Distribution and determinants of trihalomethane concentrations inindoor swimming pools. (Original Article).(Statistical DataIncluded)

Author: H. Chu and M.J. Nieuwenhuijsen

COPYRIGHT 2002 British Medical Association

Objectives: For many decades chlorination has been used as a major disinfectant process for public drinking and swimming pool water in manycountries. However, there has been rising concern over the possible linkbetween disinfectant byproducts (DBPs) and adverse reproductive outcomes. Thepurpose of this study was to estimate the concentrations of trihalomethanes(THMs) in some indoor swimming pools in London and their variation within andbetween pools and any correlation with other factors.

Methods: Water samples were collected from eight different indoor swimmingpools in London. A total of 44 pool samples were collected and analysed fortotal organic content (TOC) and THMs. Water and air temperature were measuredalong with the pH during the collection of pool samples. The level ofturbulence and the number of people in the pool at the time were alsoassessed.

Results: The geometric mean concentration for all swimming pools of TOC was5.8 mg/l, of total THMs (TTHMs) 132.4 [micro]g/l, and for chloroform 113.3[micro]g/l. There was a clear positive linear correlation between the numberof people in the swimming pool and concentrations of TTHMs and chloroform(r=0.7, p<0.01), and a good correlation between concentrations of TOC andTTHMs (r=0.5, p<0.05) and water temperature and concentrations of TTHMs(r=0.5, p<0.0l). There was a larger variation in THMs within pools thanbetween pools.

Conclusion: Relatively high concentrations of THMs were found in London’sindoor swimming pools. The levels correlated with the number of people in thepool, water temperature, and TOC. The variation in concentrations of THMs wasgreater within pools than between pools.

**********

Chlorination is a process whereby harmful pathogens are eliminated from thewater. During this process, not only unwanted micro-organisms are removed butseveral organic halogenated compounds known as chlorination disinfectionbyproducts (DBPs) are formed at the same time (1). Excessive exposure to DBPsmay be harmful to humans. (2)

Trihalomethanes (THMs), generally the most common DBPs, are volatilehalogenated hydrocarbons, which can vaporise from water into the atmosphere.When chlorine is added to the water, it reacts with the organic matter in thewater such as skin scales and residuals from body care products to form various DBPs, including THMs. (1 3) The THMs include chloroform ([CHCl.sub.3]), bromodichloromethane (BDCM) ([CHCl.sub.2]Br), chlorodibromomethane (CDBM) (CHCl[Br.sub.2]), and bromoform ([CHBr.sub.3]). In general, chloroform is the most common occurring THM. The International Agency for Research on Cancer has classified chloroform as a 2B carcinogen.

Adverse reproductive outcomes such as spontaneous abortion, birthweight, neural tube defects, urinary tract defects, and others have been associated with exposure to THMs, but the evidence so far seems to be inconsistent and inconclusive. (4)

There are three different exposure routes–ingestion, inhalation, and dermal absorption–and all routes can contribute to the total uptake of THMs. (1 5) Everyday pathways include drinking tap water, showering, bathing, washing up, and boiling water. For swimmers, the greatest uptake is likely to be through dermal absorption because a large surface area of skin is exposed and inhalation from the air above the pool water surface. (1) The rate of inhalation depends on the intensity of the exercise.

Weisel and Shepard (6) measured mean chloroform concentrations of 85 [micro]g/l in the water and 87 [micro]g/[m.sup.3] in air in swimming pools. Lindstrom et al (7) reported chloroform concentrations of 68 and 73 [micro]g/l in the water. Matthiessen and Jentsch (8) measured mean concentrations of THMs of 29.7 [micro]g/l in water and 142 micro/g[m.sup.3] in air in swimming pools in Germany. Slightly lower concentrations were measured in both air and water by Camman and Hubner (9) in Germany. They also measured CDBM, BDCM, and bromoform, but the concentrations of these were much lower than chloroform with a maximum of 6.51 [micro]g/l of CDBM in water and 22.4 [micro]g/[m.sup.3] for BDCM in air. In Holland, Aiking et al (10) measured concentrations of chloroform in water of 18.4 [micro]g/l in indoor pools and 24.0 [micro]g/l in outdoor pools. Aggazzotti et al (11-14) conducted a series of studies in Modena, Italy, and found correlations between chloroform concentrations in air and water and the number of swimmer s, (11 13) and chloroform concentration in water and free and combined chlorine residual and water pH, (11) but these were generally only weak to moderate correlations.

At present there are few publications on the amount of total organic content (TOC) and concentrations of THMs in United Kingdom swimming pools. Therefore, this study aims to provide a greater understanding of the concentrations of THMs in United Kingdom indoor swimming pools, the variability in these concentrations, and any correlation with other factors.

METHODS

Sampling

A list of indoor swimming pools in London was obtained from Sportline, a sports telephone information service. A total of 29 swimming pools were identified and eight were chosen to take part in this project. The indoor swimming pools were primarily chosen for convenience of travelling to collect samples. (15)

The swimming pool water sampling was conducted between 19 June 2000 and 14 July 2000. For each pool at least one sample was collected once every week for 3 consecutive weeks. In some pools two samples were collected at the same time to estimate the coefficient of variation. Pool samples were collected in 150 ml brown bottles for analysis of both THMs and TOC. The bottles were filled to the top and the caps were tightly sealed with a screw cap to prevent THMs volatising into the environment. Samples were refrigerated and stored until the end of the week when they were sent to the Thames Water Quality Centre, a United Kingdom Accredited Scheme laboratory in Reading, to be analysed. Also, a few samples of tap water were taken for comparison.

Water and air temperature, pH, turbulence, and the number of people in the pool were recorded when the samples were collected.

Laboratory analysis

The method of TOC analysis was based on that described in the instrumental measurement of total organic carbon, total oxygen demand, and related factors. (16) An O.I. model 700 Carbon analyser was used to analyse the concentration of TOC. Samples were firstly treated with phosphoric acid, then by nitrogen to convert organic carbon to carbon dioxide. The samples were then treated with a sodium persulphate solution at 100[degrees]C, then by nitrogen to convert any organic carbon left to carbon dioxide. The carbon dioxide was trapped and concentrated on an absorbent where it was heated rapidly, and measurements were taken with an infrared detector. This process took about 10 minutes a sample. The detection limit for TOC was 0.1 mg/l.

The THMs analysis was based on the method described for chloro- and bromo-trihalomethanated methane in water (17) and halogenated solvents and haloforms in water using a static headspace technique. (18) This method can detect chloroform, bromoform, CDBM, BDCM, trichloroethene, trichloroethane (1,1,1), and carbon tetrachloride. The samples were individually sealed in a vial fitted with a crimp on septum cap. The samples were equilibrated at 70[degrees]C for 27 minutes in a Perkin Elmer HS 101 headspace analyser. A subportion of the headspace gas was then transferred through a needle (100[degrees]C) and transfer line (120[degrees]C) to a Perkin Elmer 8500 gas chromatograph fitted with a capillary column (HP5 25 mx0.32 mm or equivalent). Oven temperature started at 40[degrees]C and ramped up at 25[degrees]C/minute to 163[degrees]C after 5.5 minutes isothermal time. Detection took place with an ECD detector (300[degrees]C). The injector temperature was 150[degrees]C.

The samples had to be in equilibrium before processing. The distribution of a liquid is directly proportional to the distribution of its vapour. The samples were individually sealed in a vial fitted with a crimp on septum cap. The vial was left in an oven for a fixed time for headspace gas equilibrium with the sample. The vial was then punctured and samples were transferred onto a capillary gas chromatograph, where the components were then separated and measured. Full quality control procedures were in place. The detection limit for each of chloroform, bromoform, BDCM, CDBM, and trichloroethene was 2.5 [micro]g/l, for trichloroethane (1,1,1), and tetrachloroethene 1.0 [micro]g/l, and for carbon tetrachloride 0.3 [micro]g/l. Concentrations of trichloroethene, trichloroethane (1,1,1), and carbon tetrachloride were all below the limit of detection and are not further described in this paper.

The coefficient of variation of the method was calculated (table 1). The coefficients of variation (%) were low. Most were below 5% variability but TOC showed a 13.4% coefficient of variation.

Statistical analysis

The analyses were carried out using statistical software SPSS. Spearman rank correlation was used to estimate the correlation between the various variables. A one way analysis of variance (ANOVA) model was used to estimate the swimming pool variance components.

RESULTS

Concentrations

A summary of the swimming pool concentrations is shown in table 2. The arithmetic mean (AM) of TOC concentration of the swimming pools was 6.3 mg/l, compared with 2.3 mg/l in tap water in London. The AM of chloroform was 121.1 [micro]g/l in the swimming pools and 3.5 [micro]g/l in tap water. Similar BDCM concentrations were found in swimming pools and tap water samples; 8.3 [micro]g/l and 7.5 [micro]g/l, respectively.

Variance within and between swimming pools

The variances within and between swimming pool components were estimated and concentrations of chloroform, BDCM, CDBM, and TTHMs were found to have a much greater variation within pools than between pools whereas TOG had a greater variation between pools (table 3).

Correlation

Correlation coefficients are shown in table 4. The concentrations of TOG and TTHMs showed a good correlation; where TOG increased, TTHMs increased (r=0.5, p<0.05, fig 1). A positive linear correlation was found between water temperature and the TTHMs (r=0.5, p<0.01, fig 2). The strongest correlation was found for the number of people in the swimming pools and concentrations of TTHMs and chloroform (r=0.7, p<0.01, fig 3).

DISCUSSION

The main findings of this study were: (a) that there are relatively high concentrations of TTHMs in indoor swimming pools in London, (b) that the variation in concentrations of TOG was greater between pools whereas for chloroform, BDGM, and GDBM variation was greater within pools, (c) that there were strong correlations between concentrations of TTHMs and chloroform, TOG, water temperature, and the number of people in the swimming pools.

Concentration of TTHMs

The concentrations of chloroform collected in these swimming pools were found to be relatively high compared with other studies conducted outside the United Kingdom. In Italy, Aggazzotti et al(11-14) found concentrations of 17-47 [micro]g/l of chloroform in the water and 66-653 [micro]g/m(3) of chloroform in the air. For non-competitive swimmers, a mean of 0.4 [micro]g/l chloroform was found in the blood between 1 and 40 minutes after exposure. Weisel and Shepard(6) measured mean chloroform concentrations of 85 [micro]g/l in the water and 87 in air in swimming pools, but other studies(7 9 10) found much lower concentrations in their swimming pool studies. The concentrations of TTHMs in London swimming pools were also considerably higher than the concentrations in tap water.

Individual THMs: variation within and between pools

Although other studies generally focused on one swimming pool we included several pools and estimated the variance components within and between pools. The analyses showed that most variance in TOG was between swimming pools. This is probably because TOG is affected by few factors–such as the number of people in the swimming pool. Chloroform, BDGM, CDBM, and TTHms concentrations varied more within the swimming pools. These concentrations depend on a more complex set of factors–such as the amount of TOG in the water, pH, temperature, and number of people.

Correlation

Concentrations of TOG and chloroform were correlated and this is not surprising as when chlorine is added to water, it reacts with some components of TOG to form chloroform. Concentrations of TOG in tap water were almost three times lower than those in swimming pools, and this suggests that the greatest proportion of the TOC originated in the pool possibly from the swimmers. Concentrations of TOC should be reduced as far as is reasonably practicable to reduce the formation of THMs.

Concentrations of TTHMs were also correlated with the temperature of swimming pool water. As water temperature rose, more chloroform was formed, especially in indoor swimming pools, in which water and air temperature are generally higher than in outdoor swimming pools, and therefore more TTHMs are likely to be formed in both water and air.

The number of people in the swimming pool was positively correlated with the concentrations of TTHMs and chloroform. Also Aggazzotti et al (14) found that the number of people in the swimming pools affected the concentration of TTHMs. In one study they found that 40-50 competitive swimmers in the pool doubled the concentration of TTHMs in air and water compared with a pool without swimmers. The TTHMs and chloroform concentrations in the water increased probably because as there were more swimmers in the pool, the turbulence and splashes increased and more organic material was released, which allowed TTHMs to form.

Uptake of THMs

In this study we only measured the THMs concentrations in water, but some other studies have measured the actual uptake, which was consiberable. Levesque et al (19) measured the body burden (based upon 11 male swimmers) resulting from exposure to chloroform in water and air of an indoor swimming pool. A 1 hour swim was postulated to result in a chloroform dose of 65 [micro]g/kg/day, 141 times the dose from a 10 minute shower (0.46 [micro]g/kg/day) (19) and 93 times greater than exposure by ingestion of tap water as demonstrated by Jo et al. (20) Lindstrom et al (7) estimated that the dermal route of exposure accounted for 80% of the blood chloroform concentration during swimming. Aggazotti et al (11) found a correlation between chloroform concentrations in plasma and number of swimmers ([r.sub.s] = 0.32), time spent swimming ([r.sub.s] = 0.57), chloroform concentrations in water ([r.sub.s] = 0.48), and chloroform concentrations in environmental air ([r.sub.s] = 0.74), whereas 4.7% of the variance in plasma co ncentrations was explained by the intensity of physical activity. Aggazotti et al (14) reported a mean chloroform uptake of 25.8 [micro]g/h (range 22-28 [micro]g/h) at rest and 176.8 [micro]g/h (134-209 [micro]g/h) after 1 hour swimming (arithmetic mean of chloroform concentration in pool water was 33.7 [micro]g/l). Lower concentrations of uptake were reported for CDBM and BDCM. Also other studies, [6,8-10] recorded considerable uptake of chloroform during swimming. Potential uptake for people swimming in the pools in this study is likely to be higher than reported in other studies as the concentration of THMs in water were higher. However, it is important to note that inhalation is an important route of exposure and the uptake through this route is affected by various factors including for example, the number of swimmers, turbulence, and breathing rate. As we did not take any measurements in air it is difficult to estimate the actual uptake in our population. Implications of risk to health Most of the reproductive health studies of DBPs have been carried out focusing on drinking water. Swimming seems to have a greater risk of exposure to DBPs as uptake may occur through three different routes; inhalation, dermal absorption, and, to a certain extent, ingestion and the amount of TTHMs concentration seems to be higher compared with drinking water. Therefore it is essential to gain a better understanding of the possible determinants of TTHMs in swimming pools and this pathway should be included in epidemiological studies where possible. Of course it is important to remember that a major determinant of the total uptake is likely to be the frequency and duration of swimming and more information should be collected on this to allow the estimation of any potential health risks.

REFERENCES

(1.) Nieuwenhuijsen MJ, Toledano MB, Elliot P. Uptake of chlorination infection by products; a review and a discussion of its implications of epidemiological studies. J Expo Anal Environ Epidemiol 2000:10:586-99.

(2.) International Programme far Chemical Safety (IPCS). Disinfectants and disinfectant by-products. Geneva: World Health Organisation, 2000. (Environmental Health Criteria 216.)

(3.) Mannschott P, Erdinger L, Sonntag HG. Determination of volatile haloforms in indoor swimming pool air, Indoor Environment 1994;3:278-85.

(4.) Nieuwenhuijsen MJ, Toledano M, Eaton N, et al. Chlorination disinfection byproducts in water and their association with adverse reproductive outcomes: a review. Occup Environ Med 2000;57:73-85.

(5.) Weisel CP, Jo WK. Ingestion inhalation and dermal exposures to chloroform and trichloroethene from tap water. Environ Health Perspect 1996;104:48-51.

(6.) Weisel CP, Shepard TA. Chloroform exposure and the body burden associated with swimming in chlorinated pools. In: Wang RGM, ed. Water contamination and health. New York: Marcel Dekker, 1994

(7.) Lindstrom AB, Pleil JD, Beerkoff DC. Alveolar breath sampling and analysis to assess trihalomethane exposures during competitive swimming training. Environ Health Perspect 1997;105:636-42.

(8.) Matthiessen A, Jentsch F. Trihalamethanes in air of indoor swimming pools and uptake by swimmers. Proceedings Indoor air conference 1999. Edinburgh, 1999.

(9.) Cammann K, Hubner K. Trihalomethane concentrations in swimmers’ and bath attendants’ blood and urine after swimming or working in indoor swimming pools. Arch Environ Health 1995;50:61-5.

(10.) Aiking H, Ackert van MB, Scholten RJPM, et al. Swimming pool chlorination: a health hazard? Toxico) Left 1994;72:375-80.

(11.) Aggazzotti G, Fantuzzi G, Righi E, et al. Environmental and biological monitoring of chloroform in indoor swimming pools. J Chromatogr A 1995;710:181-90.

(12.) Aggazzotti G, Fantuzzi G, Righy E, eta1. Chloroform in alveolar air of individuals attending indoor swimming pools. Arch Enviran Health 1993;48:250-4.

(13.) Aggazzotti G, Fantuzzi G, Tartoni PL, et al. Plasma chloroform concentrations in swimmers using indoor swimming pools. Arch Environ Health 1990;45:175-79.

(14.) Aggazzotti G, Fantuzzi G, Righi E, et al. Blood and breath analyses as biological indicators of exposure to trihalomethanes in indoor swimming pools. Sci Total Environ 1998;217:155-63.

(15.) Chu H. A report to estimate the amount of DBP exposure and the possible health effects to pregnant women who attend indoor swimming pools in London [MSc report]. London: Imperial College of Science, Technology and Medicine, University of London, 2000.

(16.) Standing Committee of Analysts. The instrumental determination of total organic carbon, total oxygen demand and related determinants. London: The Stationery Office, 1979. (ISBN 0 11 751458 6.)

(17.) Standing Committee of Analysts. Chloro-ond bromo-trihalomethanated methane in water. London: The Stationery Office, 1981. (ISBN 0 11 751544 2.)

(18.) Standing Committee of Analysts. Halogenated solvents and haloforms in water using a static headspace technique. In: Determination of very low concentrations of hydrocarbons in water 1984-5. London: The Stationery Office, 1985:19-23. (ISBN 0 11 752004 7.)

(19.) Levesque B, Ayotte P, LeBlanc A, et al. Evaluation of dermal and respiratory chloroform exposure in humans. Environ Health Perspect 1994;102:1082-7.

(20.) Jo WK, Weisel CP, Lioy PJ. Chloroform exposure and the health risk associated with multiple uses of chlorinated tap water. Risk Anal 1990;10:581-5.