Sulphur Poisoning

Far from being benign and inert, sulphur, even elemental sulphur, that escapes into the environment is damaging in a variety of ways.

Sulphur in a nutshell

From Merriam-Webster Online Dictionary

sul·fur
Variant(s): also sul·phur  /'s&l-f&r/
Function: noun
Etymology: Middle English sulphur brimstone, from Latin sulpur, sulphur, sulfur
1 : a nonmetallic element that occurs either free or combined especially in sulfides and sulfates , is a constituent of proteins, exists in several allotropic forms including yellow orthorhombic crystals, resembles oxygen chemically but is less active and more acidic, and is used especially in the chemical and paper industries, in rubber vulcanization, and in medicine for treating skin diseases -- see ELEMENT table
2 : something (as scathing language) that suggests sulfur
- sul·fury or sul·phury  /-E/ adjective
usage The spelling sulfur predominates in U.S. technical usage, while both sulfur and sulphur are common in general usage. British usage tends to favor sulphur for all applications. The same pattern is seen in most of the words derived from sulfur. (Source)

sulfur bacterium
Function: noun
: any of various bacteria (especially genus Thiobacillus) capable of metabolizing sulfur compounds (Source)

sul·fide
Pronunciation: 's&l-"fId
Function: noun
1 : any of various organic compounds characterized by a sulfur atom attached to two carbon atoms
2 : a binary compound (as CuS) of sulfur usually with a more electropositive element or group : a salt of hydrogen sulfide (Source)

hydrogen sulfide
Function: noun
: a flammable poisonous gas H₂S that has an odor suggestive of rotten eggs and is found especially in many mineral waters and in putrefying matter (Source)

[More on hydrogen sulphide)

sulfuric acid
Variant(s): or sul·phu·ric acid  /"s&l-'fyur-ik-/
Function: noun
: a heavy corrosive oily dibasic strong acid H₂SO₄ that is colorless when pure and is a vigorous oxidizing and dehydrating agent (Source)

sulfur dioxide
Function: noun
: a heavy pungent toxic gas SO2 that is easily condensed to a colorless liquid, is used especially in making sulfuric acid, in bleaching, as a preservative, and as a refrigerant, and is a major air pollutant especially in industrial areas (Source)

[More on sulphur dioxide]

Some properties of solid sulphur that are of concern:

• Specific gravity or density: 2.07 at 20 °C (meaning that it is a little more than twice as heavy than water and about the same density as grain produced in agriculture)
• Melting point: 113 - 119 °C (Depends on the sulphur's crystalline state)
• Viscosity: The viscosity of sulphur near the melting point is about that of water and increases to 50,000 or more times that of water at a temperature of 188 °C, subsequently falling rapidly with increase in temperature.
• Flash point: 168 °C (The flash point is the temperature at which vapours above a volatile combustible substance ignite in air when exposed to flame)
• Auto ignition temperature: 248 °C (The temperature at which sulphur will burst into flame when air is present)
• Extinguishing Media: Water fog, dry chemical, foam, carbon dioxide. Small fires can be smothered with an inert materials.
• Special Fire Fighting Procedures: Prevent water run-off entering streams, sewers or drinking water.
• Sensitivity to Mechanical Impact: Friction may cause sulphur to ignite.
• Sensitivity to Static Discharge: Yes, static charge release may ignite dust in air.
• Unusual Fire and Explosion Hazards: Keep away from ignition sources (e.g., heat, sparks, and open flames). Due to the production of sulphur dioxide and H2S, firefighters should wear self-contained breathing apparatus (SCBA). Other personnel with the same equipment should stand by for rescue purposes.
• Health Hazards (acute and chronic): Dust may be irritating to the eyes, nose, throat and lungs. Solid sulphur (especially when freshly produced) may release hydrogen sulphide gas, which can accumulate in confined, non-ventilated areas. Hydrogen sulphide may cause irritation, breathing failure, coma and death, without necessarily any warning odour being sensed. Residual effects after exposure can include shortness of breath, wheezing and delayed pulmonary oedema (may be fatal). Research on animals has shown effects on the respiratory, nervous and reproductive systems at concentrations above 10 ppm. Long term effects of exposure may include respiratory problems and inflammation of the eyes. Frequent or prolonged contact may irritate the skin and cause a skin rash.
• Steps to be Taken in Case Material is Released or Spilled: Assess situation, ensuring own safety, eliminate sources of ignition. Keep public away. Prevent additional discharge of material, if possible to do so without hazard. Recover spilled material and place in suitable containers for recycling or disposal.
• Waste Disposal Method: Consult an expert on disposal of recovered material. Ensure disposal is in compliance with federal and provincial government regulations.
• Precautions to be Taken in Handling and Storing: Store in cool, well ventilated place away from incompatible materials. Do not breathe dust or gas. Minimize dust generation during handling. Material will accumulate static charges which may cause a spark and become an ignition source.

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Sources: The Encyclopedia Americana, 1956 Edition, Vol. 26, p. 1; Sulphur, Lenntech; Product Identification, Solid Sulphur, Burlington Industries

Some properties of liquid sulphur that are of concern:

• WHMIS Class D - Division 1: Subdivision A: Very Toxic Material
• Extinguishing Media: Water fog, dry chemical, foam, carbon dioxide. Small fires can be smothered with inert materials, such as sand.
• Special Fire Fighting Procedures: Isolate fuel source. Water or foam may cause frothing. Use water to keep fire exposed containers cool. Firefighters must use self-contained breathing apparatus (SCBA). Other personnel equipped with SCBA should stand by for rescue purposes. Prevent water run-off entering sewers or drinking water.
• Sensitivity to Static Discharge: Hydrogen sulphide gas from material may be ignited by static discharge.
• Unusual Fire and Explosion Hazards: Extremely high hydrogen sulphide and sulphur dioxide concentrations may build up in tank headspaces. [At HAZCO's open house Nov. 4, 2005, Robert Mann of HAZCO denied that would be a problem.  He also stated that, if such gases would be present in their liquid sulphur storage vessels, they would not be flared but vented into the atmosphere.]
• Incompatibility (materials to avoid): Oxidizing agents, halogens, mineral acids/alkalies, zinc, tin, and copper.
• Hazardous Decomposition or By-Products: Will produce sulphur dioxide when burned.
• Health Hazards (acute and chronic): Contact with eyes or skin causes severe injury. High concentrations of hydrogen sulphide and sulphur dioxide may be present, especially in head spaces. These gases are irritant to the eyes, nose, throat and lungs. Hydrogen sulphide may cause respiratory failure and possible death above 600 ppm, without necessarily any warning odour being sensed. Residual effects after exposure can include shortness of breath, wheezing and delayed pulmonary oedema, which may be fatal. Research on animals has shown effects on the respiratory, nervous and reproductive systems at concentrations above 10 ppm. Long term effects of exposure may include respiratory problems and inflammation of the eyes.
• Sign and Symptoms of Exposure: Eye, nose, throat and lung irritation.
• Medical Conditions Generally Aggravated by Exposure: Pre-existing inflammation of the eyes, nose, throat, or lungs, bronchitis, asthma, pneumonia.
• Steps to be Taken in Case Material is Released or Spilled: Assess situation, ensure own safety. Sound alarm. Eliminate sources of ignition. Keep public away. If liquid, dike to contain, allow to cool. Shovel up and drum for disposal.
• Waste Disposal Method: Consult an expert on disposal of recovered material. Ensure disposal in compliance with federal and provincial government regulations.
• Precautions to be Taken in Handling and Storing: Store in cool, well ventilated place away from incompatible materials. Do not breathe gas. Material will accumulate static charges which may cause a spark. Static charge buildup may become an ignition source.

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Source: Product Identification, Liquid Sulphur, Burlington Industries
 

Sulphur

Sulphur is a multivalent non-metal, abundant, tasteless and odourless. In its native form sulphur is a yellow crystalline solid. In nature it occurs as the pure element or as sulphide and sulphate minerals. Although sulphur is infamous for its smell, frequently compared to rotten eggs, that odour is actually characteristic of hydrogen sulphide (H2S). The crystallography of sulphur is complex. Depending on the specific conditions, sulphur allotropes form several distinct crystal structures. Applications The major derivative of sulphur is sulphuric acid (H2SO4), one of the most important elements used as an industrial raw material. Sulphur is also used in batteries, detergents, fungicides, manufacture of fertilizers, gun powder, matches and fireworks. Other applications are making corrosion-resistant concrete which has great strength and is frost resistant, for solvents and in a host of other products of the chemical and pharmaceutical industries. Sulphur in the environment Life on Earth may have been possible [only] because of sulphur. Conditions in the early seas were such that simple chemical reactions could generate the range of amino acids that are the building blocks of life. Sulphur occurs naturally near volcanoes. Native sulphur occurs naturally as massive deposits in Texas and Louisiana in the USA. Many sulphide minerals are known: pyrite and marcaiste are iron sulphide ; stibnite is antimony sulphide; galena is lead sulphide; cinnabar is mercury sulphide and sphalerite is zinc sulphide. Other, more important, sulphide ores are chalcopyrite, bornite, penlandite, millerite and molybdenite. The chief source of sulphur for industry is the hydrogen sulphide of natural gas, Canada is the main producer.  (Full Article) _______________________ Source: Sulphur, Lenntech Water treatment & air purification Holding B.V. Rotterdamseweg 402 M 2629 HH Delft, The Netherlands

Health effects of sulphur

All living things need sulphur. It is especially important for humans because it is part of the amino acid methionine, which is an absolute dietary requirement for us. The amino acid cysteine also contains sulphur. The average person takes in around 900 mg of sulphur per day, mainly in the form of protein. Elemental sulphur is not toxic, but many simple sulphur derivates are, such as sulphur dioxide (SO2) and hydrogen sulphide (H2S). Sulphur can be found commonly in nature as sulphides. During several processes sulphur bonds are added to the environment that are damaging to animals, as well as humans. These damaging sulphur bonds are also shaped in nature during various reactions, mostly when substances that are not naturally present have already been added. They are unwanted because of their unpleasant smells and are often highly toxic. Globally, sulphuric substances can have the following effects on human health: - Neurological effects and behavioural changes - Disturbance of blood circulation - Heart damage - Effects on eyes and eyesight - Reproductive failure - Damage to immune systems - Stomach and gastrointestinal disorder - Damage to liver and kidney functions - Hearing defects - Disturbance of the hormonal metabolism - Dermatological effects - Suffocation and lung embolism (Full Article) _______________________ Source: Sulphur, Lenntech Water treatment & air purification Holding B.V. Rotterdamseweg 402 M 2629 HH Delft, The Netherlands

Effects of sulphur on the environment

Sulphur can be found in the air in many different forms. It can cause irritations of the eyes and the throat with animals, when the uptake takes place through inhalation of sulphur in the gaseous phase. Sulphur is applied in industries widely and emitted to air, due to the limited possibilities of destruction of the sulphur bonds that are applied. The damaging effects of sulphur with animals are mostly brain damage, through malfunctioning of the hypothalamus, and damage to the nervous system. Laboratory tests with test animals have indicated that sulphur can cause serious vascular damage in veins of the brains, the heart and the kidneys. These tests have also indicated that certain forms of sulphur can cause foetal damage and congenital effects. Mothers can even carry sulphur poisoning over to their children through the mother's milk. Finally, sulphur can damage the internal enzyme systems of animals. (Full Article) _______________________ Source: Sulphur, Lenntech Water treatment & air purification Holding B.V. Rotterdamseweg 402 M 2629 HH Delft, The Netherlands

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Toxicity Data

Hydrogen Sulfide

ACUTE TOXICITY DATA:

Lethal concentration data:
 

Species	Reference	LC50 (ppm)	LCLo (ppm)	Time	Adjusted 0.5-hr LC (CF*)	Derived value
Rat	Back et al. 1972	713	-----	1 hr	977 ppm (1.37)	98 ppm
Mouse	Back et al. 1972	673	-----	1 hr	922 ppm (1.37)	92 ppm
Human	Lefaux 1968	-----	600	30 min	600 ppm (1.0)	60 ppm
Mouse	MacEwen and Vernot 1972	634	-----	1 hr	869 ppm (1.37)	87 ppm
Human	Tab Biol Per 1933	-----	800	5 min	354 ppm (0.44)	35 ppm
Rat	Tansey et al. 1981	444	-----	4 hr	1,141 ppm (2.57)	114 ppm

Source: Hydrogen sulfide, IDLH Documentation, CAS number: 7783­06­4,  US  Center for Health and Human Services, Centers for Disease Control and Prevention

Hydrogen sulphide is a poisonous gas. It can react with the alkali constituent in human tissues to form a caustic sulphide salt, causing eye and respiratory irritation at concentrations below 500 parts per million (ppm). Above 500 ppm, the concentration is strong enough to cause unconsciousness and death due to respiratory paralysis. Its characteristic odor of rotten eggs can be detected at concentrations typically in the 0.005 - 0.02 ppm range while at 3 - 5 ppm the odor is strong and offensive. Above this concentration it may fatigue the sense of smell and provide no warning of dangerous concentrations (SCC 1999).
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Source: Environmental Assessment Document, Sulphur Forming, Handling and Storage Facility, Ridley Island, BC (February 2007), by Keystone Environmental Ltd., p. 16; (11.45 MB, PDF file, off-site)

Sulfuric acid

ACUTE TOXICITY DATA:

Lethal concentration data:
 

Species	Reference	LC50	LCLo	Time	Adjusted 0.5-hr LC (CF)	Derived value
G. pig	Amdur et al. 1952a	50 mg/m3	-----	8 hr	125 mg/m3 (2.5)	13 mg/m3
Rat	Izmerov et al. 1982	510 mg/m3	-----	2 hr	816 mg/m3 (1.6)	82 mg/m3
Mouse	Izmerov et al. 1982	320 mg/m3	-----	2 hr	512 mg/m3 (1.6)	51 mg/m3
G. pig	Raule 1954	18 mg/m3	-----	?	?	?
G. pig	Treon et al. 1950	-----	87 mg/m3	2.75 hr	154 mg/m3 (1.77)	15 mg/m3

Human data: In exposures of 5 to 15 minutes, some volunteers found 5 mg/m³ to be very objectionable, while others found it less so [Amdur et al. 1952b]. The lethal oral dose has been reported to be 135 mg/kg [Arena 1970]. [Note: An oral dose of 135 mg/kg is equivalent to a worker being exposed to about 6,300 mg/m³ for 30 minutes, assuming a breathing rate of 50 liters [of air] per minute and 100% absorption.]

Source: Sulfuric acid, IDLH Documentation, CAS number: 7664­93­9,  US  Center for Health and Human Services, Centers for Disease Control and Prevention

Sulfur dioxide

ACUTE TOXICITY DATA:

Lethal concentration data:
 

Species	Reference	LC50 (ppm)	LCLo (ppm)	Time	Adjusted 0.5-hr LC (CF)	Derived value
Rat	Flury & Zernik 1935	-----	993	20 min	864 ppm (0.87)	86 ppm
Rat	Flury &Zernik 1935	-----	611	5 hr	1,314 ppm (2.15)	131 ppm
Mouse	Flury &Zernik 1935	-----	764	20 min	665 ppm (0.87)	67 ppm
Mouse	Hilado &Machado 1977	3,000	-----	30 min	3,000 ppm (1.0)	300 ppm
Rat	Kinkead & Einhaus 1984	2,520	-----	1 hr	3,150 ppm (1.25)	315 ppm
Human	Shupe et al. 1972	-----	1,000	10 min	690 ppm (0.69)	69 ppm
Human	Tab Biol Per 1933	-----	3,000	5 min	1,500 ppm (0.5)	150 ppm

Source: Sulfur dioxide, IDLH Documentation, CAS number: 7446­09­5, US  Center for Health and Human Services, Centers for Disease Control and Prevention

Sulphur dioxide has a sharp, pungent odor, characteristic of burning sulphur, and is noticeable in the air by odor and taste at minimum concentrations of 0.3 - 1.0 ppm (Dangerous Properties of Industrial Materials, Fifth Edition). The maximum permissible concentration for 15-minute exposure is 10 ppm, up to four times per day according to the Workers Compensation Board.
________________
Source: Environmental Assessment Document, Sulphur Forming, Handling and Storage Facility, Ridley Island, BC (February 2007), by Keystone Environmental Ltd., p. 16; (11.45 MB, PDF file, off-site)

Sodium Lauryl Sulphate

According to the EEC Regulations concerning the quality of drinking water, sodium lauryl sulphate (SLS) levels are not to exceed 200 µg (0.2 mg or 0.0002 g) per liter.  There appear to be no Canadian regulations pertaining to SLS.
   Although SLS is a common ingredient in soaps, shampoos and tooth pastes (sued to increase foaming), it is a skin irritant, that can cause rashes and itches.  It is not to be taken internally, as it will cause diarrhea and vomiting.

SLS is used in animal tests (typically 0.5 ml of 10% sodium lauryl sulphate in vaseline, in order to create a local irritation) to provide a standard of reference for skin reactions relative to substances to be tested.

SLS has been studied in other health contexts.

1: J Clin Periodontol. 1994 Nov;21(10):717-9. Related Articles, Links

Triclosan protects the skin against dermatitis caused by sodium lauryl sulphate exposure.

Barkvoll P, Rolla G.

Department of Oral Surgery and Oral Medicine, University of Oslo, Norway.

Abstract: It has recently been suggested that the lipid-soluble, antibacterial agent triclosan possesses an anti-inflammatory effect in the oral cavity. The aim of the present study was to examine whether triclosan can protect the skin from the irritation or inflammation that may be caused by exposure to sodium lauryl sulphate (SLS). Finn Chamber patch tests on the forearms of 10 volunteers showed that a mixture of SLS and triclosan caused no inflammation, whereas SLS alone caused reactions in all the subjects. Pre-treatment with triclosan before SLS exposure had a slight effect whereas treatment after exposure showed a significant effect. It is suspected that the reported anti-gingivitis effect of triclosan may at least in part be explained by an anti-inflammatory effect.

PMID: 7852618 [PubMed - indexed for MEDLINE] (Source)

7.1.2.4 Examples of combined action

Local toxic effects to the skin include irritation and corrosion (tissue necrosis).  Examples of dermal irritants are strong bases and acids, oxidising or reducing substances, organic solvents and surfactants. When the skin is mildly irritated the dermal blood flow will increase and a local erythema may be produced. More severe irritants can induce capillary leakage to produce manifestations as local oedema or blisters. Very severe intoxications may result in cell and tissue necrosis, and the formation of scars.
Substances and preparations (mixtures) may be classified as corrosive due to their physical-chemical properties on the basis of the pH value and the acidic or alkaline capacity.
Changes in transepidermal water loss may be the cause of combined effects of dermal irritants. Tandem application of topical retinoic acid and sodium lauryl sulphate has been shown to cause synergistic effects concerning non-specific skin irritation.
Transepidermal water loss increases dramatically shortly after application of sodium lauryl sulphate, but the increase is delayed after application of retinoic acid (Ale et al., 1997). [The Toxicological Effects of Exposure to Mixtures of Industrial and Environmental Chemicals, FødevareRapport 2003:12, 1st Edition, 1st Circulation, August 2003, Danish Veterinary and Food Administration; p. 75]

The addition of lipids to the skin may prevent loss of skin lipids due to e.g. exposure to organic solvents or replace skin lipids extrinsically. Lipid ingredients of cream bases have been demonstrated to protect industrial workers against the effects of exposure to organic solvents (Menczel, 1985). Other skin-protective materials include different types of waxes, e.g. paraffin wax and bees wax. Application of the waxes to the skin of human volunteers before treatment with irritants or allergens has significantly suppressed the dermal irritancy of sodium lauryl sulphate and combined ammonium hydroxide/urea treatment and moreover appeared to protect against the induction of allergic contact dermatitis (Zhai et al., 1998). [Ibid., p. 75]

7.7.5 Sensitisation

In a study of the influence of the skin irritant sodium lauryl sulphate (SLS) on sensitisation to 2,4,-dinitrochlorobenzene Cumberbatch et al (1993) found that SLS did not enhance sensitisation by increased skin penetration but by an increase in the number of immunostimulatory dendritic cells from the skin which reach the draining lymph node. van’t Erve et al (1998) found that the cellular and humoral response to the contact allergen oxazolone was dissimilary affected by the vehicles used. A wet work environment will also enhance the possibility of sensitisation as water helps to break down the skin barrier. Occlusion e.g. gloves, armpits, will also facilitate sensitisation. Skin disease will do the same. The increased sensitisation may be induced by increased penetration of the skin, or other mechanisms as in the SLS study. [Ibid., p. 129]

371 NOVEL IN VITRO SKIN IRRITATION MARKERS IDENTIFIED USING MICROARRAY TECHNOLOGY. S. Fletcher, C. Duggan and D. Basketter. SEAC - Safety and Environmental
Assurance Center, Unilever, Sharnbrook, Bedfordshire, United Kingdom.

To develop a relevant and sensitive in vitro testing strategy for the identification of mild to more substantially irritant compounds, mechanistic information on the skin irritation response is required. This study investigated the mechanisms of mild skin irritation for a number of compounds, identifying specific and general markers. EpiDerm™ (MatTek, USA), a reconstructed human skin model, was treated in triplicate with 0.1mg/ml benzalkonium chloride (BKC), 2.5mg/ml phenol, 0.1mg/ml sodium lauryl sulphate (SLS) or media control for 15min, 2, 4 or 24 hours. The doses used were non-cytotoxic, as determined by MTT assay and histology. Microarray analysis of 5 biological replicates was performed using Cy3 and Cy5 labelled samples hybridised to an in-house skin chip comprising of 2100 skin relevant genes in triplicate. For each irritant chemical around 400 genes were upregulated. Known irritation markers found to be up-regulated, included IL-1α, IL-8, TNFα and EGF. 20% of genes were up-regulated with all three compounds and therefore could be classed as associated with general irritation, these included hsp27, integrin β3 and VCAM1 among others. In addition genes were found which were compound specific. IL-16, early growth response 1, caspase 8, caveolin 1, adenylate cyclase 8 are examples of genes up-regulated upon treatment with SLS. Treatment with BKC up-regulated, phospholipase A2, midkine, IL-12 receptor, retinoic acid receptor responder, transglutaminase 1, IL-6. Genes up-regulated in response to phenol included, fibronectin, integrin α6, calcitonin, serine protease inhibitor, transglutaminase 4 and thioredoxin. These results demonstrate that although compounds initially may use different mechanisms of action, there are nevertheless similarities and a number of genes could be investigated further as potential general markers of irritation. (Source: TOXICOLOGICAL SCIENCES, THE TOXICOLOGIST; Society of Toxicology 43rd Annual Meeting Baltimore, Maryland; a supplement to An Official Journal of the Society of Toxicology; Volume 78, Number S-1, March 2004. p. 76)

1724 CLINICAL SAFETY OF REACTIVE SKIN DECONTAMINATION LOTION (RSDL).

D. A. Tonucci¹, S. Masaschi¹, L. Lockhart¹, M. Millward¹, D. Liu², R. Clawson², V. Murphy³, P. O’Dell⁴, M. C. Lanouette⁵, T. Hayes⁶ and C. Sabourin⁶.
¹Hill Top Research, Cincinnati, OH,
²Chemical Biological Medical Systems Project Management Office, Ft Detrick, MD,
³MarCorSysCom, Quantico, VA,
⁴O’Dell Engineering, Cambridge, ON, Canada,
⁵Canadian Department of National Defense, Ottawa, ON, Canada, and
⁶Battelle, Columbus, OH.

A clinical program was designed to assess the dermal safety of a new personal skin decontaminant system. Reactive Skin Decontamination Lotion (RSDL) is a liquid, reactive lotion which removes and destroys chemical warfare agents and toxins from the skin. The clinical program included: a 21-day cumulative dermal irritation study in 30 subjects, a Repeat Insult Patch Test (RIPT; Jordan/King modified Draize design) in 200 subjects and a photo-irritancy/allergenicity study in 30 subjects. For cumulative irritancy 25 μL of RSDL applied to a 1 cm punch of sponge applicator was patched occlusively for 21 consecutive days. Results from the study indicated that RSDL/applicator was of low irritancy potential versus the positive (0.5 M sodium lauryl sulphate) and negative (normal saline) controls. For allergenicity, 25 μL of RSDL/applicator punch was patched 9 times, with continuous exposure, for a 3-week induction phase followed by a 2-week rest period where subjects received no exposure to RSDL/applicator. A single challenge application at a naive site followed the rest period. RSDL/applicator was not allergenic in the RIPT as indicated by low erythema scores reported during the challenge phase. RSDL was tested for phototoxicity by comparing the skin reaction to a single exposure of RSDL/applicator with or without UVA/B exposure. Finally, photoallergenicity was determined for RSDL in a similar manner as in the RIPT with the exception that subjects were exposed to UV radiation after patch removal during induction and challenge. RSDL was found non phototoxic and non photoallergenic. The cumulative irritation, RIPT and phototox/photoallergy studies indicate that RSDL has a low risk for the development of dermal toxicity. Supported by RSDL/Foreign Comparative Testing Program and conducted under USAMRMC Contract No.
DAMD17-99-D-0010. (Ibid., pp. 354, 355)

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Mortality from Lung Cancer in Workers Exposed to Sulfur Dioxide in the Pulp and Paper Industry

Environmental Health Perspectives Volume 110, Number 10, October 2002

Won Jin Lee,1 Kay Teschke,2 Timo Kauppinen,3 Aage Andersen,4 Paavo Jäppinen,5 Irena Szadkowska-Stanczyk,6 Neil Pearce,7 Bodil Persson,8 Alain Bergeret,9 Luiz Augusto Facchini,10 Reiko Kishi,11 Danuta Kielkowski,12 Bo Andreassen Rix,13 Paul Henneberger,14 Jordi Sunyer,15 Didier Colin,1 Manolis Kogevinas,15 and Paolo Boffetta1 1International Agency for Research on Cancer, Lyon, France; 2University of British Columbia, Vancouver, Canada; 3Finnish Institute of Occupational Health, Helsinki, Finland; 4Norwegian Cancer Registry, Oslo, Norway; 5Stora Enso Oyj, Imatra, Finland; 6Nofer Institute of Occupational Medicine, Lodz, Poland; 7Massey University, Wellington, New Zealand; 8University Hospital Department of Occupational and Environmental Medicine, Linköping, Sweden; 9Claude Bernard University, Lyon, France; 10Federal University of Pelotas, Pelotas, Brazil; 11Graduate School of Medicine, Hokkaido, Japan; 12National Centre for Occupational Health, Johannesburg, South Africa; 13Danish Cancer Society, Copenhagen, Denmark; 14National Institute for Occupational Safety and Health, Morgantown, West Virginia, USA; 15Municipal Institute of Medical Research, Barcelona, Spain

Abstract

Our objective in this study was to evaluate the mortality of workers exposed to sulfur dioxide in the pulp and paper industry. The cohort included 57,613 workers employed for at least 1 year in the pulp and paper industry in 12 countries. We assessed exposure to SO₂ at the level of mill and department, using industrial hygiene measurement data and information from company questionnaires; 40,704 workers were classified as exposed to SO₂. We conducted a standardized mortality ratio (SMR) analysis based on age-specific and calendar period-specific national mortality rates. We also conducted a Poisson regression analysis to determine the dose-response relations between SO₂ exposure and cancer mortality risks and to explore the effect of potential confounding factors. The SMR analysis showed a moderate deficit of all causes of death [SMR = 0.89; 95% confidence interval (CI), 0.87-0.96] among exposed workers. Lung cancer mortality was marginally increased among exposed workers (SMR = 1.08; 95% CI, 0.98-1.18). After adjustment for occupational coexposures, the lung cancer risk was increased compared with unexposed workers (rate ratio = 1.49; 95% CI, 1.14-1.96). There was a suggestion of a positive relationship between weighted cumulative SO₂ exposure and lung cancer mortality (p-value of test for linear trend = 0.009 among all exposed workers; p = 0.3 among workers with high exposure). Neither duration of exposure nor time since first exposure was associated with lung cancer mortality. Mortality from non-Hodgkin lymphoma and from leukemia was increased among workers with high SO₂ exposure; a dose-response relationship with cumulative SO₂ exposure was suggested for non-Hodgkin lymphoma. For the other causes of death, there was no evidence of increased mortality associated with exposure to SO₂. Although residual confounding may have occurred, our results suggest that occupational exposure to SO₂ in the pulp and paper industry may be associated with an increased risk of lung cancer. Key words: epidemiology, lung neoplasms, mortality, pulp and paper industry, sulfur dioxide. Environ Health Perspect 110:991-995 (2002). [Online 15 August 2002]

Table 2. Standardized mortality ratios of selected causes by SO2 exposure

(See table in full resolution)

....In summary, our findings are compatible with the hypothesis that exposure to SO₂ in the pulp and paper industry is associated with an increased risk of lung cancer, especially in high-exposure groups. Although confounding, particularly from smoking, may have been occurred, our results are compatible with the notion that SO₂ may have a cancer-promoting effect when it occurs in combination with other carcinogens in the pulp and paper industry.

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Full report: <http://www.ehponline.org/members/2002/110p991-995lee/lee-full.html>

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Sulfur pentafluoride

ACUTE TOXICITY DATA:

Lethal concentration data:
 

Species	Reference	LC50	LCLo	Time	Adjusted 0.5-hr   LC (CF)	Derived value
Rat	NDRC 1946	2,000 mg/m3	-----	10 min	130 ppm (0.69)	13 ppm
Mouse	NDRC 1946	1,000 mg/m3	-----	10 min	66 ppm (0.69)	6.6 ppm
Rabbit	NDRC 1946	4,000 mg/m3	-----	10 min	262 ppm (0.69)	26 ppm
G. pig	NDRC 1946	4,000 mg/m3	-----	10 min	262 ppm (0.69)	26 ppm
Dog	NDRC 1946	4,000 mg/m3	-----	10 min	262 ppm (0.69)	26 ppm

Source: Sulfur pentafluoride, IDLH Documentation, CAS number: 5714­22­7,  US  Center for Health and Human Services, Centers for Disease Control and Prevention

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Sulfur (in Beef Cattle Mineral Nutrition)

Sulfur (S) is unique in that it is the only trace mineral incorporated into amino acids (specifically, methionine and cystiene). Amino acids are the building blocks for protein. Rumen microorganisms use inorganic sulfur to form their own sulfur-containing amino acids. Sulfur has many dietary sources. Soybean products, alfalfa hay and corn byproducts have relatively high levels of sulfur.

Thiamin and biotin (vitamins), as well as certain enzymes, also are sources of S. Water can contain high levels of sulfur, as well. Cereal grains, such as corn or oats, generally range from 0.14 percent to 0.23 percent S; protein sources, such as soybean meal, can contain as much as 0.5 percent sulfur. Forages tend to be more variable. Alfalfa, for example, typically will range between 0.25 percent and 0.50 percent S, whereas grass hays, such as brome or prairie, contain little or no sulfur. Cattle on pasture require 0.15 percent S in their diet.

Deficiencies in S are not common. However, when a deficiency exists, signs include poor appetite, emaciation and dullness. In addition, low levels of dietary S can result in poor utilization of nonprotein nitrogen (NPN), which in turn reduces microbial growth and fermentation.

The sulfur level is critical in growing and finishing rations. These diets, which typically are high in S and low in fiber, can induce an S toxicity. Sulfur toxicity can interfere with selenium, copper, molybdenum and thiamin metabolism.

South Dakota State University (Patterson, et al., 2003) recently reported data indicating intake and average daily gain decreased in feedlot cattle as sulfate levels in water increased. In addition, cattle developed a disease known as polioencephalomalacia (PEM; commonly referred to as polio), when S levels in the water were greater than 100 milligrams/liter. This disease affects the nervous system. Symptoms include blindness, difficulty walking, muscle tremors, convulsions and ultimately death. Producers concerned about sulfur should have their water tested before they implement a sulfur supplementation program.

________________________
Source:
North Dakota State University
NDSU Extension Service

Beef Cattle Mineral Nutrition
AS-1287,  June 2005
Marcy Ward, Ph.D. candidate, research associate, NDSU Department of Animal and Range Sciences
Greg Lardy, NDSU Extension beef specialist, Department of Animal and Range Sciences

See also:

• SO₂ Emissions linked to poor health in cattle

• Polioencephalomalacia (Cerebrocortical necrosis)
  The Merck Veterinary Manual

Polioencephalomalacia (PEM) is an important neurologic disease of ruminants that is seen worldwide. Cattle, sheep, goats, deer, and camelids are affected. The term PEM denotes a lesion with certain gross and microscopic features that are not specific for a particular etiology or pathogenesis. Historically, PEM has been associated with altered thiamine status, but more recently an association with high sulfur intake has been observed....

A variety of sulfur sources can result in excessive sulfur intake, including water, feed ingredients, and forage. Many geographic areas have surface and deep waters high in sulfate. When evaporation occurs, water sulfate concentrations increase. Water consumption by cattle is temperature dependent and increases greatly at high temperatures, leading to increased sulfur intake due to concurrent increases in water consumption and sulfate concentrations in water....
(Full Article)

• Sulphur-Containing Compounds in Drinking Water for Cattle
  Stefanie J.W.H. Oude Elferink, Gerwin A.L. Meijer.
  ID TNO Diervoeding, Postbus 65, 8200 AB, Lelystad.
  
  The discussion paper shows an Dutch version of the following abstract, but the rest of the text is in English.  The paper contains an exhaustive treatment of the toxicity and other aspects of many forms of sulphur compounds and their impact on the health of ruminants.

1. Abstract

Inorganic sulfur-containing compounds (S-compounds) can be present in surface water in high concentrations. These compounds provoke effects on animal health and production.  Sulfate (SO₄^2-) and sulfide (S^2-) are the most common S-compounds in surface water. Of these two, sulfide is the most toxic compound. A high sulfide concentration in the rumen can cause the deadly brain necrosis, polioencephalomalacia (PEM). Furthermore, chronic exposure to an elevated sulfide concentration in the rumen can cause secondary copper (Cu) deficiency, because Cu²⁺ ions will precipitate with S^2- ions to form copper sulfide (CuS).  Molybdenum (Mo) increases this reduced availability of Cu, due to formation of insoluble thiomolybdates. Other symptoms of high sulfide concentrations in the rumen include respirational problems, reduced feed intake, and reduced rumen motility.  The rumen microflora plays an important role in the formation of sulfide from inorganic and organic S-compounds. Rumen sulfide formation is mainly due to the activity of dissimilatory sulfate-reducing bacteria, that can use S-compounds (e.g. sulfate, sulfite (SO₃^2-), and thiosulfate) as electron acceptor under anaerobic conditions. Desulfovibrio sp. and Desulfotomaculum sp. appear to be the dominant sulfate-reducing bacteria in the rumen. An S-rich diet will not immediately lead to sulfide intoxication, because the rumen microorganisms need a few days to adapt to the high levels of S-compounds in the rumen, before sulfide production is maximal. Inhibiting the development of a sulfate-reducing flora in the rumen could help to reduce sulfide-related diseases. However, thus far this has not been successful in practice.  The Dutch reference values for sulfate and sulfide in surface water, are 250 mg l and 0.02 mg l, respectively. With these current values, approximately 15-20 % of the total dietary S-content is originating from water. Furthermore, a sulfate concentration of 250 mg l in drinking water decreases the Cu-absorption from feed [by] 5-15 %, depending on the S and Mo-content of the diet, thus increasing the risk of secondary Cu-deficiency. For a better evaluation of the risk of the development of secondary Cu-deficiency in cattle, accurate S and Mo-concentrations in the feed should be available to the farmer.

7. Conclusions

Although the reference values for sulfate in surface water vary considerably between the different countries, it appears that the Dutch reference value of 250 mg l is not too strict for grazing cattle. Especially, since grass generally contains far more than the recommended dietary S concentration of 2.0 g S kg DM basis, and can even contain more than the maximum tolerated level of 4.0 g S kg DM. Adding additional S to the diet via the water, increases the risk of S-related diseases such as secondary Cu deficiency. Under Dutch conditions dairy cows can easily develop a Cu deficiency at high S intake or high Mo concentrations in the feed. A sulfate concentration in water of 250 mg l will increase this risk by decreasing the Cu absorption [by] 5-15 %. In the Netherlands, little information is available on S and Mo concentrations in the feed, thus farmers cannot determine in advance if their cattle will develop a secondary Cu deficiency when the S concentration in the water is high. Furthermore, an update of the model of Suttle & McLauchlan (1976) might be appropriate, but recent information on the interactions between Cu, Mo, and S in feed is scarce, and current recommended concentrations of Cu, Mo and S in feed do not take the interactions into account.  With the current Dutch reference value for sulfide in surface water (0.02 mg l), intake of this compound via water is negligible. Furthermore, concentration of CS₂ and MITC that can be present in surface water under normal circumstances, are below the recommended levels for cattle drinking water.
(Full Article)

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Posted March 15, 2005
Updates:
2006 03 17 (added more information on properties of sulphur)
2006 03 19 (added more information on sodium lauryl sulphate and a reference to a report on sulphur and sulphur compounds in the diet of ruminants)
2006 10 16 (reformated)