Sulphur Dioxide (SO2) is a poisonous gas with a sharp, nasty smell which has an odour like burnt matches in low concentrations and a choking, intense sulphur smell in higher concentrations.
It reacts easily with other substances (including water vapour in the air) to form harmful compounds, such as sulphuric acid, sulphurous acid and sulphate particles which are a source of acid rain and can have serious deleterious effects upon human health.
What are the effects of exposure to sulphur dioxide?
The Canadian Centre for Occupational Health and Safety has stated that sulphur dioxide “May harm the respiratory system. Can irritate and inflame the airways.”
In the case of children, exposure to sulphur dioxide may cause serious long term injury.
This is illustrated in Public Health Statement CAs#: 7446-09-5 issued by the Division of Toxicology of the US Agency for Toxic Substances and Disease Registry which states:
“Most of the effects of sulphur dioxide exposure that occur in adults (i.e. difficulty breathing, changes in the ability to breathe as deeply or take in as much air per breath, and burning of the nose and throat) are also of potential concern in children, but it is unknown whether children are more vulnerable to exposure. Children may be exposed to more sulphur dioxide than adults because they breathe more air for their body weight than adults do. Children also exercise more frequently than adults. Exercise increases breathing rate. This increase results in both a greater amount of sulphur dioxide in the lungs and enhanced effects upon the lungs.”
“Long term studies surveying large numbers of children have indicated possible associations between sulphur dioxide pollution and respiratory symptoms or reduced breathing ability. Children who have breathed sulphur dioxide pollution may develop more breathing problems as they get older, may make more emergency room visits for treatment of wheezing fits, and may get more respiratory illnesses than is typical for children.”
“It is known that exercising asthmatics are sensitive to low concentrations of sulphur dioxide. Therefore, increased susceptibility is expected in children with asthma, but it is not known whether asthmatic children are more sensitive than asthmatic adults.”
The U.S. National Library of Medicine website posted an article on line on 8 August 2016 (at toxtown.nlm.nih.gov) which states:
”Short-term exposure to high levels of sulphur dioxide in the air can be life- threatening by causing breathing difficulties and obstructing airways, especially for people with lung disease. Long-term exposure to persistent levels of sulphur dioxide can cause chronic bronchitis, emphysema, and respiratory illness. It can also aggravate existing heart disease. When sulphur dioxide reacts with other chemicals in the air to form tiny sulphate particles, these particles can gather in the lungs and cause increased respiratory problems and difficulty breathing. Long-term exposure to sulphate particles can cause respiratory disease and even premature death.”
The Ministry for the Environment in New Zealand, in an article posted on their website and reviewed on 14 January 2016 states:
“Sulphur dioxide can cause respiratory problems such as bronchitis, and can irritate your nose, throat and lungs. It may cause coughing, wheezing, phlegm and asthma attacks. The effects are worse when you are exercising. Sulphur dioxide has been linked to cardiovascular disease.”
Sulphur dioxide is a dangerous and toxic substance which requires prudent regulation if it is not going to cause irreparable harm to communities exposed to it.
Where does sulphur dioxide come from?
Apart from volcanoes, the main source of sulphur dioxide is industrial activity that processes materials containing sulphur such as coal fired factories and in cement making.
Cockburn Cement Limited (CCL) uses an estimated 250,000 tonnes of coal every year as fuel for the lime kilns at its Munster factory, producing large quantities of sulphur dioxide. The actual processes of lime and cement making also create sulphur dioxide, so this toxic gas is an inherent problem for all such businesses (although new processes and kilns and stringent environmental controls can reduce SO2 levels). In the financial year ending 30 June 2017 CCL’s factory produced 140,000 kgs of sulphur dioxide, about 7 times more than it reported in the year ending 30 June 2013. CCL also draws the equivalent of 1,428-1,749 Olympic-sized swimming pools of groundwater to cool its kilns and transport raw materials. The local groundwater also contains sulphur which is converted to sulphur dioxide and emitted from the factory. Further, CCL reuses the groundwater which is stored in artificial “wetlands” on site so the sulphur content of the water being used has probably increased in the 20 years it has been using this system.
How can we tell if we are being exposed to sulphur dioxide?
We sense the odour of sulphur dioxide as being a strong and intense smell, extremely pungent, disgusting, annoying, irritating to the nose and irritating psychologically, causing a range of symptoms from prickling sensations in the nose or sneezing to coughing, sharp or burning feeling in the nose, eyes and/or throat, depending on the concentration and duration of the exposure.
At what concentration can we detect this gas?
The scientific evidence is that humans can detect the odour of sulphur dioxide at levels ranging from 1.766 mg/m3 to 8.307 mg/m3 and the median odour threshold is around 2.77 mg/m3 (Odour Detection levels). This unit of measurement can be converted to another type of measurement called parts per million (PPM), using a standard formula.
In Australia, there are national air quality standards called NEPM which provide guidelines as to the maximum levels of exposure to certain gases, including sulphur dioxide in PPM.
Comparing the established Odour Detection Levels with the NEPM for sulphur dioxide we can say that humans can detect by smell the irritating, pungent odour of sulphur dioxide at a level about 3 times to about 16 times higher than the prescribed maximum National Standard of 0.20 ppm over a one hour period.
In other words, if you can smell the distinctive pungent odour of sulphur dioxide outside your home then the NEPM maximum limits have been exceeded by at least 3 to 5 times but it could be many times higher.
Nitrogen oxides, being nitric oxide (NO), nitrogen dioxide (NO2) and nitrous oxide (N2O),(collectively, “NOx”) are poisonous gases, the most significant being nitrogen dioxide (NO2). Nitrous oxide (“laughing gas”), although it is benign and of use, under heat and exposed to oxygen becomes nitric oxide which is a toxic pollutant.
Nitrogen dioxide has a strong, biting odour which can cause coughing, laboured breathing, a choking feeling and chest pain depending on its concentration in the air. Nitric oxide has a sharp, sweet-smelling odour but as it rapidly reacts with oxygen in the air, it converts to nitrogen dioxide quite quickly.
These noxious gases are produced at CCL’s factory in Munster. Nitrogen dioxide is monitored by CCL but its licence does not limit or control the amount or concentration of this gas being produced or released.
CCL is allowed to emit as much NOx as it wants to produce its products. In the financial year ending 30 June 2017 CCL’s factory produced 930,000 kg of nitrogen dioxide.
The concern is that CCL has a very poor record of monitoring its toxic emissions (e.g. in January 2016 the data relating to NOx and SO2 emissions from Kiln 5 was only available 68.1% and 65.5% of the time respectively). Consequently, no one really knows how much nitrogen dioxide has been released by the Munster factory in the past 20 years.
What are the effects of nitrogen dioxide?
It is scientifically accepted internationally that nitrogen dioxide is a pollutant in the environment and can be a hazard to human health if high level exposure occurs in the short term or low level exposure is experienced in the longer term. It has been said that:
“…nitrogen dioxide (NO2) has been most frequently studied and an extensive data base links it to a number of specific health and welfare effects. Generally speaking, the effects of NO2 on the respiratory system have been most extensively studied, and the potential of this compound to induce both acute and long-term effects appears to be fairly convincingly documented.” (Steven M. Horvath, Ph.D., Director, Institute of Environmental Stress, University of California in 1980)
The US Environmental Protection Agency (EPA) has stated:
“Breathing air with a high concentration of NO2 can irritate airways in the human respiratory system. Such exposures over short periods can aggravate respiratory diseases, particularly asthma, leading to respiratory symptoms (such as coughing, wheezing, or difficulty breathing), hospital admissions and visits to emergency rooms. Longer exposures to elevated concentrations of NO2 may contribute to the development of asthma and potentially increase susceptibility to respiratory infections. People with asthma, as well as children and the elderly are generally at risk for the health effects of NO2. NO2 along with other NOx reacts with other chemicals in the air to form particulate matter and ozone. Both of these are harmful when inhaled due to the effects on the respiratory system.”
The Final Report about NO2 by the US EPA in 2016 found that:
1. Short-term exposure to NO2 can cause respiratory effects, in particular, effects related to asthma exacerbation.
2. The respiratory effects of short-term NO2 exposure are independent of the effects of many other traffic-related pollutants.
3. There is now stronger evidence for a relationship between long-term exposure to NO2 and respiratory effects, particularly the development of asthma in children.
4. Short-term exposure to NO2 may be associated with cardiovascular effects and premature mortality.
5. Long-term exposure maybe associated with cardiovascular effects, diabetes, poorer birth outcomes, premature mortality, and cancer (but it is uncertain whether NO2 exposure has an effect on these health outcomes that is independent from the effects of other traffic-related pollutants).
Therefore, great care needs to be taken to ensure that urban populations (and especially vulnerable groups such as children, the elderly, sufferers of heart disease and asthma and those who have other pre-existing, or are predisposed to, respiratory conditions) are not exposed to nitrogen dioxide at levels where their life or health may be compromised.
It is also scientifically accepted that the reaction of nitrogen dioxide with chemicals produced by sunlight leads to the formation of nitric acid, a major component of acid rain. Nitrogen dioxide also reacts with sunlight, which leads to the formation of ozone and smog conditions. Nitrogen oxides react with water (in humid air) to from nitric acid. The risks posed by NOx require a prudent and conservative approach when Government is considering allowing such toxic agents to be released by industry located in urban areas.
What exposure levels to nitrogen dioxide are acceptable?
The National Environmental Protection Measures (NEPM) set out guidelines for maximum limits of exposure to nitrogen dioxide as follows:
- 0.12 parts per million (ppm) averaged over a one hour period (not more than 1 day’s exposure per year)
- 0.03 ppm averaged over a one year period (no exposure to this level whatsoever)
These limits recognize the potential danger to the amenity and health of the Australian community posed by this toxic gas.
Nitrogen dioxide, the most toxic of the oxides of nitrogen, has the following effects at different concentrations:
- at at 10-20 ppm it can cause mild irritation of the nose and throat
- 25-50 ppm it can cause edema (fluid on the lung) leading to bronchitis or pneumonia
- levels above 100 ppm can cause death due to asphyxiation from fluid in the lungs.
Often, there are no symptoms at the time of exposure other than a transient cough, fatigue or nausea, but over hours inflammation in the lungs causes edema.
In effect, this means that symptoms may only become apparent after exposure has occurred for some time at levels which may be many times higher than the maximum prescribed level under the NEPM for urban environments in Australia.
It is clear that without specialist gas monitoring equipment people cannot detect the presence of nitrogen dioxide as our capacity to detect this toxic gas by smell is well beyond the recommended maximum level of exposure.
If residents living near the Munster factory can be detect nitrogen dioxide by irritation of the nose or throat then the level in their environment is many times higher then the prescribed NEPM.
Carbon monoxide (CO) is a colourless, odourless, and tasteless gas that is slightly less dense than air. It is therefore undetectable by humans and we must rely on sensitive gas monitors to identify its presence.
Carbon monoxide is toxic to all cold and warm blooded animals (including humans) when encountered in concentrations above about 35 ppm. It does have a role in normal animal metabolism in low quantities and is thought to have some normal biological functions.
What effects does this gas have?
Carbon monoxide poisoning occurs after breathing in too much of this gas. Symptoms of acute poisoning include lightheadedness, confusion, headache, feeling like the world is spinning, and flu-like effects. Larger exposures can lead to toxicity of the central nervous system and heart, and death. After acute poisoning, long-term problems may occur. Carbon monoxide can also have negative effects on a baby if exposed during pregnancy. Chronic exposure to low levels of carbon monoxide can lead to depression, confusion, and memory loss.
What makes carbon monoxide?
Carbon monoxide is a product of the incomplete combustion of organic matter. It is often produced by motor vehicles that run on gasoline, diesel, methane, or other carbon- based fuels and from tools, gas heaters, and cooking equipment that are powered by carbon-based fuels such as propane, butane and charcoal.
It is produced in the lime burning process used by CCL at its Munster factory, as a result of burning coal. In the year ending 30 June 2017, CCL self-reported that 990,000 kgs of carbon monoxide was produced at its Munster factory.
How hazardous is carbon monoxide?
The hazard to human health posed by carbon monoxide is a significant public health problem. Carbon monoxide poisoning is the most common type of fatal poisoning in many countries.
The National Environmental Protection Measures (NEPM) prescribes that exposure to carbon monoxide should not exceed 9.0 parts per million (ppm) over an 8 hour period.
CCL’s licence does not limit the amount of carbon monoxide it can produce and emit from its Munster factory.
While carbon monoxide emitted by the factory begins to be diluted once it hits the outside atmosphere at the present time we do not know the levels of concentration of this toxic gas when it reaches the homes of nearby residents.
The Department of Water and Environmental Regulation, which has responsibility for controlling CCL’s pollution, has not yet conducted any independent scientific studies using portable gas chromatography technology to measure carbon monoxide emitted from the factory.
Hydrogen chloride is also known as anhydrous hydrochloric acid and spirits of salts.
Under normal conditions, hydrogen chloride is a colourless gas, which has a choking, pungent smell. It is highly corrosive and toxic. Hydrogen chloride readily dissolves in water to give hydrochloric acid. In moist conditions, hydrogen chloride gas reacts with water in the air to give clouds of hydrochloric acid (which falls as acid rain).
Where does it come from?
The most significant releases of hydrogen chloride occur when coal is burned (particularly from coal-fired power stations) and when waste is incinerated. This occurs because coal and waste foods contain common salt (sodium chloride), which reacts with hydrogen to give hydrogen chloride. Incineration of plastics such as PVC also results in releases of hydrogen chloride. Relatively small quantities of hydrogen chloride are released naturally from volcanoes.
CCL’s factory produces hydrogen chloride from burning coal, using groundwater containing chlorides and from sodium chloride in shell sand and seawater that CCL extracts from Cockburn Sound. In the financial year ending 30 June 2017 CCL’ self-reported that it Munster factory produced 23,000 kg of hydrochloric acid as well as 4,500 kg of chlorine and chlorine products.
How might it affect the environment?
Hydrogen chloride gas is highly corrosive and will damage metal structures and buildings or monuments made of limestone. If high levels of hydrogen chloride gas dissolve in a water body, aquatic organisms will be harmed and even killed. This is only likely as a result of an accidental spill of much larger amounts of hydrogen chloride than are typically released to the environment. The very high solubility of hydrogen chloride gas means that releases to the atmosphere are quickly washed out by rain and moisture in the air. Some soils and lakes may be sensitive to this acid rain if amounts of it falling are above certain amounts defined as “critical loads”. This makes hydrogen chloride pollution a global as well as local environmental problem.
How might exposure to it affect human health?
Hydrogen chloride can enter the body either by inhalation of air containing hydrogen chloride, accidental ingestion of liquid hydrogen chloride or hydrochloric acid, or by dermal (skin) contact with liquid hydrogen chloride or hydrochloric acid (dissolved hydrogen chloride). Dermal contact mainly occurs in the occupational setting. Inhalation of air containing low levels of hydrogen chloride over short periods of time can cause throat irritation. Exposure to higher levels may result in effects including rapid breathing, blue colouring of the skin, fluid accumulation in the lungs and in extreme cases severe swelling of the throat, suffocation and death. Inhalation of hydrogen chloride can also lead to reactive airways dysfunction syndrome (asthma caused by inhalation of corrosive substances) in some individuals. Contact with the eyes can cause irritation and burns.
What steps are being taken to limit the potential impacts?
The current conditions on CCL’s licence to operate the factory have no requirements to limit chlorine/chloride inputs to reduce production of hydrogen chloride.
CCL no longer makes cement at its Munster factory but it imports ‘clinker’ which is used to make its Portland cement and related cement products. Clinker are small nodules of cement often created in coal fired cement kilns from limestone or other source containing calcium carbonate together with waste products of blast furnaces.
We do not presently know the country (or countries) from where CCL imports ‘clinker’ but it is probably China. This imported clinker contains a number of elements (including heavy metals) which are potentially toxic if inhaled. Tests conducted at the National Measurement Institute have established that the ‘clinker’ CCL uses contains, in addition to aluminium compounds and sulphur, a significant quantity of titanium as well as antimony, arsenic, barium, beryllium, cadmium, cesium, chromium, cobalt, copper, lead, manganese, mercury, nickel, and uranium. Blast furnace slag is used in CCL’s Portland cement and this contains a range of heavy metals and their compounds.
The ‘clinker’ is ground into a fine powder at CCL’s Munster factory and mixed with additional ‘ingredients’ to make its Portland cement product.
Because this area of the Munster factory is not sealed, clouds of very fine Portland cement are frequently blown into the air and fall on residences up to at least 4 kilometres away.
How does Portland cement affect human health?
The hazard to human health occurs when Portland cement is inhaled because it contains a range of substances which are toxic to the human body. Larger particles (> 2.5 PM) can lodge in the nose, throat and lungs and cause respiratory symptoms and disease, depending on the quantity and the duration of the exposure. Smaller particles (< 2.5 PM) can enter the lung and pass into the bloodstream where they can lodge in organs. If these small particles contain elements such as cadmium and others they may cause long term illness such as cancer.
More technical information about Portland cement follows.
ASTM C150 defines Portland cement as “hydraulic cement (cement that not only hardens by reacting with water but also forms a water-resistant product) produced by pulverizing clinkers which consist essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulphate as an inter ground addition.” The European Standard EN 197-1 uses the following definition:
Portland cement clinker is a hydraulic material which shall consist of at least two-thirds by mass of calcium silicates (3 CaO·SiO2 and 2 CaO·SiO2), the remainder consisting of aluminium- and iron-containing clinker phases and other compounds. The ratio of CaO to SiO2 shall not be less than 2.0. The magnesium oxide content (MgO) shall not exceed 5.0% by mass.
(The last two requirements were already set out in the German Standard, issued in 1909).
Clinkers make up more than 90% of the cement along with a limited amount of calcium sulfate (which controls the set time) and up to 5% minor constituents (fillers) as allowed by various standards. Clinkers are nodules (diameters, 0.2–1.0 inch [5–25 mm]) of a sintered material that is produced when a raw mixture of predetermined composition is heated to high temperature. The key chemical reaction which defines Portland cement from other hydraulic limes occurs at these high temperatures (>1,300 °C (2,370 °F)) and is when the belite (Ca2SiO4) combines with calcium oxide (CaO) to form alite (Ca3SiO5).
Portland cement clinker is made by heating, in a cement kiln, a mixture of raw materials to a calcining temperature of above 600 °C (1,112 °F) and then a fusion temperature, which is about 1,450 °C (2,640 °F) for modern cements, to sinter the materials into clinker. The materials in cement clinker are alite, belite, tri-calcium aluminate, and tetra-calcium alumino ferrite. The aluminium, iron, and magnesium oxides are present as a flux allowing the calcium silicates to form at a lower temperature and contribute little to the strength. For special cements, such as Low Heat (LH) and Sulfate Resistant (SR) types, it is necessary to limit the amount of tricalcium aluminate (3 CaO·Al2O3) formed. The major raw material for the clinker-making is usually limestone (CaCO3) mixed with a second material containing clay as source of alumino- silicate. Normally, an impure limestone which contains clay or SiO2 is used. The CaCO3 content of these limestones can be as low as 80%. Secondary raw materials (materials in the rawmix other than limestone) depend on the purity of the limestone. Some of the materials used are clay, shale, sand, iron ore, bauxite, fly ash, and slag. When a cement kiln is fired by coal, the ash of the coal acts as a secondary raw material.
To achieve the desired setting qualities in the finished product, a quantity (2–8%, but typically 5%) of calcium sulfate (usually gypsum or anhydrite) is added to the clinker and the mixture is finely ground to form the finished cement powder. This is achieved in a cement mill. The grinding process is controlled to obtain a powder with a broad particle size range, in which typically 15% by mass consists of particles below 5 μm diameter, and 5% of particles above 45 μm. The measure of fineness usually used is the “specific surface area”, which is the total particle surface area of a unit mass of cement. The rate of initial reaction (up to 24 hours) of the cement on addition of water is directly proportional to the specific surface area. Typical values are 320–380 m2·kg−1 for general purpose cements, and 450–650 m2·kg−1 for “rapid hardening” cements. The cement is conveyed by belt or powder pump to a silo for storage. Cement plants normally have sufficient silo space for one to 20 weeks of production, depending upon local demand cycles. The cement is delivered to end users either in bags or as bulk powder blown from a pressure vehicle into the customer’s silo. In industrial countries, 80% or more of cement is delivered in bulk.
Typical constituents of Portland clinker plus gypsum Cement chemists notation under CCN.
|Tricalcium silicate (CaO)3 · SiO2||C3S||45–75%|
|Dicalcium silicate (CaO)2 · SiO2||C2S||7–32%|
|Tricalcium aluminate (CaO)3 · Al2O3||C3A||0–13%|
|Tetracalcium aluminoferrite (CaO)4 · Al2O3 · Fe2O3||C4AF||0–18%|
|Gypsum CaSO4 · 2 H2O||CSH2||2–10%|
Typical constituents of Portland cement Cement chemists notation under CCN.
|Calcium oxide, CaO||C||61–67%|
|Silicon dioxide, SiO2||S||19–23%|
|Aluminum oxide, Al2O3||A||2.5–6%|
|Ferric oxide, Fe2O3||F||0–6%|
|Sulfur (VI) oxide, SO3||S||1.5–4.5%|
What are they?
In essence, particulates are ‘dust’ particles which leave CCL’s Munster factory at or near ground level from activities on site or they are emitted from the 180 metre factory kiln tower and shower down in the wind shadow of the tower, the distance away depending on prevailing winds and weather. The particulates have different sizes and are made up of different toxic substances, including sulphates and heavy metals.
How do they affect human health?
The larger particulates (> 2.5 micrometres) can lodge in different parts of the nose, mouth, throat and lungs. Some of these particles lodge in the nose and throat, are absorbed into the body and converted to other chemicals, and pass out of the body. They may cause sneezing, coughing and other respiratory symptoms.
However, small particles (< 2.5 micrometres) can lodge in the lungs causing a reduction in respiratory capacity and ultimately respiratory diseases of various kinds like asthma and emphysema, cardiac impairment and premature death. Some small particles containing heavy metals (e.g. lead, arsenic, cadmium and mercury) can pass from the lungs and be absorbed into the blood where they can lodge in various organs causing long term damage to the body; a source of cancer in those organs.
What are these particulates?
The particulates of concern are coal dust (stockpiled on site), lime kiln dust (dumped as waste on site), Portland cement ‘clinker’ (ground on site into a fine powder which becomes airborne) and shell sand (stockpiled on site). Quicklime dust is also regularly emitted from the kiln stacks and deposited on nearby residences. During 2017/8 local residents had dust samples from their backyards tested at the National Measurement Institute (NMI) in Sydney and every sample was found to contain the main constituent elements of the Portland cement and quicklime products produced at the factory. The quicklime produced at the factory has a pH of 12 which exceeds the maximum pH level of alkali permitted to be released into the environment (being a pH of 10). A set of tests by NMI in April 2018 established that “dusts” from the factory contain several or all of the following: aluminium, antimony, arsenic, barium, beryllium, cadmium, cesium, chromium, cobalt, copper, lead, manganese, mercury, nickel, sulphur, titanium and uranium.
Heavy Metals and other potential toxic metals
A range of metals and their compounds are unwanted by-products of the lime making process, while others are incorporated into CCL’s lime and cement products (e.g. magnesium, aluminium)
Adverse health effects of metals and their compounds
Some of these metals are more toxic than others. Heavy metals such as arsenic, cadmium, mercury and lead are the better known environmental hazards. Some of these metals (for example, mercury) also accumulate in the human body as a poison.
Mercury can affect the fetus, lead can be neurotoxic (especially in children) and arsenic in drinking water has been related to skin and other cancers. The risk to the community living around the Premises is that some of these metals can bind to particulate emissions from burning coal or other particulates emitted from the kiln stacks and can be inhaled by residents and their children.
On 20 February 2018 the results of tests conducted by the National Measurement Institute in Sydney on ‘dust’ samples supplied by four residents of Beeliar became available. In addition to these four samples containing the same elements as CCL’s Portland cement and quicklime products, they also contained heavy metals. Tests had been conducted to determine if any of the ‘dust’ contained the heavy metals mercury, lead, arsenic and cadmium.
One sample, taken in [address redacted], contained all four heavy metals. One sample, taken in [address redacted], contained three of the four heavy metals (cadmium was below the testable threshold) and the other two contained arsenic and lead (cadmium and mercury being below the respective testable thresholds).
The results are set out below:
Streets in Beeliar
East of factory
North of factory
< 0.5 mg/kg
Northeast of factory
< 0.2 mg/kg
< 0.5 mg/kg
Northeast of factory
< 0.2 mg/kg
In other words, particulate matter emitted by the factory contains heavy metals known to have adverse health impacts.
There is also evidence from one resident that particulate emissions containing heavy metals emanating from the Premises may have caused adverse health effects. A 41 year old male who has lived and worked near the factory for many years attributes his poor health to heavy metal poisoning he suffered from his long term exposure to particulate emissions from the Premises. On 30 October 2015 and again on 15 April 2016 tests were conducted by InterClinical Laboratories Pty Limited of Alexandria, New South Wales, on hair samples supplied by this resident. The tests in 2015 showed the presence of (amongst others) arsenic, beryllium, mercury, chromium, cadmium, lead, aluminium, rubidium, copper, nickel and strontium. The level of lead was assessed by the laboratory as high. The 2016 test showed the continuing presence of arsenic, an elevated level of lead and very high levels of aluminium. Aluminium has been associated with early onset Alzheimer’s disease. Aluminium is present in some of the raw materials (e.g. blast furnace slag) used by CCL at the factory to manufacture its products. Aluminium compounds are an inherent component of its quicklime and Portland cement products (as either Aluminium Oxide [Al2O3] or as tetracalcium aluminoferrite. Chromium is also a component of CCL’s Portland cement product from ‘clinker’ which is ground, screened, mixed and packaged at the factory.
Sources of metals and their compounds
Some of the more toxic substances such as mercury are introduced into the manufacturing process by burning coal and others are found in raw materials such as limestone/shell sand and some from dissolved substances in the groundwater used to cool the kilns and to transport slurries of shell sand.
Detection of metals and compounds
Condition 13 (and Table 8) of the conditions on CCL’s licence require annual monitoring of the following metals: mercury, thallium, cadmium, antimony, arsenic, lead, total chromium, cobalt, copper, manganese and nickel.
Regulation of metals and their compounds
Large proportions of metals entering the kilns adhere to particulate matter and therefore are removed in the “baghouse” filter systems for Kilns 5 and 6. No other specific controls are presently employed to remove metals in the waste gas stream. In the year ending 30 June 2017, the following metals were recorded in flue stack emissions at the Premises:
Nickel and Compounds
Zinc and compounds
Chromium and compounds
Copper and compounds
Mercury and compounds
Arsenic and compounds
Manganese and compounds
Cobalt and compounds
Beryllium and compounds
DWER acknowledges that:
“Typical measures to reduce metals emissions include controlling and minimising the metal content of fuels and feed.”
In other words, there is scope to further reduce metals emissions by replacing coal as a fuel (which contains mercury and other toxic contaminants) and replacing it with natural gas. This change would also further reduce particulate emissions, the vector for metals emissions.
The main product produced at the factory is quicklime (calcium oxide) which is made by heating shell sand dredged from Cockburn Sound. The shell sand is delivered to the factory in a watery slurry via a 7 kilometre pipeline. The shell sand is mainly calcium carbonate and when heated it breaks down into calcium oxide and carbon dioxide. The production of large quantities of carbon dioxide is an inherent part of making quicklime.
The community’s concern is that quicklime is frequently emitted from the kiln stacks from CCL’s Munster factory, usually at night. This form of ‘dust’ falls on residences causing a nuisance to residents who have to incur cleaning time and costs every week trying to remove this highly alkaline substance from their vehicles and other property on the exterior of their homes. There is also a risk this ‘dust’ may be inhaled by residents or their children.
Calcium oxide (CaO), commonly known as quicklime or burnt lime, is a widely used chemical compound. It is a white, caustic, alkaline, crystalline solid at room temperature. The broadly used term lime connotes calcium-containing inorganic materials, in which carbonates, oxides and hydroxides of calcium, silicon, magnesium, aluminium, and iron predominate. By contrast, quicklime specifically applies to the single chemical compound calcium oxide. Calcium oxide that survives processing without reacting in building products such as cement is called free lime.
Quicklime is relatively inexpensive. Both it and a chemical derivative (calcium hydroxide, of which quicklime is the base anhydride) are important commodity chemicals.
Calcium oxide is usually made by the thermal decomposition of materials, such as limestone or seashells, that contain calcium carbonate (CaCO3; mineral calcite) in a lime kiln. This is accomplished by heating the material to above 825 °C (1,517 °F), a process called calcination or lime-burning, to liberate a molecule of carbon dioxide (CO2), leaving quicklime.
CaCO3(s) → CaO(s) + CO2(g)
The quicklime is not stable and, when cooled, will spontaneously react with CO2 from the air until, after enough time, it will be completely converted back to calcium carbonate unless slaked with water to set as lime plaster or lime mortar.
Approximately 1.8 t of limestone is required per 1.0 t of quicklime. Quicklime has a high affinity for water and is a more efficient desiccant than silica gel. The reaction of quicklime with water is associated with an increase in volume by a factor of at least 2.5.
The lime/cement factory in Munster operated by Cockburn Cement Limited (CCL) is required to report to the National Pollution Inventory each year on the range and quantity of toxic substances it produces. This text explains what some of those toxins are and how they can affect human health.
1.0 Volatile Organic Compounds
Volatile Organic Compounds (VOCs) are chemicals that contain carbon and are found in all living things. They are organic compounds that easily become vapours or gases. Along with carbon, they contain elements such as hydrogen, oxygen, fluorine, chlorine, bromine, sulphur or nitrogen. VOCs are released from burning fuel, such as petrol, wood, coal, or natural gas. They are also emitted from oil and gas fields and diesel exhaust. Many VOCs are hazardous air pollutants. VOCs, when combined with nitrogen oxides, react to form ground-level ozone, or smog, which contributes to climate change.
1.1 Adverse health effects of VOCs
Long term exposure to VOCs can cause damage to the liver, kidneys, and central nervous system. Short term exposure to VOCs can cause eye and respiratory tract irritation, headaches, dizziness, visual disorders, fatigue, loss of coordination, allergic skin reactions, nausea, and memory impairment.
Some VOCs are suspected to cause cancer in humans and have been shown to cause cancer in animals. The health effects caused by VOC’s (like other airborne pollutants) depend on the concentration and length of exposure to the chemicals.
1.2 Sources of VOCs
VOCs are generated at CCL’s factory in the rotary kiln by the combustion process and heating of shell sand. There are a variety of VOCs generated some of which are more toxic than others. Compounds known to present a risk to public health above determined concentrations include Benzene, Toluene, Ethylbenzene and Xylenes (B-TEX compounds).
From a draft report by Katestone Environmental Limited prepared for the CCL we know some of the VOCs emitted from the Premises are 1,2 dibromoethane, toluene-2,4-diisocyanate, xylene and benzene.
1,2-Dibromoethane (ethylene dibromide) [Br(CH2)2Br or C2H4Br2] is a clear, colourless, volatile liquid with a mild, sweet, chloroform-like odour that emits corrosive and toxic fumes when heated to decomposition. Exposure severely irritates the skin, eyes and respiratory tract and causes depression and collapse. Prolonged inhalation may cause liver necrosis. It can reasonably be anticipated to be a carcinogen.
Toluene-2, 4-diisocyanate [C9H6N2O2 or CH3C6H3(NCO)2] (toluene) is a volatile, colourless to pale yellow liquid. It has a smell associated with paint thinners. When heated to decomposition toluene emits toxic fumes of cyanides and nitrogen oxides. Exposure of humans to toluene causes tissue irritation, especially to the mucous membranes, and can produce severe respiratory problems. Chronic inhalation exposure to toluene has resulted in significant decrease in lung function in workers, an asthma-like reaction characterised by wheezing, dyspnea (shortness of breath), and bronchial constriction. Animal studies have reported significantly increased incidences of tumours of the pancreas, liver and mammary glands from exposure (by placing the chemical in the stomach).
It is reasonably anticipated to be a carcinogen.
Xylene (dimethylbenzene) [CH3)2C6H4] is a colourless, flammable liquid with a “sweet” odour which occurs naturally in petroleum, coal and wood tar. Its smell has been likened to the smell emitted by whiteboard markers. The main effect of inhaling xylene vapour is depression of the central immune system, with symptoms such as headache, dizziness, confusion, change in sense of balance; skin, eyes, nose and throat irritation; breathing difficulties; stomach discomfort, possible changes in lung and kidney; nausea and vomiting.
Benzene is a toxic, volatile, colourless, highly flammable, liquid aromatic hydrocarbon with a petrol-like odour. It is a byproduct of coal distillation. Exposure to benzene causes neurological symptoms and affects the bone marrow causing aplastic anemia, excessive bleeding and damage to the immune system. Benzene causes central nervous system damage and is a known carcinogen. It has been linked to an increased risk of developing lymphatic and hematopoietic (blood/bone marrow/lymphatic) cancers, acute myelogenous (blood/marrow) leukemia, as well as chronic lymphocytic (blood/bone marrow) leukemia.
In 2015, as part of an Odour Verification Plan mandated by the Department of Water and Environmental Regulation (DWER) in conditions 63 and 64 of the Licence, CCL was required to test for a wide range of VOCs but it successfully opposed release of the results of these tests in a recent FOI application made on behalf of the Cockburn Pollution Stoppers group. Thus the range and levels of VOC emissions from the factory are not publicly available.
1.3 Detection of VOCs
In December 2016 DWER issued its Decision Report (Decision Report) on CCL’s licence. Its assessment of the potential risk of VOCs generated by activity at the Munster factory was not based on actual frequent monitoring of these substances but only on predictive “modelling”. “Modelling” of pollution levels is a bit like educated guessing where the assumptions you make determine what the predictions will be. The use of modelling of pollution levels by CCL was criticised by the Department of Health and independent experts in the 2010 parliamentary Inquiry into CCL. The Decision Report does not refer to any scientific or medical evidence concerning the potential for adverse health effects of VOCs when they are aggregated. In other words, while the emissions of particular VOCs (such as those specified in paragraph 1.2) may each fall below the accepted safe limit for that VOC, it may well be the case that the potential health risk is being underestimated as exposure to all of the VOCs produced at the factory may have cumulative or enhanced adverse health effects. DWER’s determination that VOC levels emitted from the Premises are “safe” is based on predictive monitoring and not on actual measurements taken at and around the factory (except for the tests conducted for the Odour Verification Plan in 2015 to which CCL has prevented public access).
The actual range and concentrations of VOCs emitted from the factory remain unknown to our community.
1.4 Regulation of VOCs
Condition 13 (and Tables 7 and 8) of CCL’s licence requires weekly point source monitoring of VOCs.
In the year ending 30 June 2017, 13,000 kg of VOCs were generated at the factory plus 0.49 kg of cumene (isopropyl benzene).
There is evidence that transitioning from coal burning to using natural gas as fuel will reduce the production of VOCs. In 1998 the UK Department of Trade and Industry calculated that VOCs emissions were substantially reduced by burning gas (5 grams/gigajoule) instead of coal (18 grams/gigajoule).
2.0 Polycyclic Aromatic Hydrocarbons
Polycyclic Aromatic Hydrocarbons (PAHs) are a class of chemicals that occur naturally in coal, crude oil and petrol. They are also produced when coal, oil gas, wood, garbage, and tobacco are burned. PAH’s generated from these sources can bind to or form small particles in the air.
2.1 Adverse health effects of PAHs
The health effects from environmental exposure to low levels of PAH’s are presently not fully known. Several of the PAHs and some specific mixtures of PAHs are considered to be cancer-causing chemicals.
DWER considers that short term exposure to PAHs may cause minor health impacts such as skin irritation while long term health effects include impacts on immunity, respiratory problems and cancer. Toxicity of PAHs is influenced by the nature of PAHs, dose and exposure.
The National Pollution Inventory website that states:
“Exposure can irritate the eyes, nose, throat, and bronchial tubes. Skin contact can cause irritation or a skin allergy. Very high levels can cause headaches, nausea, damage the red blood cells, damage the liver and kidneys, and may even cause death. The International Agency for Research on Cancer has cited a number of polycyclic aromatic hydrocarbons as ‘probably carcinogenic to humans’, a number of others are cited as being ‘possibly carcinogenic to humans’.”
2.2 Source of PAHs
PAHs are formed by the incomplete combustion of coal.
2.3 Detection of PAHs
CCL is no longer required under the conditions of its licence to monitor PAHs from kiln stack emissions. DWER claims the 2015 monitoring results indicate maximum ground level concentrations are less than 1% of the annual health criteria (Air Toxics NEPM). Given CCL’s history as to self-monitoring and problems associated with “modelling” pollution levels instead of actually measuring them, our community considers the present controls are inadequate. There is simply no basis for assuming that the levels of PAHs are as “modelled” and they may pose an ongoing risk to the health of local residents and their children.
2.4 Regulation of PAHs
PAHs are no longer regulated under the conditions of CCL’s licence to operate the Munster factory.
In the year ending 30 June 2017, CCL self-reported that the factory produced 2.4 kg of PAHs.
Any potential risk of adverse health effects from PAHs produced at the factory could be virtually eliminated if CCL was required to use gas exclusively instead of coal. This change would also enable a far more sophisticated approach to be taken to controlling kiln conditions so as to minimise pollution produced in the kilns.
3.0 Hydrogen Fluoride
Hydrogen fluoride (HF) is a colourless gas or liquid. It is a highly dangerous gas, immediately forming corrosive and penetrating hydrofluoric acid upon contact with moisture.
3.1 Adverse health effects of hydrogen fluoride
Any exposure to hydrogen fluoride requires immediate medical attention. Breathing in hydrogen fluoride at high levels or in combination with skin contact can cause death from an irregular heartbeat or from fluid build-up in the lungs. Hydrogen fluoride gas, even at low levels, can irritate the eyes, nose, and respiratory tract.
3.2 Sources of hydrogen fluoride
Fluorine occurs in trace amounts in most coals. The average fluorine content of Australian coals ranges from 20 to 300 micrograms/gram [mean ≈ 110 μg g-1F]. Fluorine is released into the atmosphere during the combustion of coal.
According to a US National Academy of Sciences report, coal combustion accounts for a significant fraction (10%) of the total atmospheric emissions of fluorine in the United States. Because of its effect upon environmental quality and health, fluorine has been classified as an element of moderate concern in the development of the coal resource.
The general public may breathe in higher amounts of fluoride in areas near coal-fired power plants or fluoride related industries or near hazardous waste sites. Higher levels may also be present in the soil where coal fired power plants or fluoride-releasing industries are located. It is not presently known what the health impacts are of long term exposure to low levels of hydrogen fluoride or air borne particles of hydrofluoric acid. Hydrogen fluoride is generated in lime kilns and, in particular, in the lime kilns at the factory.
3.3 Detection of hydrogen fluoride
The concentration of the acid gases Hydrogen Chloride and Hydrogen Fluoride emitted from a lime kiln are dependent on operating conditions within the kiln, specifically the contact of kiln gases with shell sand. There are presently no specific controls adopted by CCL or mandated by DWER for the minimisation of theses gases other than CCL optimising process controls.
3.4 Regulation of hydrogen fluoride
Under condition 13 (tables 7 and 8) of its licence conditions CCL is merely required to monitor and report hydrogen fluoride emissions on an annual basis.
There are no mandated requirements under the proposed licence conditions for CCL to implement improvements to its operations to reduce its output of hydrogen fluoride and other fluoride compounds.
In the year ending 30 June 2017, CCL self-reported that the factory generated 480 kg of fluoride compounds.
CCL dredges shell sand from Cockburn Sound and seawater is thereby potentially introduced into the slurry of raw material used by CCL at the factory. Seawater contains fluorine. Seawater fluoride levels are usually in the range of 0.86 to 1.4 mg/L, and average 1.1 mg/L (milligrams per litre.
CCL could reduce emissions of fluorine and its compounds by:
(a) converting to 100% gas fired kilns;
(b) mandating more rigorous process monitoring and controls, such as washing sand shell in clean filtered water to remove as much seawater as is technically possible.
4.0 Polychlorinated dioxins and furans
Dioxins (a family of 75 compounds) are highly toxic, environmentally persistent compounds which are generated by various industrial processes. Dioxins are a varied class of compounds of various toxicity, therefore toxic equivalence factors (TEF) have been derived to facilitate risk assessment based on the most toxic of these substances. Given they are persistent environmental pollutants, dioxins tend to accumulate in the food chain and the majority of human exposure to dioxins is through food.
Furan is a colourless, flammable, highly volatile liquid with a boiling point close to room temperature. The furans are a family of 135 compounds.
4.1 Adverse effects of dioxins and furans
Dioxins are highly toxic and considered endocrine disrupters. They may cause reproductive and developmental problems, damage the immune system, interfere with hormones and cause cancer.
Furan is toxic and may be carcinogenic in humans.
4.2 Source of dioxins and furans
Raw materials or fuels that contain chlorides may potentially cause the formation of dioxins and furans when exposed to a particular range of temperatures. Therefore dioxins and furans may be generated in the lime kilns and emitted by the kiln stacks.
Dioxins and furans are byproducts of manufacture and incomplete combustion.
4.3 Detection of dioxins and furans
DWER states that the results of monitoring in 2015 indicated that dioxin and furan emissions from kiln stacks at the Premises were O.25% and 4.5% of the 24 hour assessment criteria (World Health Organisation, 2000) in the first and third quarters respectively.
4.4 Regulation of dioxins and furans
CCL does not presently use any specific controls to minimise the potential for generation of dioxins and furans. The formation of these compounds is typically controlled by CCL by managing the chlorine content of fuels and minimising the residence of kiln gases in the temperature range where these substances are formed.
No specific controls are contained in the proposed conditions on its licence.
In the year ending 30 June 2017, 100,000 micrograms of dioxins and furans were produced at the Premises.
Emissions of these highly toxic pollutants may be reduced by reducing the amount of common salt (sodium chloride) entering the process by washing the shell sand in fresh filtered water before it enters the production process and by changing to burning natural gas to provide better kiln temperature control.