Month: October 2019

Happy Diwali (Deepavali)!

No doubt Diwali will be celebrated across the world, as are many important events on the calendar, through the setting off of lots of fireworks. The spectacles produced are brilliant, of course ~ but they are costly, and not only in terms of the cost of the fireworks and the impacts on our pets. Fireworks are also highly polluting and have the potential to impact negatively environmental quality and our health.

Aside from the littering caused by all those spent fireworks – no surprises there, what goes up has to come down – ever wondered what all those bright colours are formed from? They are formed from the high temperature combustion of compounds containing heavy metals (“heavy metal salts”). Sparkling green colours are produced by barium chloride, blue is produced by copper chloride. Strontium carbonate is used to produce red fireworks, calcium chloride ~ orange fireworks, sodium nitrate ~ yellow fireworks. Purple fireworks are typically produced by use of a mixture of strontium (red) and copper (blue) compounds. The list goes on and on ….

Combustion also yields other pollutants, notably fine particulate matter (including PM10 and PM2.5, but no doubt even finer particles too), sulfur dioxide (SO2), persistent organic pollutants (PoP) polycyclic aromatic hydrocarbons (PAHs) and highly toxic dioxins. None of these are good for us. And that is not all, of course we have developed fireworks that make louder bangs and travel to higher altitudes in the sky. This is all based on chemistry and chemical reactions, but also involves some very old technology – gunpowder, which is believed to have been invented in China over 1000 years ago! Thus as Licudine et al. (2012) reported in the journal Public Health Reports, based on their study of air pollution linked to new year firework celebrations on Hawaii (see paper linked below), “chlorates or perchlorates can be used to achieve noise levels equivalent to trinitrotoluene and result in more violent explosions than traditional nitrates … Lead (Pb) salts are widely used as igniters to initiate fireworks explosions. Manganese (Mn) and Mn dioxide serve as fuel and oxidizer for brighter lights, chromium (Cr) is used as a burn rate catalyst for propellants,and nickel (Ni) acts as an electric firing device for fireworks.” The health effects of heavy metals are well-known, and many of the emissions from fireworks persist in the environment long after the spectacle of the display is over. The authors go on to state that “perchlorates have been associated with thyroid problems, and toxic byproducts (e.g., dioxins) could be produced as a result of atmospheric reactions between metal oxides and organic fuels.”

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Licudine et al. (2012) is not the only study on fireworks as a source of environmental pollution. In fact there have been many such studies. One of these investigated air quality in Delhi, India, during the Diwali celebrations. Delhi is already one of the world’s most polluted cities, particularly during the Northern Hemisphere autumn and winter months (which is when Diwali takes place) when local weather conditions and the burning of fossil fuels and biomass for heat, transport and cooking conspire to produce some of the poorest air qualities ever recorded globally. The study by Peshin et al (2017 – and see link below to the paper) recorded substantial increases in SO2, nitrogen dioxide (NO2) – a greenhouse gas and cause of environmental acidification, ozone (O3), fine particulate matter (including black carbon, or soot) and trace metals during firework displays associated with Diwali celebrations.

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Similar findings have also been reported for Jamshedpur in the east Indian state of Jharkhand, suggesting that firework-related pollution is a widespread problem in India during Diwali celebrations (Ambade, B. The air pollution during Diwali festival by the burning of fireworks in Jamshedpur city, India. Urban Climate 26, 149-160). The setting-off of firecrackers is highlighted in this article as a particularly rich source of pollution, as it is here (for Delhi) and here (for China).

An even more recently published article – just out in the Journal of Cleaner Production, emphasises that “[r]ecreational fireworks use causes some of the most extreme urban particulate matter pollution: Hourly peaks over 1000 ug/m3 PM10 have been measured during the Chinese New Year and Indian Diwali festivals …. [f]ireworks plumes can be detected over a long range, between regions and countries, in the form of elevated particulate matter (PM10 and PM2.5) and water-soluble potassium … [i]n Western Europe, fireworks celebrations have contributed to significant annual atmospheric metal emissions, to the urban background of trace metals, and to a localized perchlorate pollution in surface and groundwater” (Andradottir and Thorsteinsson, 2019). Unfortunately this article is not available for public download, but it is accessible via NUS’s excellent library in digital form: Andradottir, H.O. and Thorsteinsson, T. (2019) Repeated extreme particulate matter episodes due to fireworks in Iceland and stakeholders’ response. Journal of Cleaner Production, 236, 11711.

One of the points raised by Andradottir and Thorsteinsson (2019) is the “passiveness” of the general public when it comes to the pollution and health risks of firework displays. The authors of the paper claim that this in part stems from a lack of awareness of the link to pollution. The authors argue that the general public should be made more aware and that the purchasing of less environmentally damaging fireworks should be encouraged (for example, Disney uses fireworks that are propelled by compressed air rather than gunpowder – why cannot others follow suit?).

We need also to be mindful of the costs of producing and transporting fireworks to their point of use, and the risks posed to those involved in their manufacture. An estimated 90% of the world’s fireworks are manufactured in China – often in rural areas, with women predominantly involved in actually making the fireworks, handling dangerous chemicals with little formal training. Accidents happen, often with lethal consequences – as is evident from the webpage linked here. Accidents are also commonplace in Sivakasi, the city in Tamil Nadu that is commonly regarded as India’s “fireworks capital“. Whoever thinks about the conditions fireworks are produced under, and what health-threatening substances and practices those involved in the manufacture of fireworks are exposed to, when purchasing fireworks or going along to a display? Do we really think that those toxic substances used in manufacturing never leak out into the environment even before the fireworks are used? And what about all that packaging that comes with fireworks – where does that all end up?

It could be argued that what we are actually celebrating through our firework displays is our reckless disregard for our environment, for the economically marginalised and, ultimately, for ourselves.

By now Environmental Pollution students at NUS are probably either bored or confused by my seemingly constant references to pH, acid deposition, acidification and their role in environmental pollution and its effects. The truth is, pH, and more particularly variations in pH, has a major part to play in discussions concerning environmental pollution; changes in pH can be an effect (a result) of pollution. Moreover, pH variations can influence the amount of human and ecosystem harm caused by other chemicals in the environment, such as heavy metals, but also impact the availability of nutrients essential to the fertility of soil and hence to plant growth and crop productivity. Already in GE3246 we have discussed acid deposition – its sources and effects. A major source is air pollution in the form of carbon, sulfur and nitrogen oxides [CO₂, SO₂ & NO] released from power stations etc. Ammonia (‎NH₃), associated with traffic pollution and the misuse of fertliizer, is also a source of acidification pressure. These gases combine with moisture in the atmosphere to form acid and when deposited go on to cause acidification of lakes and rivers and the ocean. In the lecture this coming week we will add the acidification of soils and its effects to this list ….

Environmental acidification occurs naturally, of course, particularly where the underlying geology is base-poor. Humans have through their activities made the situation far worse, however, by causing anthropogenic (or cultural) acidification.

So what is pH and how is it linked to environmental acidification and anthropogenic acidification in particular?

The Danish scientist S. P .L. Sørensen first introduced the term pH (though he denoted it as p_H) to mean the amount (or power) of hydrogen (H⁺) ions (protons) in a solution. If a solution (e.g. lake or ocean water, or even the water between individual particles of soil, known as soil pore water) becomes more or less acidic, the concentration of H⁺ ions becomes stronger or weaker. Acidity (or its converse alkalinity) is the amount of hydrogen and hydroxide (OH^–) ions present in solution, or relative concentrations of these. As acidity increases, the amount of H⁺ ions increases while levels of OH^– ions decline. The table below shows the reciprocal relationship between H⁺  and OH^– ions.

Note that the pH scale ranges from 0 to 14.  Solutions with a pH less than 7 are generally referred to as acidic, while those with a pH greater than 7 are basic or alkaline. A pH of 7.0 is taken to be neutral, because the H⁺ and OH^– ions balance one another. It is perhaps worth pointing out that temperature directly effects pH. An increase in temperature causes ionisation to proceed at a higher rate than at lower temperature, causing more H ions to be freed from water molecules ( H2O ⇌ 2H⁺ + OH^– ). It is also worth pointing out that pH is the negative log of the molar hydrogen ion concentration (-log₁₀[H⁺], or [H⁺] = 10^-pH). What that means in English is that as pH falls, acidity increases, and a pH fall of 1.0 unit represents a 10x increase in acidity (or 10 x more H⁺ ions)!

So how is pH linked to anthropogenic acidification and its environmental effects, such as coral and forest death?

Hydrogen ions are highly positively charged (the ⁺ indicates that). Hence acids can be highly reactive and corrosive (ever spilt battery acid on your clothes?). OH^– is also highly reactive, hence strong alkaline solutions, such as bleach, are highly caustic (common bleach is Sodium hypochlorite, NaClO, composed of one sodium (Na) atom, one chlorine (Cl) atom and one oxygen (O) atom.). Heavy metals are also positively charged (positively charged atoms are known as cations – e.g. copper (Cu²⁺), magnesium (Mg²⁺), manganese (Mn²⁺),  lead (Pb²⁺), zinc (Zn²⁺)), in fact most inorganic contaminants are positively charged (or cations). Many nutrients that plants required (e.g. Potassium, K⁺, Calcium, Ca²⁺) are also cations. This sounds confusing, but some metals, including some heavy metals (copper, iron, zinc etc), are classed as nutrients at low concentrations (i.e. they are micro-nutrients) but are toxic at higher concentrations. As mentioned in an earlier lecture, the dose makes the poison (although hopefully everyone realises by now that this is a gross over-simplification).

Acidification has direct effects on biota. Generally however its effects are less direct, and take place through the effects on concentrations of heavy metals, water transparency, availability of nutrients, including calcium carbonate (CaCO3), the material for coral exoskeletons. The infografic below shows how key aquatic organisms may be lost as the pH of their habitat becomes more acidic.

Acidification impacts soils through changing the availability of chemical elements, some of which can be harmful to biota and have negative impacts on agricultural productivity. Soil particles, organic matter etc, tend to be negatively charged – and therefore they can hold (adsorb) cations on their surface (when something is adsorbed on a surface it is basically adhered, or stuck/glued, to the surface). Soils differ in this ability – known as Cation Exchange Capacity (CEC), depending on their texture (e.g. proportion of clay, silt and sand sized particles, amount of organic matter). Generally  organic-rich, finely textured soils have have high CEC – they are sticky as far as nutrients and other cations go – and are therefore often relatively “fertile”, and good for agriculture. Coarse-grained (with a high proportion of sand-sized particles) soils with low organic matter content tend to have low CEC, and any nutrients present may be easily lost to leaching and flooding of the soil. The schema below shows how the finest plant roots (root hairs) interact with surrounding soil particles and soil pore water, and the cations attached to negatively-charged soil particles.

Note that in order to obtain essential nutrients (cations) from soil a plant must pump out H⁺ ions. These H⁺ ions are swapped for the cations (such as K⁺ and Ca²⁺). For an excellent, short video on the Cation Exchange process between plants and soil/soil pore water (and the influence of soil texture) – see here. More on the influence of soil texture is available via the short video linked here.

Interestingly, the video explaining Cation Exchange linked above states that the vast majority of cultivated soils are negatively charged but some soils, mostly in the tropics, are positively charged. We’re in the tropics – so which soils are positively charged? The answer is those soils that are ancient and that have been subjected to intense and deep weathering over a long period of time. As a result of prolonged, intense weathering clay minerals disintegrate, losing their silicon (Si) in the process. As a result, the weathered soil has a lower negative charge (and may even have a positive charge), and thus a lower CEC. This reduced CEC is one of the reasons why lateritic soils in the tropics are less fertile than their younger, less intensively weathered counterparts in more temperate latitudes.

Increased acidity (increased concentration of H⁺ ions) results in many more H⁺ ions in the soil pore water competing with dissolved cations for attachment sites on soil particles. Because the H⁺ ions are generally more reactive they tend to attach to vacant attachment sites on soil particles and displace already attached cations of, for example, heavy metals. The latter are then dissolved in the soil pore water where they are much more biologically available, and can be taken up by plants through their roots. In solution, heavy metals such as Aluminium (Al) bind with phosphorus fertilizers (generally in the form of Phosphate, PO₄), forming – for example, AlPO₄, which is a form of phosphate that plants cannot use (cannot take up). Hence fertilizer applications to acid soils are often ineffective, and farmers must first find a way of neutralising the acidity (generally by liming, the application of quicklime, CaO).

The pH of solution also influences solubility of heavy metals. Generally heavy metals are in solution in acidic water. At higher pHs (strongly alkaline), the OH^– ions bind with the heavy metal cations forming solid compounds, which precipitate-out (they form “precipitates”). Varying the pH of wastewater, reservoir water etc entering water treatment plants is the main way of removing heavy metals from large volumes of water that are then used for human consumption, irrigation etc., as mentioned in an earlier lecture.

I’ve been enjoying reading my copy of Eleanor Herman’s excellent book “The Royal Art of Poison: Filthy Palaces, Fatal Cosmetics, Deadly Medicine, and Murder Most Foul“, a review of which can be found here. Chapter 3 “Dying to be Beautiful  Dangerous Cosmetics” has been particularly fascinating, in part because in addition to some rather startling revelations about the lengths people went to in the past to make themselves what they and others at the time considered beautiful, and then stay beautiful, the chapter also raised some questions that are relevant to GE3246. One of these is whether we are any more knowledgeable now about the true personal and wider costs of our luxury consumption. Luxury consumption is geared to meeting our wants, rather than our needs. Luxury consumption is largely avoidable (it is not necessary) – but it also involves the use of valuable resources (including energy, water etc) in their production and transport, thereby denying others of those resources, and generates pollution. Everything we consume causes pollution- it comes with embodied pollution, in other words. In some cases, our luxury consumption actually does us harm. Certainly the problems it causes – often in distant parts of the world – can end up causing food insecurity, water shortages, harmful pollution etc for others. But more about all that later in GE3246 ….

Back to The Royal Art of Poison. You can actually view a short and very enjoyable video summary of Chapter 3 of Eleanor Herman’s book here. I enjoyed the account (in the book) of how Queen Elizabeth the First (QE 1), who died at what was then the ripe old age of sixty-nine in 1603, had led a generally healthy life, at least according to standards at the time. For a member of royalty, she ate healthily and exercised often ~ she was, apparently, fearful of ending up like her father, the morbidly obese King Henry VIII. Unfortunately QE 1 contracted smallpox during her 20s, and this left scars on her body and face. Not only were blemishes considered unattractive at the time, they were also considered “proof of God’s displeasure” – even manifestations of sexual urges and desires. QE 1 seems to have been so-encouraged to apply, liberally, a ceruse, a pigment that contained highly poisonous white lead and often arsenic too, to cover her blemishes. Unfortunately the lead leached into the body through the skin, and this is thought to have caused QE 1 to lose her hair, become less active (lead poisoning causes muscle paralysis) and to suffer declining metal acuity and major swings in her mood. It also likely corroded her skin, causing QE 1 to have to apply even more ceruse, thus kick-starting a positive cause-effect-cause cycle involving ever thicker applications of ceruse. Herman argues that rather than simply aging, heavy metal poisoning may have contributed to mood swings, odd decisions (such as to have her friend Robert Devereux executed) and depression that characterised the last years of QE 1’s life, and ultimately her death.

Herman describes other cases, a notable one of which is that of Diane de Poitiers, the mistress of French King Henri II, who died in 1566. De Poitiers was commonly regarded as one of the most beautiful women of her time. She went to extraordinary lengths to stay youthful looking, including bathing in assess’ milk, to remove body hair and prevent the signs of aging, and taking an elixir that was meant to promote a youthful complexion. The elexir contained gold – and gave a person who drunk it a white skin because the gold caused anemia. Gold is a heavy metal and anemia can be caused by heavy metal poisoning. The elixir that De Poitiers took was meant to be used sparingly ~ no more than once a month (even back in the 16th century people knew that excessive use was not good for you), but it is thought that De Poitiers took the elixir once a day over many years. She accumulated so much gold from the elixir that when her remains were discovered centuries later the soil in which she had been buried was heavily contaminated with gold that had leached from her body as it decayed!

Of course, we’re much more mindful consumers these days – aren’t we? I am not sure that we are. We still use urine in face creams (pee is a great moisturiser, apparently) just as folk did in the 16th century, and heavy metals (e.g. titanium dioxide) in sunscreens and other cosmetics. And botox injections are popular. These involve injecting a toxin produced by the gram positive bacterium Clostridium botulinum. The same toxin causes the potentially fatal illness Botulism.  Botulism through normal routes (e.g. food poisoning – especially from eating fish that has not been properly stored or cured/fermented and canned foods that have “gone off”) is now relatively rare. Although we are told that the cosmetic use of botox is generally safe, because of the relatively low concentrations used, different people are likely to have different levels of sensitivity, and deaths do occur (including one in Singapore earlier this year – see here).

For an excellent account of current cosmetic use – and the toxins involved, many linked to petrochemicals – see the short video here. The video “examines the pervasive use of toxic chemicals in our everyday personal care products, from lipstick to baby shampoo” and is by The Story of Stuff Project, a project dedicated to mindful consumerism and de-materialisation.

Perhaps if we are willing to risk our own health through our luxury consumption we shouldn’t be surprised that we are also willing – at the same time – to risk the health of our planet.

A more mindful approach to consumerism would seem to be needed – perhaps urgently. There is now guidance out there to help us to be more mindful, or literate, consumers. See, for example, the Campaign for Safe Cosmetics webpage.

Several news agencies are today reporting research that appears to suggest that, in addition to everything else, air pollution may cause (or contribute to) baldness. More precisely it seems that fine particular matter in the air that we breathe may cause hair loss. One article goes further and suggests that men living near busy roads are particularly vulnerable!

The American Association for the Advancement of Science (AAAS) is also reporting the finding through its EurekAlert! website ~ see here.

The research described was presented at the 28th EADV Congress in Spain earlier this week and found that fine particulate material in the air can interfere with a body’s production of proteins (β-catenin, cyclin D1, cyclin E and CDK2) that are responsible for hair growth and hair retention.

The lead researcher on the study, Dr Hyuk Chul Kwon (Future Science Research Centre, Republic of Korea) opined “[w]hile the link between air pollution and serious diseases such as cancer, COPD [Chronic obstructive pulmonary disease] and CVD [Cardiovascular disease] are well established there is little to no research on the effect of particular matter exposure on the human skin and hair in particular. Our research explains the mode of action of air pollutants on human follicle dermal papilla cells, showing how the most common air pollutants lead to hair loss”.