Review of Hydrogen Sulfide and Sour Gas Effects On The Eye - A Historical Perspective

Science of the Total Environment 367 (2006) 1 22 www.elsevier.
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Review
Hydrogen sulfide (H2S) and sour gas effects on the eye. A historical perspective
Timothy William Lambert a,, Verona Marie Goodwin b , Dennis Stefani a , Lisa Strosher a
a
Environmental Health, Calgary Health Region, 1509 Centre St SW, Calgary Alberta, T2G 2E6, Canada b VM Goodwin Research and Consulting Ltd., Canada Received 18 May 2005; received in revised form 19 December 2005; accepted 16 January 2006 Available online 2 May 2006
Abstract The toxicology of hydrogen sulfide (H2S) and sour gas on the eye has a long history beginning at least with Ramazzini's observations [Ramazzini B. Diseases of WorkersDe Morbis Artificum Diatriba1713. Wright WC (trans). New York, C. Hafner Publishing Co Inc.; 1964. 9899 pp.]. In contrast, a recent review by Alberta Health and Wellness (AHW Report) concluded that there is little evidence of eye irritation following short-term exposures to H2S at concentrations up to 100ppm and that the H2S literature on the eye is a series of unsubstantiated claims reproduced in review articles dating back to the 1930s [Alberta Health and Wellness (AHW report). Health effects associated with short-term exposure to low levels of hydrogen sulfide: a technical review, Alberta Health and Wellness, October 2002, 81pp.]. In this paper, we evaluated this claim through a historical review of the toxicology of the eye. Ramazzini noted the effects of sewer gas on the eye [Ramazzini B. Diseases of WorkersDe Morbis Artificum Diatriba1713. Wright WC (trans). New York, C. Hafner Publishing Co Inc. 1964. 9899 pp.]. Lehmann experimentally showed eye effects in men at 7090 ppm H2S and also in animals [Lehmann K. Experimentalle Studien uber den Einfluss technisch und hygienisch wichtiger Gase und Dampfe auf den Organismus. Arch Hyg 1892;14:135189]. In 1923, Sayers, Mitchell and Yant reported eye effects in animals and men at 50 ppm H2S. Barthelemy showed eye effects in animals and men at 20 ppm H2S [Barthelemy HL. Ten years' experience with industrial hygiene in connection with the manufacture of viscose rayon. J Ind Hyg Toxicol 1939;21:14151]. Masure experimentally showed that H2S is the causative agent of eye impacts in animals and men [Masure R. La Keratoconjunctivite des filatures de viscose; etude clinique and experiementale. Rev Belge Pathol 1950;20:297341]. Michal upon microscopic examination of the rat's cornea, found nuclear pyknosis, edema and separation of cells in the eye following exposures for 3 h at 36 ppm H2S [Michal FV. Eye lesions caused by hydrogen sulfide. Cesk Ophthalmol 1950;6;58]. In 1975, in Alberta, irreversible eye damage and photophobia were experimentally produced in calves exposed to 20 ppm H2S for 1 week [Nordstrom GA. A study of calf response of ammonia and hydrogen sulfide gases. Thesis, University of Alberta, Department of Agricultural Engineering, Edmonton Alberta; 1975, 218 pp.]. Alberta Environmental Centre documented clinical irritation of the eye at 40 ppm H2S in 6 hours in rats [Alberta Environmental Centre. Morphological observations in rats exposed for six hours to an atmosphere of 0, 56, or 420mg/m3 hydrogen sulfide. AECV86-A1. Alberta Environmental Centre, Vegreville, Alberta; 1986b. 28 pp.]. In two sour gas blow-outs in Alberta, in the early 1980s, eye injury was documented in humans and animals at 0.5 ppm H2S. Community studies in the United States, Europe and New Zealand suggest that acute exposure to 25 ppb H2S is the lowest concentration to irritate the eyes; with chronic exposure, serious eye effects are suggested. In contrast to the conclusion, all of the studies, except one, cited in the AHW Report indicate toxic effects on the eye below 100ppm H2S [Alberta Health and Wellness (AHW report). Health effects associated with short-term exposure to low
Corresponding author. Tel.: +1 403 943 8048; fax: +1 403 943 8056. E-mail address: tim.lambert@calgaryheathregion.ca (T.W. Lambert). 0048-9697/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.scitotenv.2006.01.034
T.W. Lambert et al. / Science of the Total Environment 367 (2006) 122
levels of hydrogen sulfide (H2S): a technical review, Alberta Health and Wellness, October 2002, 81pp.]. In addition, the AHW Report (2002) mis-presented two studies as clinical studies, claiming they reported no evidence of eye effects in humans from 2 and 30 ppm H2S for 3040 minutes [Alberta Health and Wellness (AHW report). Health effects associated with short-term exposure to low levels of hydrogen sulfide (H2S): a technical review, Alberta Health and Wellness, October 2002, 81pp.]. 2006 Elsevier B.V. All rights reserved.
Keywords: Hydrogen sulfide; H2S; Sour gas; Eye; Conjunctivitis; Historical review; Mechanism
Contents Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 An historical perspective of hydrogen sulfide and the eye . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3.1. Lehmann (1892) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3.2. U.S. Bureau of Mines: Sayers et al. (1923), Mitchell and Davenport (1924), Mitchell and Yant (1925), Aves et al. (1929) and Yant (1930) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3.3. Sjorgen (1939) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 3.4. Viscose rayon spinning rooms: Kranenburg and Kessener (1925), Lewey (1938), McDonald (1938), Barthelemy (1939), Rubin and Arieff (1945), Masure (1950), Nyman (1954), Nesswetha (1969) and Vanhoorne et al. (1995) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.5. Occupational, experimental and community exposures: Michal (1950), Ahlborg (1950), Carson (1963), Beasley (1963), US Department of Public Health Service, Terre Haute (1964), Luck and Baye (1989) and Schiffman et al. (2005). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 3.6. Chronology of Alberta studies: Nordstrom (1975), Burnett et al. (1977), Lodgepole Blowout Report (1984), Drummond Blow-Out (Alberta Environmental Centre, 1984), Arnold et al. (1985), Alberta Environmental Centre (1986a,b) and Lefebvre et al. (1991) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3.7. South Karelia air pollution studies: Haahtela et al. (1992) and Marttila et al. (1994, 1995) . . . . . . . . . . . 14 3.8. Community study in Rotorua: Bates et al. (1998, 2002). . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 4. Critique of Alberta Health and Wellness Report (2002) of H2S . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 4.1. Comparison of AHW Report (2002) review of H2S effects on the eye with other major reviews . . . . . . . . . . 15 4.2. Review of the scientific studies to support AHW Report (2002) conclusion that there is bvery little evidence of eye irritation following short-term exposures to H2S at concentrations up to 100ppmQ. . . . . . . . . . . . 17 4.2.1. Non-clinical studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 4.2.2. Clinical studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 4.2.3. Case-control and observational studies from sour gas releases . . . . . . . . . . . . . . . . . . . . . 18 4.3. AHW Report (2002) critique of Alberta Health (1988) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 1. 2. 3.
1. Introduction Public and occupational exposure to hydrogen sulfide (H2S) can result from many industries, including petrochemical, agricultural and wastewater treatment. Eye irritation from hydrogen sulfide has been described as the first health effect to manifest at low concentrations. Ramazzini (1713) made an articulate observation of the effect of privy gas on the eyes in his book the Diseases of Workers: I pitied him at that filthy work and asked him why he was working so strenuously and why he
did not take it more quietly so as to avoid the fatigue that follows overexertion. The poor wretch lifted his eyes from the cavern and gazed at me, and said: No one who has not tried it can imagine what it costs to stay more than four hours in this place; it is the same thing as being struck blind. Later when he had come up from the cesspit, I examined his eyes carefully and observed that they were extremely bloodshot and dim. I asked whether cleaners of privies regularly used any particular remedy for this trouble.
Only this he replied, they go back at once to their homes as I shall do presently, shut themselves in a dark room, stay there for a day and bathe their eyes now and then with lukewarm water; by this means they are able to relieve the pain somewhat. Then I asked him: Had they a burning sensation in the throat or any respiratory troubles or attacks of headache? Did that stench hurt their nostrils or cause nausea? Nothing of that sort he replied, in this work our eyes only are injured and no other part. If I consented to go on with it any longer I should very soon become blind as has happened to others. Thereupon he wished me good-day and went home, keeping his hands over his eyes I am inclined to think that some volatile acid is given off by this camerine of filth when they disturb it, and what makes this probable is the fact that copper and silver coins carried by these scavengers in their purses turn black. (Ramazzini, 1713, pp. 9899) Ramazzini did not have knowledge of H2S. However, Ramazzini presumed the release of a molecule from the tarnishing of the silver coins; this observation formed the basis of technical measurements of H2S well into this century. At the concentration of the gas experienced, only the eyes were afflicted. Furthermore, the observation detailed that, with increasing time, the severity of the effect increased, such that a 4-h exposure was the maximum someone could endure and that continued exposure risked blindness. Ramazzini observed the characteristic signs described today from H2S exposure: conjunctivitis, photophobia and, in the extreme, loss of vision. Ramazzini's account is consistent with that presented by Grant (1974) in his book on the toxicology of the eye: Effects of hydrogen sulfide on the eyes are notable only at sublethal concentrations, most commonly at concentrations so low that they have no discernable systemic effect. At least 120 articles have been published describing the highly characteristic superficial injury of the cornea and conjunctiva occurring in workmen exposed to low concentrations of hydrogen sulfide in sewers, caissons, tunnels, sugar beet refineries, rayon and artificial silk manufacture, sulfur baths, refining of sulfur containing petroleum, tanneries and sulfur mining. (Grant, 1974, p. 561)
In contrast to the observations of Ramazzini (1713) and Grant (1974), a recent Alberta Health and Wellness Surveillance Branch (AHW Report) (2002) claimed that: There is very little evidence of eye irritation following short-term exposures to H2S at concentrations up to 100 ppm. This is in sharp contrast to the earlier report (Alberta Health, 1988), wherein it was concluded that the eye is susceptible to the irritant action of H2S and irreversible eye tissue damage can occur at 20 ppm H2S. This discrepancy may be explained in part by reliance placed on review articles in the earlier assessment. It would appear that the earlier conclusions relied heavily on statements made by Milby (1962) and Gosselin et al. (1976) attesting to irreversible eye tissue damage at concentrations > 20 ppm for several hours exposure. Neither statement represents original research. Instead the following statement by Milby cites Yant (1930), exposure to concentrations above 50ppm for a period exceeding 1 hour may produce irritation of the conjunctival and corneal tissues. The statement does not suggest irreversible eye damage, nor does it make reference to effects at 20ppm. Moreover the report by Yant also does not represent original research. Alberta Health (1988) also reported blurred vision at 0.08ppm (Kleinfeld et al., 1964); however, this exposure concentration was not stated in the cited document. Thus it appears that unsubstantiated opinions have been propagated through several review articles, dating as far back as 1930. (AHW Report, 2002, p. 58) The first part of this paper presents a historical review of the literature and the latter half a critique of the AHW Report (2002) claims. This historical review addresses the question of the likelihood that the eye will respond to H2S at concentrations below 100 ppm H2S. The review develops the observations of Ramazzini, providing details of the signs of exposure, the different environments in which they have been experienced and the specific levels of H2S. 2. Methods Toxline and Pubmed databases were searched for all papers relating to H2S. All papers cited in review articles were obtained including English and other languages. The review focuses primarily on English papers published in the last 100 years and emphasizes the key findings on the toxicological effects on the eye. Three key papers in non-
English were translated into English: Lehmann (1892), Masure (1950) and Michal (1950). There are a large number of studies in non-English which were not translated due to financial limitations. The specific details of each paper are presented such that the reader can understand the scientific quality of the particular study. We obtained and compared all of the literature cited in the AHW Report (2002). We also compared the AHW Report (2002) citations with NIOSH (1977), Alberta Health (1988) and WHO (2003), to illustrate the citations which the AHW Report (2002) is relying on for its conclusions. In contrast to the AHW Report (2002) method, our approach to the historical perspective was not to simply select the best scientific papers. We did not simply collect the harmonious statements to suggest the definitive perspective on H2S effects on the eye. Our approach has been to present the papers such that a reader can appreciate the divergence, consistency and coherence of the perspectives and observations of H2S eye toxicity. 3. An historical perspective of hydrogen sulfide and the eye Mitchell and Davenport (1924) reviewed much of the early literature from 1773 to 1924. Most of the early reports were conducted in France and they note the following in their paper with respect to the eye. In 1785, Halle identified two toxicological observations in sewer workers: a condition called mitte, inflammation of the eyes and mucous membranes, and plomb, a type of asphyxia. In 1832, Christison observed that these two types of toxicological effects were due to H2S and that the eye effects were related to sub-acute exposures. In 1911, Oliver reported numerous cases of conjunctivitis in the workmen in the sulfur mines of Sicily. 3.1. Lehmann (1892) One of the earliest experimental studies is that of Lehmann (1892), who conducted a series of acute chamber study exposures on men and animals. Lehmann (1892) conducted experiments on six men at a range of H2S concentrations; observations of eye effects that he tabulated are presented in Table 1. Lehmann described eye effects of one subject and himself: Kwilecki's (subject) observation of mucous membrane irritation symptoms both before and after the onset of headache is notable. I also noted the onset of a most pronounced and painful irritation of the nasal and eye mucous membranes, even before any sign of headache. Lehmann noted that no significant observa-
tions were noted for any of the animals that Kwilecki regularly took into the test chamber with him. Lehmann had difficulty with measurement of the H2S concentrations and observed his method tended to overpredict the concentrations. After adjusting his experimental apparatus to improve H2S measurement, Lehmann noted the following from exposure of two additional subjects: The trial results indicated that a H2S concentration of 0.020.04 per thousand [20 40ppm H2S] over a 1-h exposure period did not yet induce any symptoms of irritation. A concentration of 0.070.09 parts per thousand [7090ppm H2S] induced a mild biting sensation in the throat and eyes. Similarly, 0.140.15 per thousand [140150 ppm H2S] and 0.12 0.13 parts per thousand [120130 ppm H2S] in a different trial also caused uncomfortable, pronounced and immediate biting sensation in the eyes and throat. One observation which Lehmann reported in many trials was the sudden decrease in eye pain during the exposure (Table 1); this suggests development of nerve effects very similar to olfactory fatigue described from H2S exposure. Even with only a few test subjects, Lehmann reported different sensitivity in the men to the effects of H2S and varying health effects aside from the eye. In summary, Lehmann noted that all test subjects showed symptoms of intense irritation targeting the eyes, nose, and tracheal mucous membranes. Lehmann observed similar effects in animal experiments, and claims his results were in agreement with Eulenberg (1865). 3.2. U.S. Bureau of Mines: Sayers et al. (1923), Mitchell and Davenport (1924), Mitchell and Yant (1925), Aves et al. (1929) and Yant (1930) A series of papers were produced by the Bureau of Mines in the United States on health effects from H2S in the petroleum industry from 1923 to 1930. Two papers, Sayers et al. (1923) and Mitchell and Yant (1925), might be of the same experimental results. It is unclear if men were exposed to 50 ppm H2S by Sayers et al. (1925) and if additional experiments at 100 ppm H2S were conducted by Mitchell and Yant (1925). The experiments on animals began at 3550ppm H2S (Table 1). Sayers et al. (1923) stated: a few experiments were carried out on men, using low percentages of hydrogen sulfide (Sayers et al., 1923, p. 2). In a table of effects under sub-acute exposures, they all begin at 0.005 per cent (50 ppm H2S). In the conclusion, the paper says: the exact low limit of
T.W. Lambert et al. / Science of the Total Environment 367 (2006) 122 Table 1 Select experimental studies of hydrogen sulfide on the eye Study Experiment design and H2S concentration Observations/comments
Lehmann, 1892 Men and animals were exposed
None of the tabulated trials specifically mention the 2040 ppm and 7090ppm exposures; the trials only document Mr. Kwilecki and Mr. Greulich symptoms Men were exposed to 2040ppm, 7090ppm and Mr. Kwilecki test subjecteye observations 100138ppm. Several other exposure regimes Test 1: 100150 ppm: after 18 min mucous membranes, nose, and times were reported throat and larynx irritated, followed by eye inflammation and tearing. Symptoms were increased with time. Irritation continued after the trial for some time 5 men in total were exposed in different trials, Test III: 200ppm for 1h: after 5min irritation of mucous membranes, for up to 4 h eyes irritated Method of H2S analysis was reaction with Test IVa: 210ppm for 3h: irritation of mucous membranes led to marked inflammation and swelling of conjunctiva potassium iodide; the H2S concentration in Test VIII: 530 ppm for 40min: after 11 min biting pain in the eyes, the 29m3 room was mixed via a ceiling fan. after 14min eye catarrh Lehmann notes the ceiling fan carried away the Test IX: 575ppm 3h: after 14min biting pain in eyes, 35min iodine vapours, which resulted in strong eye catarrh persisting for duration of trial; after test symptoms over-estimation of the H2S concentrations. of eye catarrh increasing accompanied with lively pain. A constant value of H2S could not be obtained Lehmann suggested Mr. Kwilecki was the least sensitive of all subjects. because of leakage in the room 2nd series of tests with Mr. Greulich Thus, H2S concentrations were not accurate Test 1: 230ppm: irritation of conjunctiva in 13min; 19 min tearing; and concentration varied within the test room. 27min pain in the eyes and lots of tearing; 33min increasing pain and light sensitivity; 40 min eyes open only with difficulty; 46min pain and secretion in eyes almost completely disappears Test 2 (2 weeks later): 490 ppm for 30min and 400ppm for 60min: after 18min eye irritation. 45min no complaints, 1.5h eye itching after trial: 3min significant eye soreness, strong tear secretion, cramping closure of eyes, light sensitivity, swelling of eyelids, redness of conjuctiva; several hourspain in eyes when subject to light Test 3: 300ppm for 2h: 38min eye irritation, 52min painful tear secretion, light sensitivity; 1h. Immediately afterinfection of the conjunctiva, 15min extreme pain in eyes for next 2h; at nightinterruptions in sleep because pain in eyes; light sensitivity Test 4: 532ppm for 30 min: 10min irritation of conjunctiva; 20 min significant eye soreness, difficulty opening eyes, completely adverse to light; 30min extreme pain in eyes. After test: 10min lesioning eye soreness Test 5: 100ppm for 2 and 3 h sessions in 1 day: 48min slight irritation of eyes, light sensitivity; 1h 25min eye soreness and sensitivity almost completely vanished; 2h light sensitivity with continuous increasing frequency of stabbing sensation in eyes; 2h 15min blurred vision 2nd exposure 4h later: 5min stabbing in eyes; 15min start light sensitivity; 29min burning pain in eyes; 1h 45 min significant eye irritation. Left eye hurts; 2h no irritation in eyes After: 1h blurred vision, light sensitivity, eye soreness; at night 5 h latersudden awakening due to eye pain, continuous tears, can only open eyes with force and extreme pain; following morning, eye clinic examinationextreme conjunctivitis, continued development of conjunctivitis, advise to keep eyes closed for hours; 4 pmfirst lesioning of eye pain but remain closed; next morningconjunctiva still red, minor stabbing sensation; 4th dayblurred vision continues, squinting to improve vision causes tear secretion (continued on next page)
6 Table 1 (continued) Study Mitchell and Yant, 1925
Experiment design and H2S concentration Experiments conducted within a 1000ft3 chamber H2S produced with a Kipp generator charged with FeS and HCl H2S mixed in chamber with a fan. H2S analyzed periodically CaCl method Control experiments were conducted and all were negative
Observations/comments Rats: 3565 ppm: 48 h irritation of eyes, 1848h pus in eyes 310350ppm: 230min eyes closed Guinea pigs: 3565 ppm: 1848h pus in eyes Dogs: 100ppm: 48h lacrimation, 816 h pus in eyes, death intense 350ppm: 230min lacrimation Men: (Mitchell and Yant note: compiled from the Work of Lehmann (1892) and the writers of this report) 100150ppm: 215min irritation to eyes, loss of smell; 1530min pain in eyes; 14h sharp pain in eyes 150200ppm: 1530min eye irritation; 14 h indistinct vision, light shy; 48 h serious irritating effect
Masure, 1950
A. H2S, CS2 and H2SO4 alone and in combination Exposed rabbits and guinea pigs B. Exposed rabbits and guinea pigs to the rayon spinning room at three different levels where worker effects observed (50cm, 1.6m and 2.4m), three animals per level Evaluated the mechanism of H2S eye toxicity. C. Investigated local or general action; sutured one eye closed with three rabbits and three guinea pigs and exposed them for 5days in the spinning room D. After acute and after 5-day exposure, treated cells with fixing agent and colouring agent to conduct cell histology. Treated eyes with ferricyanure ferrique which is reduced by SH groups and forms Prussian blue. Masure used a lead acetate colour technique to analyze H2S
A. Concentrated H2S alone resulted in keratitis after 2 h. With 36 to 71ppm H2S, no lesions were observed. When 40 to 70 mg/m3 CS2 was added, they observed lesions in 3 days. With 1429ppm H2S and 70mg/m3 CS2, no lesions were observed after 5 days. No effect was observed with 70mg/m3 CS2 and 300mg/m3 H2SO4 alone. B. First assay 10h/day for 6 days. Only rabbits at the high level had eye effects observed with the slit lamp. Second assay was 5 days continuously. All animals had eye effects but those at top levels had greater effect even though H2S concentration was similar or slightly higher at lower levels. Suggested denser aerosols at higher levels lower the threshold of H2S. C. Found that only the eye exposed to the gas was affected and not the eye sutured closed. The action of H2S is therefore local impact on the eye and not a general affect. D. With exposure in the spinning room, they observed reduction of the epithelium to the basal layer and a flattening of the epithelium, mainly in the central part of the cornea but on the periphery it was a normal thickness. Observed an increase in mitosis at the basal layer suggesting regeneration of the cells. They observed a decrease in attachment to the Bowman's capsule. With pure H2S, observed desquamification process by formation of slits between epithelial layers. Observed individual cylindrical cells that remain individually attached to the Bowman's membrane. Observed this after 2h of exposure to pure H2S which shows the speed of action. After 5-day exposure, observed the central part of the cornea a loss of colourability, translating as a decrease in SH groups. A transition zone of colourability to the edge of unit where it was coloured normally. With concentrated H2S, they did not observe the colour effect and thus the mechanism for acute eye injury and total desquamification is different. No colour change was noted with just CS2 or H2SO4.
hydrogen-sulfide concentration at which it ceases to act as a poison has not as yet been determined, but it is evidently below 0.005 per cent. (Sayers et al., 1923, p. 5). There is no experimental detail in the paper.
Mitchell and Davenport (1924) stated in their review: In an experimental study on the effects of hydrogen sulfide upon animals (canary birds, white rats,
guinea pigs, dogs, and goats) and upon men by Sayers, Mitchell and Yant, it was found that as low a concentration as 0.005 per cent (50 ppm H2S) would cause toxic symptoms and on continued exposure covering a number of days, with a concentration of 0.02 percent (200 ppm H 2S) death occurred. (Mitchell and Davenport, 1924, p. 9) Sayers et al. (1925) stated in a review: the toxic action of H2S has been studied on animals and men. H2S has been found to be toxic in concentrations as low as 0.005 percent (50 ppm H2S) and men exposed daily to such percentages would in all probability suffer irritation of the eyes and respiratory tract, or subacute poisoning. (Sayers et al., 1925, p. 5) Mitchell and Yant's (1925) experimental results on men are difficult to understand as they report them compiled' with Lehmann's (1892) experimental results in a table (see Table 1). In the text Mitchell and Yant (1925) stated: some men were exposed for short periods to H2S in low concentrations (p. 64), and the lowest concentration of H2S to which men were subjected was 0.01 percent, which was definitely irritating. From the experience with canaries and animals, symptoms of irritation were observed in 0.005 percent, and in all probability further experiments will demonstrate that exposures to even lower concentrations over long periods will cause poisonings. (Mitchell and Yant, 1925, p. 73) With respect to occupational exposure, Sayers et al. (1923) presented a typical sub-acute case of H2S poisoning: A laborer worked all night in an atmosphere containing a small amount of hydrogen sulfide. He complained that it pained his eyes, and the following day his cornea was lusterless and pained exceedingly; he suffered marked lacrimation (tears in eyes) and photophobia (pain on exposure to light) existed. He was placed under the care of a specialist. The exposed part of the cornea became cloudy, and later peeled. For several days the patient was unable to use his eyes, but at the end of a week the conjunctivitis cleared up, and his eyes were not permanently affected. He was able to return to work after 10 days treatment. (Sayers et al., 1923, p. 2)
Mitchell and Yant (1925) have virtually the same paragraph as above, but described this as a severe case from a man working several hours in a tank steamed and declared safe. There is no documentation on how it was determined that the eye was not permanently affected, i.e., no comment that the eye was examined with a microscope. Sayers et al. (1923) provided a general description of eye damage. The paper reported: the cases of conjunctivitis range from mild to severe. The eyes itch and smart, and the lids feel dry and rough. The eyes become red and swollen due to inflammation of the conjunctiva. The secretion is increased and may become mucoid or mucopurulent (pus). Photophobia (pain caused by light) is usually marked. In the severe cases the cornea (transparent membrane over the coloured part of the eye) may become cloudy, and the outer cell layer may be destroyed with accompanying pain, photophobia, lacrimation and blurring of vision (Sayers et al., 1923, p. 4). Mitchell and Yant (1925) concluded their paper with a definition of conjunctivitis, which is virtually the same as the above description by Sayers et al. (1923). Mitchell and Yant (1925) stated with respect to occupational exposures that: conjunctivitas, pharyngitis, or bronchitis usually occurred after exposure to low concentrations (0.005 to 0.02 percent) (50 to 200 ppm H2S) of the gas for several hours; occasionally however, they resulted from an exposure of 510 minutes to a relatively high concentration 0.05 to 0.06 percent of gas. These symptoms of poisoning may not appear for some hours after exposure. (Mitchell and Yant, 1925, p. 60) Aves et al. (1929) described cases of eye damage in the Mexican sour gas industry. Similar to Mitchell and Yant (1925), they distinguished between eye damage from exposure to low concentrations over time and acute reactions from high concentrations during blow-outs. Yant (1930) published a review of the Bureau of Mines experimental work citing verbatim wording of the earlier papers. 3.3. Sjorgen (1939) Sjorgen (1939) presented case reports of workers exposed to sulfurated hydrogen in a paper mill and a brief
review of the literature on eye damage from H2S. There is no indication that Sjorgen had knowledge of the work by Ramazzini (1713), Lehmann (1892), Sayers et al. (1923) or Mitchell and Yant (1925). In this respect, the paper provided a relatively independent account of eye damage from H2S from the previous papers reviewed. The source of the H2S exposure was process water that was being used. There were no recordings of the H2S concentration in the air but the room had a pronounced smell. When the plant ceased using the water with H2S, all the health symptoms on the eyes ceased suggesting that the causative agent was H2S. Sjorgen stated the onset of symptoms in the one case were: diffuse annoyance, burning and friction. At an early stage he had symptoms of dimness and saw rainbow haloes around flames of light. By and by the symptoms became enhanced, with abundant lachrymation, dread of light, and redness of the eyes. Finally the burning and friction got so bad he had to leave his work. These symptoms attain their maximum either after one day or after several days. (Sjorgen, 1939, p. 166) Sjorgen stated: it is emphasized by all that keratitis cannot be observed with the naked eye but only with a pocketlens or microscope. The picture one then discovers is marked by a grayish muddy or a fine tiny pin point stippling of the outermost corneal layers within the rima area. According to Strebel it is due to a cystiform swelling of the epithelian cells which are filled with an opalescent exudiation. Later on there are blister formations which burst and leave behind epithelian defects colourable with fluorescein, sometime forming large continuous erosions. (Sjorgen, 1939, p. 169) This is the first record that we found of using fluorescein as a stain to observe the keratitis (although perhaps it is mentioned in the early German papers which we have not translated). The emphasis on the need of using a microscope to see the eye damage was not mentioned by Lehmann (1892), Sayers et al. (1923) or Mitchell and Yant (1925). Sjorgen (1939) stated that people do not become accustomed to the effect of H2S and there has often been observed after the lapse of time increased sensitivity in persons who work in air polluted with H2S (Sjorgen, 1939, p. 170). Lehmann (1892) also
commented that they did not observe any development of habituation and that older workers show heightened sensitivity to the effects of H2S. 3.4. Viscose rayon spinning rooms: Kranenburg and Kessener (1925), Lewey (1938), McDonald (1938), Barthelemy (1939), Rubin and Arieff (1945), Masure (1950), Nyman (1954), Nesswetha (1969) and Vanhoorne et al. (1995) There are several papers that presented eye problems in the spinning industry where exposure to H2S occurs with other compounds present, most notably carbon disulfide (CS2) and sulfuric acid (H2SO4). Kranenburg and Kessener (1925) reported eye pain, photophobia and inability to open eyes as a result of H2S exposure. Based on differential air monitoring data, a concentration of 1625ppm H2S was associated with conjunctivitis and at 1115 ppm H2S was not associated with symptoms. A report by Lewey (1938) reviewed the literature on eye effects from H2S and suggested that the workplace limit of H2S exposure should be 10ppm H2S to protect the eyes. McDonald (1938) discussed eye damage from H2S noting the variability of eye effects: The workers first notice a slight blurring of vision; they see haloes about lights, and have pain in their eyeballs. Their eyes soon begin to tear, and because of the pain and tearing are obliged to stop work. Many of the workers are apparently immune and we frequently heard the story that they were free from sore eyes but that the man next to them would be hardly able to work because pain and tearing (McDonald, 1938, p. 39). McDonald also notes the development of sensitivity that was suggested by Lehmann (1892). McDonald says: once they [the symptoms] have appeared, they are likely to occur repeatedly and some claimed that they [the workmen] had been moved to other parts of the plant because they were susceptible to sore eyes (McDonald, 1938, p. 39). McDonald noted that the blisters in the epithelium heal rapidly as a rule without leaving any scar or impairment of vision and the workers are able to return to work. Barthelemy (1939) presented concentrations of H2S and CS2 that were found to cause keratoconjunctivitis and reported on an experiment with rabbits which reproduced the eye injury observed in workers. Barthelemy recounted a specific incident in the spinning room, when the ventilation system was not adequate to handle the vapours and resulted in many cases of conjunctiva at once. The eye specialist said: none of the patients presented symptoms of CS2 poisoning, but each case has the following symptoms,
varying in degree: intense photophobia, spasm of the lids, excessive tearing, intense congestion, pain, blurred vision, the pupils were contracted and reacted sluggishly, the cornea was hazy and sometimes numerous blisters could be seen. The acute symptoms subsided rapidly and the corneal epithelium regenerated without scarring (Barthelemy, 1939, pp. 148149). Barthelemy discounted CS2 as the causative agent: We were indeed very much puzzled because we knew that in many instances operators had been accidentally exposed for a few hours in another department of the plant to a concentration as high as 0.40 mg CS2 per litre [400 mg/m3] without apparent detrimental effect (Barthelemy, 1939, p. 149). H2S is produced in the spinning room only while CS2 is found in the churn and spinning rooms. Barthelemy presented measurements of air concentration with eye cases (Table 2). The reduction of eye cases from December 1933 to December 1934 was the result of installing a ventilation system. The increases in cases in December 1936 were a result of an increase in H2S and CS2 concentrations. From this data, Barthelemy concluded a threshold for eye injury: it was found that if CS2 was kept below 0.1 mg/L [or less than 30 ppm] and H2S below 0.03 [or less than 20ppm], no trouble whatever was experienced (Barthelemy, 1939, p. 151). Barthelemy stated: we are now inclined to believe that the simultaneous presence of CS2 and atomized particles of spinning bath promote a hypersensitiveness of the conjunctiva and cornea to H2S which gas was recognized long ago as capable of causing severe eye cases (Barthelemy, 1939, p. 150). To confirm their observations on workers, Barthelemy reported an experiment conducted with white rabbits in an environment that reproduced as closely as possible the spinning room conditions. Barthelemy stated that: Dr. Smith found a marked reaction in the conjunctiva and cornea of both eyes of each rabbit
treated, with considerable cornea deposit (Barthelemy, 1939, p. 149), and one of the rabbits was given a very severe exposure and developed a very cloudy cornea with a slight loss of corneal epithelium, probably the beginning of ulcerative process. However, after 8 days, the rabbit had recovered completely (Barthelemy, 1939, p. 150). There is no discussion of the number of rabbits used, nor the eye examination to determine that the rabbit recovered completely. Rubin and Arieff (1945) described a clinical study, although it is perhaps a symptom survey, of 100 workers exposed to low concentrations of CS2 (517 ppm) and H2S (23 ppm). Of the entire group, 1% reported inflamed lids, 1% burning sensation in the eyes, and 1% pain in eyes and circles before eyes, 2% occasional blurring of vision and 1% cloudiness of vision. They found that the day shift reported more burning of eyes (4.5% or 1 of 22 persons) than the shift operators (1.3% or 1 person of 78). However, the other eye symptoms were found only with the shift operators. Rubin and Arieff (1945) noted that 16% of the group had diminished or absent corneal reflexes compared with 12% in the control group. Potential exposures of the control group were not described. Masure (1950) conducted a detailed investigation into eye injury in the viscose rayon industry in Belgium, including animal experiments to identify the causative agents, and the mechanism of H2S eye toxicity (Table 1). Masure described similar symptoms: perception of looking through fog or veil, coloured rings around lamps, lively pains in the eyes, feeling of grains of sand in the eyes, tugging on the eyeball, tearing and photophobia. With a microscope, Masure (1950) described fine superficial lesions of the anterior epithelium of the eye, developed at the level of the centre of the pupil. The lesions were present as fine punctuation, tinged light whitish by fluorescein, corresponding to a desquamation of the epithelium. In most cases, the symptoms were bilateral although 17% of cases were unilateral. Masure (1950) noted human variability.
Table 2 Data reproduced from Barthelemy (1939) of cases of conjunctivitis in the spinning room, December 19321937, and gas concentrations Year Cases reported including recurrent ones None 332 85 None 71 None Average air analysis (mg/L) [ppm] H2SO4 0.031 0.055 0.043 0.032 Not made Not made CS2 0.066 [21] 0.162 [51] 0.122 [38] 0.063 [20] 0.120 [38] 0.103 [32] H2S 0.012 [9] 0.041 [30] 0.032 [23] 0.019 [14] 0.032 [23] 0.025 [18] Increased production Increased production Remarks
December 1932 December 1933 December 1934 December 1935 December 1936 December 1937
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At the concentrations in the spinning room, it was suggested that two to four successive workdays were required for symptoms to manifest. Masure (1950) noted the frequency of eye cases varied with the concentration of H2S and not CS2 (Table 3). The concentration of CS2 remained relatively constant in all five factories. At 0.005 mg/L [5 mg/m 3 or 3.6 ppm] H2S, there were no cases of eye injury despite the same concentration of CS2 as in factory A where the greatest number of cases of eye injury were observed. Masure (1950) presented a number of animal experiments conducted on rabbits and guinea pigs both in the spinning room and laboratory (Table 1). Using a slit lamp, fine and central punctuations that quickly became marked ulcers, and that infiltrated the stroma of the cornea, were observed with fluorescein. Masure sutured an eye closed and demonstrated the eye injury was a result of topical rather than inhaled H2S; this also demonstrated that closing the eye provides protection from exposure. In the spinning room experiment, animals were placed at three heights, as the concentrations changed with height. In the first experiment, the concentration was 38 mg/m3 (27 ppm) H2S at the top and 49 mg/m3 (35 ppm) H2S at the bottom level. There was only eye damage observed at the top level. In the second experiment, the concentration was 22 and 28 mg/m3 (15.720 ppm) H2S at the top and bottom; eye damage was observed at all three levels; however, eye damage was more intense at the top levels. Masure (1950) tested each gas individually (Table 1). After 5 consecutive days of exposure to 70 mg/m3 or 150 mg/m 3 CS2 alone (no H2S), no lesions were observed using a slit lamp. At 300 mg/m3 H2SO4 (10 times higher than in the spinning room) after 5 consecutive days, lesions were not observed with the slit lamp. These findings suggest that CS2 and H2SO4 were not the causal factors in eye lesion formation.
Table 3 Data reproduced from Masure (1950) of cases of conjunctivitis in the spinning room, in different Belgium factories in 1948, and gas concentrations H2SO4 SO2 H2 S Number of % attained Machine CS2 (mg/L) (mg/L) (mg/L) (mg/L) case per spinners month A B C D E 0.063 0.044 0.09 0.06 0.066 0.03 0.03 0.017 0.008 0.005 0.023 0.19 54 13 6 2 0 41 6 4 1 0
With pure H2S, Masure (1950) observed lesions in the animal eyes after 2h. With 50 to 100mg/m3 [36 to 71ppm] H2S after 5 full days, lesions were not observed in the animals with the slit lamp. With the addition of 40 to 70mg/m3 CS2 and the same concentration of H2S, lesions were observed after 3 days. When the concentration of H2S was reduced to 20 to 40 mg/m3 [14 to 29ppm] H2S with 70mg/m3 CS2, lesions were not observed after 5 days. They increased the concentration of H2S on day 5 to 75 to 100mg/m3 [54 ppm and 71ppm] H2S and observed lesions on the next day. Masure (1950) conducted histological experiments to gain some insight into the mechanism of the H2S induced eye damage. Masure (1950) used ferricyanide stain to evaluate effects on the formaldehyde fixed eye tissue. Ferricyanide salts are mild oxidants that react with reducing substances including sulfhydryl groups forming a blue colour known as Prussian blue. Animal eyes exposed to CS2 and H2SO4 did not show any decrease in staining. Animal eyes that were exposed to low levels of H2S alone for several days showed markedly decreased staining for sulfhydryl groups in the central portion of the exposed eye, and a transition zone to colour formation at the periphery. In contrast, eyes exposed acutely to high concentrations of H2S did not result in significant formation of Prussian blue. Masure (1950) concluded that the decrease in free sulfhydryl groups was related to low H2S exposure after several days and that other mechanisms were responsible for the acute high dose effects. Nyman (1954) emphasized the clinical picture of eye effects caused by H2S and treatment of 237 patents with cortisone. From a historical perspective, a key point is the distinction Nyman made between conjunctivitis and keratitis: Both acute and chronic hydrogen sulfide and carbon disulfide poisoning occurs in such plants, acute conjunctivitis induced by hydrogen sulfide being the most frequent. Some patients, in addition develop keratitis. Sometimes this occurs only after the conjunctivitis has persisted for a few days, but occasionally its onset is simultaneous with the conjunctivitis. This type of keratitis has been studied by an ophthalmologist who diagnosed it as keratitis punctata superficilialis. According to the literature a characteristic of this keratitis is that the corneal epithelium remains intact. I have followed such cases of keratitis for seven years, both early and late stages, and found that the
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epithelium of the cornea is often readily broken and the surface of the cornea hence rough. It is as if a small or large epithelial vesicle had developed on the cornea and then ruptured. The edge of such a ruptured vesicle is readily discernable, and it is not unusual for the broken surface to cover practically the whole cornea. At this stage the patient has such severe pain in his eyes that he can neither sit nor lie but walks to and fro with his head bent, covers his eyes with his hands, and complains all the time. He is practically completely blind. He is unable to open his eyes and cannot move outside his room without help. He is afraid of having lost his sight. The disease picture is highly dramatic. (Nyman, 1954, p. 161) Nyman (1954) did not present any concentrations of H2S, which resulted in the above clinical picture. Nyman (1954) suggested three types of eye disease: (1) a pure conjunctivitis, (2) conjunctivitis developing into keratitis in a few days and (3) an immediate keratitis. After Nymans (1954) terminology, the potential for irreversible eye effect can be appreciated as keratitis where healing is accompanied with scar formation. In the case of cornea, a scar or tissue may form during the healing process and can result in partial loss of vision or destroy eye function completely, in particular, when compounded by secondary infection (Gosselin et al., 1976; Potts, 1986). Nesswetha (1969) studied etiologic factors in 6500 cases of keratitis superficialis punctata (spinner's eye), attributed to occupational exposure to H2S. At 15 mg/m3 (10 ppm) H2S, eye irritation occurred after 67 h of exposure. At 20 mg/m 3 (14 ppm) H2S, symptoms developed after 45h. Note, this summary is based on NIOSH (1977) and Alberta Health (1988) as we have not translated the paper. Vanhoorne et al. (1995) conducted a cross-sectional study on eye injury in viscose rayon industry. A key distinguishing feature from the cases described by Barthelemy (1939) and Masure (1950) is that H2SO4 was not detected in the work place. The highest H2S was 8.9 mg/m3 [6.4 ppm H2S] and occurred only in the spinning room, and it always occurred simultaneously with CS2. However, there was no discussion of conjunctivitis and no eye examination of impacted workers. Some workers only had CS2 exposure and the highest concentration exceeded 90mg/m3 [64 ppm]. Considering the group exposed to CS2 without H2S, versus controls, statistically significant differences were ob-
served only for exposure to 3190 mg/m3 CS2 for eye tension (P < 0.05) and photophobia (P < 0.05). For the group exposed to > 90 mg/m3 CS2, statistical significance was achieved for all eye symptoms: pain, tension, burning, hazy sight, coloured haloes, photophobia, irritation, at work. With respect to the group exposed to H2S, statistically significant differences (primarily P < 0.001) from controls were observed for the workers exposed to > 5 mg/ m3 [3.6 ppm] H2S, for all the categories above except coloured haloes. An increase in eye symptoms for all categories with increasing H2S exposure was noted: unexposed, 15mg/m3 [0.73.6ppm] and > 5 mg/m3 [3.6 ppm] H2S. In addition, to assess possible bias, a mail out survey to former workers found that 25% spontaneously responded leaving the workplace because of eye complaints, which suggests the data underestimated the health problems. Vanhoorne et al. (1995) suggested that their study could not distinguish the primary causative agent for the injury. 3.5. Occupational, experimental and community exposures: Michal (1950), Ahlborg (1950), Carson (1963), Beasley (1963), US Department of Public Health Service, Terre Haute (1964), Luck and Baye (1989) and Schiffman et al. (2005) Michal (1950) reported the sudden emergence of 27 people with eye disease after washing beets using wastewater: blepharospasm, dacryorrhea, photodyshoria and oedema of corneal epithelium. The people reported seeing coloured rings around lights, sharp stabbing pain in the eyes, delacrimation, eyelid spasms and obvious redness. Most people affected returned to work after 5 days. The odour of H2S was present in the room and was the suspected cause of the eye disease. The problem went away when they switched to artesian well water. To investigate the cause, Michal (1950) experimentally evaluated acute and chronic eye exposure effects from H2S. At 860ppm H2S, they observed rubbing of eyes and the rat died in 10 min. Microscopic examination showed pycnosis of the epithelium cell nucleus, occasional cell spacing, and oedema reaching all the way to the surface layers of the corneal stroma. Michal reported the same effects as in the acute toxicity experiment with a rat exposed for 3 h at 36ppm H2S. Our calculation suggests that testing was done by exposing a rat to 50 vol.% (50 g/m3) (36 ppm) for 3h, which is similar to the concentration calculated by NIOSH (1977). Beauchamp et al. (1983) and Alberta
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Environmental Centre (1986b) suggested that the experiment was conducted with 54 ppm H2S. Ahlborg (1950) described occupational cases of keratoconjunctivitis from brief exposure and the typical scenario as follows: a thin jet of gas has suddenly shot out against the face of the man working with pipes or pumps. Automatically he had held his breath and gone to get his gas mask. The exposure, therefore, has been extremely intense but brief. Within 12 to 24 hours keratoconjunctivitis has developed, with pain, itching, photophobia and other eye disturbances. (Ahlborg, 1950, p. 260) Carson (1963) and Beasley (1963) described the exposure of five men to H2S and ammonia (NH3), in a well ventilated room. Beasley (1963) specifically distinguished the H2S and NH3 eye effects, to suggest that three of five men developed symptoms associated with H2S. Carson (1963) described many of the symptoms of H2S exposure. Carson noted that none of the three men complained of their symptoms or the atmosphere in the plants, and, unfortunately, therefore, the measurement of H2S was not made. Carson suggested that the incident provides further support that ocular affects are the earliest symptom of H2S exposure. In Terre Haute, Indiana (USDH, 1964), June 1964, a release from a chemical lagoon resulted in community levels of H2S recorded as 0.022 0.125 ppm for 7 h. Citizens complained about burning eyes. It is stated in the NIOSH report: this study did suggest that hydrogen sulfide can irritate the eyes and respiratory system at concentrations below 1ppm (NIOSH, 1977, p. 44). Luck and Baye (1989) presented case reports of several people acutely exposed to H2S while making sausages: bilateral blepharospasm, photophobia and lacrimation, intense conjunctival infection, and superficial punctate corneal erosions (Luck and Baye, 1989, p. 748). Slit lamp biomicroscopy showed resolution of the superficial punctate corneal erosions. There were no other health conditions reported from the exposure. Schiffman et al. (2005) exposed 48 healthy participants to a complex mixture containing 24 ppb H2S, 817 ppb NH3, 0.024 mg/m3 total suspended particulates and 7.4 EU/m3 endotoxin for 1 h. Eleven participants reported eye irritation after the exposure and seven participants 2h later. Two reported eye irritation prior to exposure. A control group was exposed to filtered air; two reported eye irritation. NH3 is not reported to cause eye irritation until concentrations reach 50 ppm.
Particulate matter is generally not thought to be an eye irritant unless in concentrations exceeding 5mg/m3. Endotoxin is also not known to be an eye irritant. 24 ppb H2S appears to be the responsible agent. 3.6. Chronology of Alberta studies: Nordstrom (1975), Burnett et al. (1977), Lodgepole Blowout Report (1984), Drummond Blow-Out (Alberta Environmental Centre, 1984), Arnold et al. (1985), Alberta Environmental Centre (1986a,b) and Lefebvre et al. (1991) Nordstrom (1975) designed a study of calves which specifically evaluated the effects of H2S on the eye, among other end-points. Alberta Health (1988) cited the study as Nordstrom and McQuitty (1975). A specific chamber was built for exposure, to allow for constant and monitored concentration of H2S. A total of 8 calves were continuously exposed to 20 ppm H2S or 150ppm H2S for 7 days. Other calves were exposed to NH3 and a combination of the gases. Background concentrations of 13 ppm NH3 were noted in all trials. A 7-day control group was also included. Nordstrom concluded: exposure to 20 ppm H2S for one week apparently caused permanent tissue damage to the cornea. At 150ppm H2S induced severe corneal opacity and rupture of the eye appeared possible toward the end of the gas-exposure period (Nordstrom, 1975, p. iv). Calves' eyes were clinically examined by Dr. Beck, a veterinarian with Alberta Agriculture, who concluded the damage at 20 ppm H2S was irreversible. Nordstrom stated: bH2S appeared to have a direct degenerating effect through cytotoxic mechanisms on the viability of the exposed membranes of the eye the conjunctiva and cornea, and of the nasal mucous membranes. At both levels of H2S, definite detrimental effects were apparent. At times the calves appeared lethargic and stood with heads lowered, eyes closed and at both levels of H2S, signs of photophobia were evidenced by strabismus and refusal to open the eyesQ (Nordstrom, 1975, p. 112). On day 2 of the 20ppm H2S exposure, one calf demonstrated definite cloudiness of the cornea and another slight dullness of the eyes. At the higher levels of H2S corneal opacity was severe. Nordstrom commented that in two calves, it appeared they had become blind.
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Burnett et al. (1977) presented cases of H2S poisoning, typically acute exposure, in Alberta from 1969 to 1973. 92% of the cases occurred in the oil, gas, and petrochemical industries. Of 221 cases, conjunctivitis was observed in 5% of cases at the accident site, 9% at physician's office and 11% at the emergency room. Two case reports were presented. One case at the accident site had tearing of the eyes and photophobia and, at the hospital, he had severe photophobia, with blepharospasm but no obvious conjunctivitis. A second worker, who eventually died 34 days after vital system support, was described at the hospital as having florid conjunctivitis. In Alberta, Canada, the 1982 Lodgepole sour gas well blowout resulted in wide-spread exposure to H2S. The time of exposure is difficult to determine but occurred on and off for 28 days. The maximum concentrations of H2S in the area were 3.5ppm in Drayton Valley, 14.5ppm in Lodgepole, 14 ppm in Cynthia and 6 ppm in Violet Grove (Alberta Environment, 1982). Alberta Health reported complaints of eye and lung irritation in Cynthia after a maximum potential exposure of 14 ppm H2S for 2 h (Alberta Health, 1988). In the Lodgepole area, 43% of 189 people involved in a health survey reported eye problems and 33% of the total population (Win Consulting, 1983, p. 319). Residents described their eyes as feeling sandy or burning and several people reported having blurred vision. It was reported that: mucopurulent exudate, which is reported to accompany inflamed conjunctiva, occurred in several children of Pembina area members. These young children had to have the exudate wiped from their eyelids before they could open their eyes in the morning (Win Consulting, 1983, p. 55). Further away, in the Edmonton area, 25% of respondents reported eye irritation where the concentrations were 0.5ppm H2S and, in Drayton Valley, 37% reported eye irritation where the concentrations were up to 2.6 ppm H2S (Edmonton Board of Health, 1983). The Alberta Government Lodgepole public hearing report noted that animals in the vicinity were affected in a similar manner as humans, i.e., runny eyes and noses and that the younger animals were affected more than the older ones (Lodgepole Blowout Report, 1984, p. 72). The report stated: the panel accepts that the high rate of ocular and respiratory symptoms reflecting mucous membrane irritation in different species of animals simultaneously and the disappearance of birds and small animals was unique and cannot be explained on the basis of natural causes (Lodgepole Blowout Report, 1984, p. 72).
In the 1984 Drummond 6-30 sour gas well blow-out, many animals were exposed to sour gas (Alberta Environmental Centre, 1986a). The sour gas was released from September 2428, 1984. On one farm located 2 km from the wellhead the maximum H2S concentration measured was 0.60.7 ppm (1 hour average), with most levels <0.5 ppm H2S. On October 5, Dr. Beck, who observed the calves in the Nordstrom research, Dr. Fenton and Dr. Coppock observed 151 cattle on this farm and reported: approximately 30% of the steers were coughing, and with moderate exercise, this number increased to approximately 60%. A clear mucopurulent nasal discharge was present in approximately 60% of the animals, 30% showed excessive lacrimation and 15% photophobia (Alberta Environmental Centre, 1986a, p. 37). On October 10, Dr. Fenton indicated that one steer appeared blind on the right side. In other cattle on neighboring farms at similar concentrations, the three doctors observed conjuctivitis, lacrimation and one calf with a cloudy cornea and excessive lacrimation. Arnold et al. (1985) reported there were 18.4% or 46 clinical cases of conjunctivitis in 250 workers who submitted claims in Alberta from 1979 to 1983. They suggest that some cases persisted for several days. This was a similar rate documented in previous years. There was no reporting of the concentration of H2S. Alberta Environmental Centre (1986b) (cited also as Lopez et al., 1986) exposed Long Evans rats to 40 ppm H2S for 6h. The study was designed to evaluate the nasal and pulmonary response to H2S, but the effects on the eye were noted and the conjunctiva were examined microscopically for ocular lesions. The study reported that, even though there was lacrimation, there were no macroscopic lesions or histopathological changes observed on the cornea or conjunctiva for up to 42h post-exposure. The report stated: The lack of ocular lesions in our experiment was likely dose or time related since severe eye irritation was clinically observed during and after H2S exposure. In the present study, lacrimation was noticeable at 40 ppm H2S, in contrast to a previous report in which 76 mg/m3 (54 ppm) H2S was reported as the lower threshold for eye irritation (Michal, 1950) (Alberta Environmental Centre, 1986b, p. 13). Our review of Michal (1950) suggests that 36ppm H2S and not 54 ppm was used. Lefebvre et al. (1991) reported an objective measures of ocular irritation as a consequence of hydrogen sulfide exposure. Rats were exposed to 560 mg/m3
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(400 ppm) for 4h and 2100 mg/m3 (1500 ppm) H2S for 4min. The % of exfoliated cells was compared with controls. Corneal epithelial cells represented the majority of exfoliated cells followed by conjunctival epithelial cells. There were few exfoliated polymorphonuclear leukocytes. Masure (1950) also suggested that there was no infiltration to the leukocytes. Guidotti (1994) discussed the possibility of a linear doseresponse curve for eye injury. From Lefebvre et al. (1991), an approximation of the toxic load equation for eye toxicity can be inferred. If we assume linearity and that the two treatments had equivalent toxic load and effect, where toxic load = (concentration)n time, then the exponent on concentration would be n = 3.1. This is in the range of n values for H2S lethality, where a value of n = 2.5 has been used and justified based on animal and human data (ERCB, 1990), and an n = 4.4 calculated from rat lethality (EPA, 2002). However, Lefebvre et al. (1991) observed that 560 mg/m3 for 240min resulted in more exfoliated cells than 2100 mg/m3 at 4 min, i.e., the toxic load at 560 mg/m3 for 4 h was greater than 2100 mg/m3 at 4min. This suggests that the n value should be smaller than n = 3.1. Relative to this point, concentration becomes less important and time of exposure more significant in the H2S toxic load on the eye. However, Masure (1950) inferred different toxicological mechanisms may be involved for acute and chronic toxicity. This limits the extrapolation of this toxic load equation to low concentrations for long periods of time. In two studies on adult Sprague-Dawley rats, there were no observations of conjuctivitis from exposure to 100 ppm H2S for 3 hours (Skranjy et al., 1996) and 125 ppm H2S for 4 hours, 5 days week (Partlo et al., 2001). Since the studies were designed to evaluate the effect of H2S on the hippocamal EEG activity and memory in rats, and not designed to study the effects on the eye, the observations on the eye should be considered secondary and not a critical portion of the studies (Roth SH, 2006, personal communication). 3.7. South Karelia air pollution studies: Haahtela et al. (1992) and Marttila et al. (1994, 1995) The South Karelia air pollution studies documented public exposures to low levels of H2S and other reduced sulfides (methyl mercaptan, dimethyl sulfide and dimethyl disulfide) from pulp mills in Finland. Haahtela et al. (1992) presented survey results from a community that experienced low level acute H2S exposure: the maximum 4-h concentration 135g/m3 (96 ppb) H2S and the 24-h average of 35 and 43g/m3
(25 and 31 ppb H2S). During the peak emissions, the SO2 mean 1-h average was only 3g/m3 and therefore not a significant confounder. The authors concluded that the observed symptoms correspond to the physiological effects of acute exposure of H2S, suggesting direct irritative effect on mucous membranes and eye conjunctivitis but at lower concentrations than described previously (Haahtela et al., 1992, p. 605). The major confounding exposure was the release of mesityl oxide and there were no concentrations presented (Haahtela et al., 1992). Mesityl oxide is a liquid at 25 C with a low vapor pressure (8.7 mm Hg at 25C). Its vapor is reported to have a distinct peppermint odor and induce sensation of irritation, which is detectableat 25 ppm in air (Hazardous Substances Database, 2005). These properties suggest that the effects observed were more likely due to H2S. Marttila et al. (1994) reported in the most polluted Karelia area that the annual mean H2S concentration was calculated as 8g/m3 (5.7 ppb) H2S, the highest 24-h concentration was calculated as 100 g/m 3 (71.4 ppb) H2S and the maximum 4-h average was measured as 56 g/m3 (40 ppb) H2S. The other major compound was methylmercaptan (CH3SH), with an annual mean of 25g/m3 and a maximum 24h concentration of 150 g/m3. CH3SH is considered mildly irritating at concentrations two orders of magnitude higher, 10 mg/m3 (NIOSH, 1989). Sulfur dioxide annual mean levels were low (2 g/m 3 ) because the plants use natural gas for energy (Haahtela Haahtela et al., 1992). In the moderately polluted area, the levels were much less for H2S and CH3SH. Of note, there was no CS2 present which was the main confounder in understanding the effect of H2S in the viscose rayon industry. Marttila et al. (1995) conducted surveys of the community in a reference (non-polluted) area, medium polluted and high polluted areas evaluating daily symptom intensity in relation to exposure levels. With respect to eye symptoms, they found significant differences between the medium and reference communities (OR 3.17, 1.217.47) and high vs. reference (OR 5.0, 1.6612.65). They observed a similar increase in reporting of intensity of nasal and pharyngeal symptoms. The intensity of eye symptoms was significantly higher during days of TRS > 10 g/m3. The parents reported their children's eye symptoms over the past 12 months (OR 1.15, 95% CI 0.43-3.05) in the three communities (reference n=7/30, medium n=20/ 62, and high n=5/42) (Marttila et al., 1994). Only parents in the medium (n=2) and high (n=4) pollution
15
areas reported children's eye symptoms over the previous 4 weeks, so the risk could not be calculated. Marttila et al. (1994) commented parents have problems evaluating eye symptoms for their children compared with more noticeable symptoms like wheezing. They concluded the eye symptoms were consistent with the presence of H2S. 3.8. Community study in Rotorua: Bates et al. (1998, 2002) In Rotorua, New Zealand, seeps from a natural geotherm result in ambient levels of H2S. The median concentration was reported as 20 g/m3 (14 ppb) with 35% of the measurements > 70 g/m3 (50 ppb) and 10% > 400g/m3 (286 ppb) H2S. It was suggested that the highest exposure group in the 2002 study was exposed regularly to at least 143 ppb H 2S, with highest concentrations at 1ppm H2S for 30-min average (Fisher, Fisher, 1999). An early study in Rotorua reported several cases of conjunctivitis and one case of blindness lasting three days from H2S exposure (McDougal and Garland, 1945). Bates et al. (1998) conducted an ecological study of health effects from hospital discharge data from 1981 to 1990. They observed a statistically significant increase in disease of the eye and adnexa (SIR 1.12, 1.051.19), cataracts (SIR 1.26, 1.141.38), disorders of the conjunctiva (SIR 2.09, 1.662.59) and disorder of the orbit (SIR 1.69, 1.122.44). The limitation of the study was that all people were treated equally exposed. Bates et al. (2002) conducted an ecological study of health effects from 1993 to 1996 morbidity data comparing the community by H2S exposure: high, medium and low. They observed statistically significant disorders of the eye and adnexa comparing the communities: high (SIR 2.27, 1.972.61), medium (SIR 1.57, 1.301.89) and low (SIR 1.47, 1.331.63). They also observed statistical significance for a trend from high to low; P for trend < 0.0001. The study also found consistency in terms of exposureresponse relationships across all four ethnicitygender categories. 4. Critique of Alberta Health and Wellness Report (2002) of H2S 4.1. Comparison of AHW Report (2002) review of H2S effects on the eye with other major reviews The AHW Report (2002) relied on selection criteria to select scientific papers (Table 4). The deviations from
Table 4 Relevant AHW report (2002) selection criteria for scientific studies The review was to focus on the health effects following short-term exposure. The term short term was to include exposures of both an acute and sub-acute variety, to capture exposures lasting a few hours to a few days. In another section, the exposure duration is up to 30 days. The review was to focus on health effects from low dose exposures. The term low dose was to include concentrations of H2S up to and including 100ppm. The review was to focus on health effects per se. Although a formal definition of health effects was not adopted by the Expert Panel, the meaning was taken to be: an undesirable or harmful effect on an organism with adverse consequences affecting survival, growth, development, performance, structure and/or function. The review was to focus on scientific studies involving exposures to H2S via inhalation exposure in order to mimic the expected route of exposure of the general public. The review was to be limited to information found in peer-reviewed scientific publications. [However, the review included gray literature from Alberta and it appears only English studies were included.] The review was to focus on full-length, primary scientific papers describing original work, rather than on review articles or abstracts. The review was to include consideration of information from clinical investigations involving controlled exposure of human subjects in laboratory settings, non-clinical studies involving controlled exposures of test animals in the laboratory and population studies involving exposures following routine or accidental releases of H2S into the environment. The review was to include a critical assessment of the technical quality of each scientific paper based on consideration of experimental design, conduct and reporting. Judgement of the quality was to be used on comparison against testing protocols recommended by leading scientific authorities.
the criteria that we observed in the report are noted in the table. Table 5 documents the papers cited by the National Institute of Occupational Safety and Health (NIOSH) (1977), Alberta Health (1988), AHW Report (2002) and the World Health Organization (WHO) (2003). The AHW Report (2002) relied on different studies than NIOSH (1977) and Alberta Health (1988). The AHW Report (2002) and WHO (2003) were conducted at the same time and there is limited overlap between the cited studies. The AHW Report (2002) selection criteria should have captured most of these studies as they are original, peer reviewed, scientific work. AHW Report (2002) reviewed many studies for scientific quality. It may be that AHW Report (2002) considered many papers too poor a quality to include, however, the report stated that most studies were considered poor. There is no overview of which studies were discarded.
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Table 5 Comparison of studies cited for effects of hydrogen sulfide on the eye Reports by date [H2S], time, eye effect:a yes or no Cited in review Alberta Health and Wellness, 2002 No No No Yes Alberta Health, 1988 No No Yes Yes National Institute of Occupational Health (NIOSH), 1977 Yes Yes No No World Health Organization (WHO), 2003 No No No No
Ramazzini, 1713 Mitchell and Davenport, 1924 Sayers et al., 1923 Mitchell and Yant, 1925
no data, 4h, yes Review 50ppm, hours, yes Dogs 3550ppm, 13 h, yes Men > 50ppm, hours, yes 1626 ppm, hours, yes 1015 ppm, hours, no Review 1424 ppm, hours, yes No data, yes >20ppm, hours, yes >20ppm, hours, yes (no actual data provided) No data, yes 29132 ppm, 30 min to hours, yes No data, yes 15ppm, hours, yes 20ppm, hours, yes 14ppm, hours, yes 36ppm, 3h, yes No data, yes Up to >1000ppm, minutes, yes 100ppm, hours, yes 0.0040.021ppm, chronic, yes 0.0070.009ppm, 5min, yes No data, yes Review Review 0.0080.009ppm, 40min, yes 0.0220.125ppm, 7h, yes No comment in paper of effect on the eye <10ppm, hours, yes 510 ppm, years, yes 100ppm, hours, yes 1121ppm, 67h, yes 20ppm, 24h, yes 71ppm, 1 h, yes 20ppm, 7days, yes
Kranenburg and Kessener, 1925 Yant, 1930 Legge, 1934 Lewey, 1938, McDonald, 1938 Barthelemy, 1939 Elkins, 1939 Sjorgen, 1939 Larsen, 1944 Howes, 1943 Rubin and Arieff, 1945 Ahlborg, 1950 Masure, 1950 Michal, 1950 Zander, 1950 McCabe and Clayton, 1952 Deveze, 1956 Loginova, 1957 Duan, 1959 Carson, 1963, Beasley, 1963 Grant, 1974 Milby, 1962 Baikov, 1963 United States Health Department, Terre Haute, 1964 Kleinfeld et al., 1964
No Yes No No No No No No No No No No No No No No No No No No No No
Yes Yes No Yes Yes Yes No Yes No Yes Yes No No No Yes Yes Yes Yes No Yes Yes No Yes No Yes Yes No
No No No No No No No No No No Yes No No No No No No No No No No No No
Yes No Yes Yes Yes Yes Yes
No No Yes Yes No Yes
No
Yes
No
No
Poda, 1966 Benini and Colamussi, 1969 Brown, 1969 Nesswetha, 1969 Hays, 1972 Kosmider et al., 1971 Nordstrom, 1975; Nordstrom and McQuitty, 1975 Gosselin et al., 1976
No No No No No Yes No
No Yes No Yes Yes No Yes
Yes
No No No No No No No
Yes Yes b No b No No
Review
Yes
Yes
No
No
T.W. Lambert et al. / Science of the Total Environment 367 (2006) 122 Table 5 (continued) Reports by date [H2S], time, eye effect:a yes or no Cited in review Alberta Health and Wellness, 2002 No Yes No No Alberta Health, 1988 Yes No No Yes National Institute of Occupational Health (NIOSH), 1977 c NA NA NA
17
World Health Organization (WHO), 2003 Yes Yes Yes No
NIOSH, 1977 Haider et al., 1980 IPCS, 1981 CIIT, 1983
Alberta Lodgepole Blowout, 1984 Audeau et al., 1985 Arnold et al., 1985 Alberta Environmental Centre, 1986a Alberta Environmental Centre, 1986b; Lopez et al., 1986 Kangas and Savolainen, 1987 Luck and Baye, 1989 Haahtela et al., 1992 Vanhoorne et al., 1995 Jappinen et al., 1990 Jaakkola et al., 1990 Bhambhani and Singh, 1991; Bhambhani et al., 1994, 1996a, 1996b Skranjy et al., 1996 Kilburn, 1997 Bates et al., 1998 Kilburn, 1999 Riffat et al., 1999 Bates et al., 2002
Review 20ppm, 1h, yes Review 10:20:80ppm, 6h/day, 5days/week for 90 days, yes <5ppm, hours to days, yes No data, yes No data, yes 1ppm, hoursdays, yes 40ppm, 6h, yes
Yes No No No Yes
No No No No
NA NA NA NA NA
No Yes Yes No No
No comment in paper of effect on the eye No data, yes 0.028ppm2 days, 0.096ppm4h peak, yes 0.146ppm, hours, yes No comment in paper of effect on the eye 0.004ppm, 0.071ppm, annual: peak, yes No eye exposure
Yes No No No Yes No Yes
c NA
NA NA NA NA NA NA NA
No Yes No Yes No Yes No
NA NA NA NA NA NA
100 ppm, 3h, no 140ppm, hours, yes 0.014ppm, annual, yes No comment on the eye 70ppm, hours, yes 0.014ppm, annual, yes
Yes Yes No Yes No No
NA NA NA NA NA NA
NA NA NA NA NA NA
No NA Yes No Yes No
a Effect means simply that the eye was said to respond to hydrogen sulfide. In many studies, other compounds were also present. The effect differs in each of the studies. The point of the variable is only to distinguish positive and negative studies. b NIOSH reviewed the paper, but does not mention the effect on the eye. c NA means not applicable as the study was released after the review period.
4.2. Review of the scientific studies to support AHW Report (2002) conclusion that there is very little evidence of eye irritation following short-term exposures to H2S at concentrations up to 100 ppm AHW Report (2002) concluded there was little information available suggesting eye involvement following short-term exposure up to 100ppm H2S.The findings on the eye were discussed in three sections: non-clinical, clinical and case-control studies (AHW Report 2002, pp. 2829).
4.2.1. Non-clinical studies AHW report (2002) stated that most of the nonclinical study effects were typically non-descript, and less than 10% of studies reported eye irritation at less than 100ppm H2S. Only one study cited in the AHW Report (2002), Skranjy et al. (1996), reported no effect of H2S on the SpragueDawley rat eye at an exposure concentration of 100 ppm H2S for 3 h. The full context of their comment is: exposure to 50 ppm causes severe eye irritation or gas eye in humans. However, eye
18
irritation was never observed in the rats in the present experiments which suggests that the rat may be more resistant to the effects of H2S (Skranjy et al., 1996, p. 52). The AHW Report (2002) cited Lopez et al. (1986), which is the Alberta Environmental Centre (1986b) study (see Section 3.6). The AHW Report (2002) stated that researchers observed lacrimation at 40ppm H2S. AHW Report (2002) stated that Mitchell and Yant (1925) (see Section 3.2, Table 1) reported irritation of the eyes progressing to pus in the eyes among rats, guinea pigs and dogs following continuous exposure to 35 to 100 ppm H2S for 8 to 48 hours, and that lacrimation was also noted among dogs. Haider et al. (1980) evaluated the effect of H2S on the levels of total lipids in the brain of guinea pigs. Guinea pigs were exposed to 20ppm H2S for 1h/day for 11days. The publication has one sentence that includes the eye: following exposure of guinea pigs to H2S such signs as fatigue, somnolence, dizziness, itching and eye irritation were observed (Haider et al., 1980, p. 419). WHO (2003) cited this study as providing information of the lowest concentration showing effects from short-term exposure. Kosmider et al. (1971) evaluated the effect of vitarel, a vitamin and mineral supplement, on mineral and enzyme disturbances as a result of H2S. Kosmider et al. (1971) exposed rabbits to 71ppm for 1h/day for 14days. There is one statement in the paper that references the eye: quicker breathing and pulse-rate as well as congestion of the conjunctivas could be observed (Kosmider et al., 1971, p. 67). Thus, the effect on the eye was a result of a brief exposure to H2S. WHO (2003) cited this paper but did not mention the eye effect in its review. The AHW Report (2002) stated that none of the other non-clinical studies showed eye effects; there is no indication of which studies these are. In contrast to the AHW Report (2002) conclusion, four of five non-clinical studies cited in the report provided evidence of eye irritation from short-term exposure below 100ppm H2S. The lowest concentration and time indicating eye irritation was 20 ppm H2S after 1h (Haider et al., 1980). 4.2.2. Clinical studies The AHW Report (2002) stated: Jappinen et al. (1990) found no evidence of eye irritation following controlled whole body exposure of asthmatics at 2ppm H2S for 30 minutes, nor did Kangas and Savolainen (1987) report eye irritation among subjects exposed to H2S at concentrations up to 30 ppm for 30 to 40minutes (AHW Report, 2002, p. 28).
In Jappinen et al. (1990), the eye is mentioned in one sentence in the discussion: malodorous sulfur compounds existing in the ambient air have been shown to cause mucosal and conjunctival irritation even at low concentrations (Jappinen et al., 1990, p. 827). Kangas and Savolainen (1987) evaluated the use of thiosulfate as a urinary biomarker of H2S exposure. There is no mention of the eye in the paper. AHW Report (2002) presented the results of Mitchell and Yant (1925) (see Section 3.2). The report stated subjects reported eye irritation in as little as 2 to 15min after exposure to 100 to 150ppm H2S and that sharp pain in the eyes was reported after 1 to 4h. Only one of the three studies cited was a clinical study evaluating effects on the eye and it provided evidence of eye irritation from short-term exposure at 100ppm H2S. 4.2.3. Case-control and observational studies from sour gas releases AHW Report (2002) reviewed two studies by Kilburn (1997, 1999) from accidental releases of sour gas. The AHW Report (2002) commented that: Kilburn (1997) found that eye effects were not reported by subjects exposed to 1 to 50ppm H2S for up to 24 hours at the time of exposure; however, upon evaluation 2 to 6 years later, eye involvement was evidenced by abnormal colour vision, and reduced fields as well as complaints of eye irritation. In Kilburn (1997), the only possible inference of eye irritation or conjuctivitis at the time of exposure is the category of mucous irritation in the symptom survey, which was reported as significantly elevated over controls. The AHW Report (2002) stated: Kilburn reported eye effects among individuals allegedly exposed to H2S at concentrations ranging from 1 to 40 ppm for up to one week as a result of emissions from refinery explosion and fire. The effects presented as abnormal colour vision and impaired visual fields based on testing performed three years after the event. Kilburn (1999) presented findings from a neurobehavioural battery and the comments of impaired visual field are in relation to neurological effects. We could not find any statements in the paper with respect to eye irritation or conjuctivitis. AHW Report (2002) cited the Lodgepole Blowout Report (1984) (see Section 3.6) and stated that: witnesses testified experiencing eye irritation at the time of the incident. The Alberta Social Service Report (1983) report was cited, indicating a: relatively high
19
incidence of eye effects, including burning eyes and double vision. Of the case-control studies cited by Alberta Health (2002), only the Alberta Lodgepole blowout report supports eye effects at concentrations significantly less than 100 ppm H2S (see Section 3.6) and it is unclear if Kilburn (1997) results indicate eye irritation. 4.3. AHW Report (2002) critique of Alberta Health (1988) The AHW Report (2002, p. 55) stated its conclusions are in sharp contrast to the earlier 1988 report. The AHW Report (2002) claimed that Alberta Health (1988) relied heavily on the review by Milby (1962), and Gosselin et al. (1976), which relied upon the review by Yant (1930), none of which can be substantiated by original research and none of it suggesting that H2S at 20 ppm H2S causes irreversible eye damage (see Section 1 for the full quotation). Table 5 indicates that Alberta Health (1988) did not rely heavily on Milby (1962) and Gosselin et al. (1976). Alberta Health (1988) cited Nordstrom and McQuitty (1975) for irreversible eye effects at 20ppm H2S (see Section 3.6). Of particular importance is that the AHW Report (2002) did not reference this study (Table 5), yet they referenced other Alberta gray literature. In the Alberta Health (1988) report, Milby (1962) was not cited in the description of the irreversible damage to the eye from 20ppm H2S: As acute conjunctivitis develops, characteristic signs and symptoms include pain, mucopurulent exudation, lacrimation, hyperemia, retroorbital aching, blepharospasm, blurred vision, photophobia, and the illusion of rainbow-like colors around the incandescent lights (Beasley, 1963). As this condition progresses vesiculation and ulceration of the corneal epithelium may result in scar formation and permanent impairment of vision (Mitchell and Yant, 1925; Yant, 1930; Gosselin et al., 1976). At H2S concentrations below 50 ppm increased exposure duration is required to elicit these effects. For example, Nordstrom and McQuitty (1975) concluded that permanent corneal tissue damage could be elicited in calves exposed to 20 ppm for 7 days. Others have reported inflammation of eye tissues (spinner's eye) after 67 hours of exposure to 11 21 ppm H2S (Elkins, 1939; Nesswetha, 1969). (Alberta Health, 1988, pp. 1314)
In conclusion, the Alberta Health (1988) report stated: to conclude, irreversible eye tissue damage can occur at 20ppm H2S, but on the basis of animal data (Alberta Health, 1988, p. 14). Milby (1962) is only cited once in the 1988 report: The current Alberta OEL for H2S is 10 ppm. Like ACGIH, the basis for this OEL is primarily the greater incidence in irreversible eye tissue damage at concentrations > 20 ppm for several hours exposure. For example, at concentrations greater than 50 ppm for 1 hour, irritation and inflammation of the conjunctival and corneal tissues may occur, a condition called gas eye. (Milby, 1962; Gosselin et al., 1976; Alberta Health, 1988, pp. 26) The Alberta Health (1988) report did not reference the 20 ppm H2S effect to Milby (1962). In fact, the Alberta Health (1988) citation is similar to the excerpt from the AHW Report (2002, p. 55): exposure to concentrations above 50 ppm for a period exceeding 1 h may produce irritation of the conjunctival and corneal tissues. Contrary to AHW Report (2002) statement that there is no original research to support the Yant (1930) review, the original research paper, Mitchell and Yant (1925), was actually cited in the AHW Report (2002). Yant (1930) provided a review and rewording of the statements from Sayers et al. (1923) and Mitchell and Yant (1925) (Section 3.2). Milby (1962) referenced the Yant (1930) paper. Therefore, the original research for citing 50 ppm H2S resulting in eye effects is Sayers et al. (1923) or Mitchell and Yant (1925). Therefore, quite clearly the AHW Report (2002) claims that in sharp contrast to the earlier report (Alberta Health, 1988) which relied heavily on statements made by Milby (1962) cannot be substantiated. 5. Conclusion The AHW Report (2002) conclusion that there is little evidence of eye irritation up to concentrations of 100 ppm H2S is not supported by the non-clinical, clinical and case-control studies that were cited in their report. Almost all the scientific studies we found that discussed the eye, reported eye effects below 100 ppm H2S in a variety of environmental contexts (Table 5). Ramazzini's observations in 1700 appear to be an accurate description of the health effects of H2S on the eye and consistent with scientific studies
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T.W. Lambert et al. / Science of the Total Environment 367 (2006) 122 Benini F, Colamussi V. Chronic or relapsing skin manifestations observed in refinery workers exposed to long-term action of hydrogen sulfide. Arcisp S Anna Ferrara 1969;22:97383. Bhambhani Y, Singh M. Physiological effects of hydrogen sulfide inhalation during exercise in healthy men. J Appl Physiol 1991;71 (5):18727. Bhambhani Y, Burnham R, Snydmiller G, MacLean I, Martin T. Comparative physiological responses of exercising men and women to 5 ppm hydrogen sulfide exposure. Am Ind Hyg Assoc J 1994;55(11):10305. Bhambhani Y, Burnham R, Snydmiller G, MacLean I, Martin T. Effects of 5 ppm hydrogen sulfide inhalation on biochemical properties of skeletal muscle in exercising men and women. Am Ind Hyg Assoc J 1996a;57(5):4648. Bhambhani Y, Burnham R, Snydmiller G, MacLean I, Lovlin R. Effects of 5 ppm hydrogen sulfide inhalation on pulmonary function in healthy men and women. J Occ Env Med 1996b;38 (10):1012-10178. Brown KE. Some toxicological problems in a rubber industry. Med J Aust 1969;1:5348. Burnett WW, King EG, Grace M, Hall WF. Hydrogen sulfide poisoning: review of 5 years' experience. Can Med Assoc J 1977;117:127780. Carson MB. Hydrogen sulfide exposure in the gas industry. Ind Med Surg 1963;32:634. Christison R. A treatise on poisons in relation to medical jurisprudence, physiology, and the practice of physic. 1832, 2nd Ed. XX; 1845. p. 6225. CIIT. Chemical Industry Institute of Toxicology. 90-Day vapor inhalation toxicity study of hydrogen sulfide in Fischer-344 rats. US EPA Office of Toxic Substances Public Files. Fiche number 0000255-0; 1983. Deveze D. Lihydrogene sulfure in pathologie miniere. Rev Med Minicre 1956;9:148. Duan FZ. Maximum permissible concentration of hydrogen sulfide in the atmosphere. Gig Sanit 1959;24:127. Edmonton Board of Health. Perceived health effects of the Lodgepole sour gas well blowout; 1983. August, 36 pp. Elkins HB. Toxic fumes in Massachusetts industries. Ind Med 1939;33:42632. Energy Resources and Conservation Board (ERCB). Gascon2: a model to estimate ground level H2S and SO2 concentrations and consequences from uncontrolled sour gas releases, ERCB report 90B, volume 5, and Volume 7 Appendix B, Alberta, Canada, October 1990, 200 pp. Environmental Protection Agency (EPA). Hydrogen sulfide: interim acute exposure guideline levels (AEGLs) for NAS/COT subcommittee for AEGLs. Environmental Protection Agency; 2002. Interim 3:6, 38 pp. Eulenberg H. Die lehre von den schadlichen und giftigen gasen. Braunschweig 1865; 26089. Fisher G. Natural levels of hydrogen sulfide in New Zealand. Atmos Environ 1999;33:30789. Gosselin R, Hodge H, Smith R, Gleason M. Hydrogen sulfide. Clinical toxicology of commercial products. Baltimore: The Williams and Wilkins Co.; 1976. 163173 pp. Grant WM. Toxicology of the eye. 3rd edition. Charles C Thomas Publisher; 1974. 561563 pp. Guidotti T. Some unresolved questions of hydrogen sulfide. J Occup Health 1994;66:15360. Haahtela T, Martilla O, Vilkka V, Jappinen P, Jaakola JK. The south Karelia air pollution study: acute health effects of malodorous
since that time. In community settings, following short-term exposure, 25ppb H2S appears to be the lowest concentration observed to irritate the eyes and, with chronic exposure, serious health effects on the eyes are suggested. Perhaps the most controversial question is whether H2S can cause irreversible health effects on the eye. Blindness was suggested by Ramazzini, however, many have claimed the eye heals completely. References
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Science of the Total Environment 367 (2006) 1 22 www.elsevier.

Lehmann, 1892 Men and animals were exposed

6 Table 1 (continued) Study Mitchell and Yant, 1925

Yes No Yes Yes Yes Yes Yes

No No Yes Yes No Yes

No Yes No Yes Yes No Yes

World Health Organization (WHO), 2003 Yes Yes Yes No

NIOSH, 1977 Haider et al., 1980 IPCS, 1981 CIIT, 1983

Yes No No No Yes No Yes

No Yes No Yes No Yes No

Yes Yes No Yes No No

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