which are usually disinfected with NaCIO or dichloroisocyanurate; also these waters have shown THM presence, sometimes at a very high concentration (Beech et al., 1980; Lahl et al., 1981; Chambon et al., 1983; Aggazzotti et al., 1984).

959

960

G. AGGAZZOTTI and G. PREDIERI

In the present work a survey is presented, made on different kinds o f water samples in E m i l i a - R o m a g n a district, mainly in M o d e n a province (Italy); ground waters, drinking waters, surface waters and swimming pool waters have been investigated. MATERIALS AND METHODS The following VHO have been studied: chloroform: CHC13 bromodichloromethane: CHC12Br dibromochloromethane: CHCIBr2 bromoform: CHBr 3 1,1,1,trichloroethane: CH3CCI 3 carbon tetrachloride: C C l 4 l,l,2,trichloroethylene: C12C = CHC1 1,1,2,2 tetrachloroethylene: C12C = CC12. VHO presence has been determined by static head-space gas-chromatographic technique (Cavallaro and Grassi, 1976; Hammarstrand, 1976; Dietz et al., 1979; Ziglio and Beltramelli, 1980). The system employed was the Varian Gas Chromatograph 3700 with 63Ni Electron Capture Detector. Two kinds of columns were used, of two different polarities, in order to obtain a complete separation and identification of each compound. A stainless-steel column (3 m long, 1/8" i.d.), was packed with 10% OV 1 on Chromosorb W-AW, 80-100 mesh; the second stainless-steel column, (3m long, 1/8" i.d.) was packed with 10% SP 1000 on Supelcoport, 8(~100 mesh. The two columns were operated at the following conditions: oven temperature: 70'C injector temperature: 150~C detector temperature: 28ff'C sensitivity: 0.05 #g I t for chloroform carrier gas flow rate: 30 cm 3 min ~. Water samples were collected in screw-capped glass vials with a volume of 40 cm s with silicone-faced septa (Supelchem); the injections (20-200#1) were made by using Hamilton gas-tight syringes. Standard solutions were made up in mineral bottled water, free from VHO, injecting known volumes of VHO solutions in methanol (analytical reagent grade). Analyses were performed equilibrating standard solutions and samples at 30'C for at least 1 h in a water bath after having removed 5 cm 3 of water, in order to create the head-space volume, and after having added 40 mg of NaC1 to each vial to homogenate ionic strength of different waters. Before use NaC1 (analytical reagent grade) was placed in a muffle furnace at 400 _+ 5~'C for 2 h, in order to be purged from volatile contaminants. Calibration and quantification of VHO used calibration factors and external standard calculation employing the Perkin-Elmer E 15 Chromatography Data System. Drinking water samples were collected from 46 drinking water supplies. Waters were examined before any treatment and after disinfection processes, at end-points of the supplies; some water supplies provided water without any kind of disinfection before distribution. Even now many waters in Italy are provided in supply without any form of disinfection before distribution, as water quality is very good at the origin and distribution systems are not very extensive. All the waters which fed plants were pumped from deep wells; they were all ground-waters from water-tables. Surface water samples were collected from 31 stations, situated on the main water-courses in Modena province; the frequence of sampling was every other month during a year. Ten swimming pools in Modena province were examined, collecting samples every 2 months for a year; every pool was

fed by disinfected water, treated either with NaCIO, or dichloroisocyanurate.

RESULTS

V H O contents, as regards to g r o u n d water samples collected before any treatment, are given in Table 1; just one sample was drawn from each water plant. Most o f the samples appeared completely free from VHO; in only one sample the total a m o u n t o f V H O appeared higher than 10 # g l t. On the basis o f this result, this water source has been further investigated, and many samples were collected. Table 2 shows which are the most represented c o m p o u n d s present in these samples; they were all belonging to chlorinated solvents (1,1,2 trichloroethylene and 1,1,2,2 tetrachloroethylene) and they reached the total a m o u n t o f 20 p g 1 -~. Table 3 shows V H O levels detected in tap-water samples collected at end-points o f the distribution systems. M o s t o f the samples collected from waters distributed without any disinfection treatment showed no V H O at all (72.7%); after chlorination treatment (with C12 or NaCIO) in the 21.9% o f samples V H O levels appeared higher than 10/~gl J. N o sample o f water disinfected with C102 revealed levels o f V H O higher than 1 0 p g 1-~. Chlorination treatments were always performed on raw waters before distribution, and were based on the chlorined e m a n d o f different waters. Since the good quality o f raw waters, neither prechlorination, nor coagulation/ sedimentation treatments were performed in all the 46 drinking water plants. As regards the nature o f V H O present in disinfected waters, they were almost exclusively T H M . Subsequently more samples were collected from a

Table 1. VHO levels in drinking water samples before any disinfection treatment VHO levels (#gl ~)

No. of samples

0 <1

33 8

1 10

4

> 10

I 46

Total

% 71.7 17.4 8.7 2.2 100

Table 2. An exampleof natural ground water contaminated by VHO VHO levels (,ugl ~) CHCI~ CHCI2Br CHC1Br2 CHBrs 1,1,1 Trichloroethane Carbon tetrachloride 1,1,2 Trichloroethylene 1,1,2,2 Tetrachloroethylene Others Total amount

Mean

Min max

%

0 0 0 0 <1 <1 10.6 7.8 0 18.4

04) 0~ 04) 04) 0< I 0< I 3 12 4 10 0 8 20

0 0 0 0 0.05 0.05 57.5 42.4 0 100

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Volatile Halogenated Organics in Italy Table 3. VHO levelsin drinkingwater samplescollectedduringdistributionin 46 water supplies V H O levels (~gl ~)

No. of waters without any treatment

0 > 1 1-10 > 10

8 2 0 1 11

Total

%

No. of waters treated with CI 2 or N a C I O

%

No. of waters treated with CIO 2

%

72.7 18.2 0.0 9.1 100

0 17 8 7 32

0.0 53.1 25.0 21.9 100

1 1 1 0 3

33.3 33.3 33.3 0.0 100

water plant in which THM showed high levels; results are given in Table 4. Chloroform is the most represented compound among all the VHO; besides it, other THM have been detected, mainly dichlorobromomethane and dibromochloromethane. The total maximum amount of VHO appeared just in one sample: 41.8#g 1-~. VHO levels in surface water samples are presented in Table 5; in more than half the stations VHO always appeared in very low amounts (just traces), while in the 16.1% of stations they were always higher than 10/~g 1-~. The most represented compounds were 1,1,2 trichloroethylene and 1,1,2,2 tetrachloroethylene; the highest amounts were found in stations just downstream of the most important towns or villages of the region. Table 6 shows the most representative example of contamination in a station situated on a surface water-course, a canal which collects the wastes of the city of Modena; in one sample drawn from this canal the total amount of VHO appeared 263 pg 1-1. The results of VHO research in swimming pool waters are represented in Table 7; total levels were always higher than 10 # g l 1. Perhaps VHO concentration is always higher than 10 #g 1-1 as pool water continuously circulating inside the chlorination plant, so that it becomes more and more enriched in VHO. When pool waters had been disinfected with NaCIO, mean total levels were higher than in waters treated with dichloroisocyanurate. As regards the quality of VHO, they were exclusively THM, as shown in Table 8, which represents an example of a swimming pool, whose water was disinfected with NaCIO. The maximum amount ever discovered was 177.4 p g l 1. All raw waters, which supplied swimming pools,

Table 4. An example of chlorinated water contaminated by V H O V H O levels (#g I i ) CHCI 3 CHC12 Br CHCIBr 2 CHBr 3 1,1,1 Trichloroethane Carbon tetrachloride 1,1,2 Trichloroethylene 1,1,2,2 Tetrachloroethylene Others Total a m o u n t

Mean

Min-max

%

28.3 9.3 3.4 0 0.3 0.2 0 0 0 30.6

14-31 5.9-11 1.4-4.4 04) 0.1~).5 0.2~).3 I~0 ff4) 043 22~,1.8

67.7 22.6 8.6 0 0.7 0.4 0 0 0 100

never evidenced VHO presence; they only appeared after disinfection. Our research now continues in this field. DISCUSSION

Drinking water results have shown that in EmiliaRomagna there is a middle level of contamination; samples drawn from eight among forty-six water supplies during public distribution have presented levels of VHO higher than 10pg 1-~. Among these eight, seven plants distributed waters which had been disinfected with NaC10 at that moment; THM were the most representative compounds, and they were absent in the same waters before chlorination. This confirms that chlorination processes with NaC10 or C12 are very likely responsible for VHO presence in disinfected waters. The eighth water-supply, whose water evidenced more than 10/~g I ~of VHO, distributed water without any disinfection treatment; the water pumped from the wells was already contaminated by VHO at the level of the water-table. The presence of VHO directly in ground water is probably due to infiltration into the ground of industrial waste-waters, since they were almost exclusively chlorinated solvents. Compared to other drinking waters, such as U.S. samples ( 2 1 # g l ~ of chloroform, Symons et al., 1975) and French samples (from 1.1 to 4 . 4 # g l 1, Montiel, 1980; Chambon et al., 1983), the EmiliaTable 5. V H O levels in surface water samples collected in 31 stations V H O levels ( # g l i)

No. of stations

%

0 < I 1-10 >10

5 15 6 5 31

16.1 48.4 19.4 16.1 100

Total

Table 6. An example of a surface water contaminated by V H O V H O levels (#g t 1) CHCI 3 CHCI 2 Br CHCIBr2 CHBr 3 1,1,1 Trichloroethane Carbon tetrachloride 1,1,2 Trichloroethylene 1,1,2,2 Tetrachloroethylene Others Total a m o u n t

Mean 2.2 0 0 0 26 < 1 32 136 0 169

Min-max

%

0.6-6.2 0~) 0q) 0~) 1040 0~ < 1 1.2 I I 1 18 168 0~) 28-263

I 0 0 0 I1 0.1 30.5 57.4 0 100

962

G. AGGAZZOTTIand G. PREDIERI Table 7. VHO levels in swimming pool samples collected in 10 pools No. of waters VHO levels treated with No. of waters treated % (#gl ~) NaCIO % with dichloroisocyanurate 0 0 0 0 0 < 10 0 0 0 0 10-100 2 40 5 100 > 100 3 60 0 0 Total 5 100 5 100

Table 8. An example of a swimming pool water contaminated by VHO VHO levels (,ugl i) Mean Min-max % CHC13 115 62-179 91.9 CHCI2Br 8.0 6.(~10 6.8 CHCIBr2 1.4 0.8 2.0 1.3 CHBr3 0 13-0 0 1,1,1 Trichloroethane 0 0~) 0 Carbon tetrachloride 0 049 0 1,1,2 Trichloroethylene 0 0~ 0 1,1,2,2 Tetrachloroethylene 0 04) 0 Others 0 0~9 0 Total amount 125.8 7(~177.4 100

R o m a g n a samples show an intermediate level of pollution, mainly as regards to chloroform. Concerning surface waters, samples levels varied widely from station to station; 1,1,2 trichloroethylene and 1,1,2,2 tetrachloroethylene were the most represented compounds, may be as a result of discharging industrial waste in surface waters. High levels of T H M appeared in swimming pools, as already mentioned in another survey in Italy (Aggazzotti et al., 1984) and elsewhere (Beech et al., 1980; Norin and Renberg, 1980; Lahl et al., 1981; C h a m b o n et al., 1983). Waters disinfected with dichloroisocyanurate showed levels of T H M lower than waters treated with different disinfectants, unlike what has been observed by C h a m b o n et al. (1983). CONCLUSION

On the basis of these results, it becomes evident that V H O pollution in Emilia-Romagna waters is widespread, but not always at high levels. Drinking waters are mainly contaminated by T H M ; it appears evident that these compounds are formed by reaction of NaCIO or C12 with organic matter present in raw waters. Many natural ground waters in Emilia-Romagna contain high amounts of organic substances, as they come from deep ground layers, whose geological origin is recent. At the moment it is quite impossible to assess long-term hazards due to the ingestion of VHO, at the levels commonly found in drinking waters; indeed a limit for V H O concentration in drinking waters in Italy has been set ( 3 0 # g l -~) and it has to be reached within the next 5 years after the law comes into force (Decreto Presidente Consiglio dei Ministri, 8 Febbraio 1985).

Swimming pool waters showed levels higher than in drinking waters; this kind of water can be ingested, most of all by children, diving and playing in the pool. It must be noted that in swimming pools T H M can be liberated as gas in the air above the water surface; sometimes they can reach high concentrations, particularly in indoor pools. This possibility has been verified in Germany (max = 384/~g m 3, Lahl et aL, 1981) and in Italy (max = 787 p g m 3, Aggazzotti et al., 1984). When evaluating total body burden of T H M , especially for chloroform, the inhaling contribution must be considered and added to the amount that can be ingested, most of all for people regularly attending indoor swimming pools. V H O presence in surface waters represents quite a different problem; these compounds are not T H M , and are due to wastewater drainage, as they are mainly chlorinated solvents, which are widely used in industrial activities. These compounds do not act directly against human health, as surface waters are not used for drinking in the region investigated. However, they can produce heavy effects on the ecological situation of water courses, as they can modify environmental biological mechanisms, as, for instance, chemioreception among fish (Jung, 1978; Browne et al., 1982). Also, it cannot be excluded that these compounds such as pesticides, and polychlorinated biphenyls, can be accumulated in aquatic flora and fauna; in this way they can enter into food chain and reach man. Acknowledgement--This research was financed by the Italian Ministry of Education. REFERENCES

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