Mercury, fish and gold miners

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mercure poissons - poissons - mercury - mercury fish

Mercury is a good example of the difficulties in assessing and managing an environmental health risk. The presence of this metal in the food chain has a demonstrated potential risk, which must be weighed against the benefits of consuming certain foods such as fish. The history of mercury and its health effects, often marked by dramatic events, has illustrated progress in environmental health for decades.

1. Mercury

paracelse - paracelsus
Figure 1. Paracelsus (1493-1541), by Quentin Metsys. [Source: After Quentin Matsys [Public domain], via Wikimedia Commons.]
Mercury, a silvery-white, shiny, dense and mobile metal, has long been called for all these reasons Quicksilver. Its chemical symbol Hg comes from its Latin name “hydrargyrum“; the word hydrargyrism is still sometimes used to describe mercury poisoning. The word “mercury” appeared in the 17th century. Professional mercury poisoning was registered on the French Occupational Disease Registry as early as 1919. In Nature, mercury is combined with sulphur to form mercury sulphide, the “cinnabar”; it is in this form that it is still exploited in Spain, Algeria and China. In France, most of the mercury used comes from waste reprocessing.

Mercury exists schematically in different forms: elemental mercury or metal mercury, inorganic mercury salts and organic mercury [1]. It is the properties of mercury metal that have long made mercury successful in the industry. Relatively chemically inert, the only metal that is liquid and volatile at room temperature, it is capable of dissolving many metals to form amalgams [2].

syphilis mercure moyen age - syphylis middle ages
Figure 2. Syphilis: application of mercury ointment in the Middle Ages. [Source: By Bartholomäus Steber [Public domain], via Wikimedia Commons.]
It is impossible not to associate Mercury to Paracelsus, a famous doctor and alchemist of the Middle Ages, a rebel of his time since he burnt the writings of Hippocrates and Galen in public places (Figure 1).

“Inventor” of Occupational Medicine by observing pulmonary pathologies in miners, he was the first to introduce mercury into therapy, particularly in the treatment of syphilis (Figure 2). When he noticed the many adverse effects of mercury, he had this phrase that has remained famous in toxicology: “it is the dose that makes the poison”. And the popular saying was then “a night with Venus, a life with Mercury”!

1.1. Mercury metal

The toxicity of mercury metal to humans comes from its high volatility at room temperature, it is the “vapour” risk. This is why any presence of metal mercury in “broad public” devices (thermometer, barometer, etc.) was banned in France in 1999. This is why no more high school student sees his teacher arriving with a few mercury balls rolled in his hand (Figure 3): the older ones could remember this. Ingested, metal mercury does not pass through the digestive barrier and therefore is not absorbed into the body. In other words, mercury in this form no longer represents a public health issue. But metal mercury will still be present in this article.

bille mercure metal - metal mercury ball
Figure 3. A metal mercury ball. [Source: By А [Public domain], from Wikimedia Commons.]
chapelier fou - mad hatter
Figure 4. The mad hatter. [Source: John Tenniel [Public domain], via Wikimedia Commons.]
About metal mercury: toxicology is full of stories, anecdotes and references to the literature. Lewis Carroll’s “Alice in Wonderland” is an example. You probably know the mad hatter (Figure 4) in this story? And you may know the English expression “mad as a hatter“? In fact, Lewis Caroll simply observed very well what was happening around him in industrial England at the end of the 19th century. Hat manufacturers used mercury that they heated to make and polish the felt on the hats. Inhalation of mercury vapours could lead to behavioural problems. Hence the idea for Lewis Carroll to choose this crazy character in this famous adventure.

1.2. Inorganic mercury

Again and apart from a few individual accidents, there is no real public health issue with this form of mercury. It is still encountered as inorganic mercury salts in some laboratories, in some button cells, but nothing very important for human health. But this does not prevent the active search for substitutes for certain industrial products such as button batteries, for example.

1.3. Organic mercury

The main issue of mercury lies here, in the general population [3],[4]! As we will see in details, it is this organic mercury to which humans are often exposed through their diet. In an almost “unstoppable” and unfortunately almost “definitive” way, for which man is largely responsible. Until 1989, organic mercury was used as a fungicide to destroy microscopic fungi present in cereals in particular: we will see the dramatic consequences. Toxic to the central nervous system, it has caused serious neurological complications in exposed individuals. As the problem is now well identified, surveillance systems for exposed populations have been set up by Santé Publique France [5] and health recommendations are regularly published by ANSES [6].

2. Organic mercury, a public health issue

A few dramatic events have marked the history of organic mercury and played an essential role in a better understanding of its toxicity and its incorporation into the food chain.

2.1. Minamata Bay

A real police thriller took place in the 1950s in Japan. The story begins with the appearance of severe neurological pathologies in fishing families living along the bay. What we would call today “clusters” of patients, i.e. patients who are well grouped in the same region.

Adults had severe paralysis, neuropsychic disorders; many children had severe malformations with very disabling neurological and psychological disorders, if not stillborn. These facts took place over several years and despite many expert opinions, the mystery remained total! The final toll will be about 600 dead and 3,000 sick! At that time, epidemiology was still a nascent science and toxicological analyses of biological fluids (blood, urine, etc.) were still quite rudimentary. We must imagine this region of Japan affected for several years by a mysterious disease whose cause no one understands.

A few clues will gradually be identified, two in particular: these families feed mainly on fishery products and the very large chemical company Chisso, which uses mercury as a catalyst for certain chemical syntheses, regularly discharges its effluents into the waters of this Pacific Bay.

As the story goes, toxicologists from Scotland found out what was going on eventually. How? First, they looked through all the patients’ medical records to find possible commonalities. Their conclusion: the pathologies described were similar to what was then known about the toxicity of organic mercury. However, the Chisso plant mostly dumped metal mercury into the Pacific! As we have seen, only the vapours of mercury metal are toxic to humans and it does not pass through the digestive barrier when ingested. The mystery persisted for some time.

Stubbornly, the experts ended up making the link between the Chisso factory, which they suspected of playing a role in this “epidemic”, and the pathologies presented by the fishing families.

methyl mercury - food chain
Figure 5. Methyl mercury and the food chain. [Source: By Lamiot (CC BY-SA 3.0), from Wikimedia Commons.]
A crucial step in understanding the entry of organic mercury into the food chain was then discovered: Hg, the metal mercury present in water, “methylated” by marine micro-organisms becomes CH3Hg ! A CH3 methyl radical was added to the metal mercury spilled by the plant [7]. It was the phenomenon known as “biomethylation” of mercury that was then highlighted. Metal mercury becomes organic mercury which once ingested is quickly and well absorbed by the body!

Another phenomenon now well known in environmental health was also highlighted, bioaccumulation. Mercury is a “cumulative” toxic that accumulates in organisms over time: the older the fish or mammal, the higher its organic mercury content. Another phenomenon has been described, bioamplification: large fish eat small fish, organic mercury accumulates throughout the food chain to humans: being at the end of the chain, humans then receive the maximum dose of organic mercury when they eat swordfish, tuna and halibut for example. Or other large fish (Figure 5).

memorial minamata japon
Figure 6. The Minamata Memorial. [Source: Quirkyjazz via Flickr (CreativeCommons BY-NC-ND 2.0)].
It was only in 2010, half a century later, that the survivors of this dramatic case, often suffering from major disabilities, were finally compensated by the company Chisso and the Japanese State. A memorial representing, among other things, many metal mercury balls was built in Minamata (Figure 6).

2.2. Fishermen and ice cores

Intrigued by the history of Minamata Bay, some scientists asked themselves the following question: is it an isolated industrial accident? Or are the seas and oceans already polluted by mercury as a result of the industrial revolution that emerged at the end of the 19th century? First, it should be noted that mercury present in the mammalian body is partially eliminated by the appendages, i.e. hair and nails in humans, and feathers in birds. As it is usual to proceed in Science since Claude Bernard, these scientists put forward a hypothesis: the seas and oceans are not contaminated, it was an isolated industrial accident in Minamata.

balbuzard pecheur - grebe huppe - osprey - crested grebe
Figure 7. Osprey and crested grebe. For the Osprey. [Source: By NASA[Public domain], via Wikimedia Commons (left image); Luciano Giussani (CC BY 2.0), via Wikimedia Commons (right image)]
But how to prove it? They then had an idea that can be coined as brilliant: they analyzed the feathers of stuffed birds in natural history museums, especially fishing birds, such as osprey and crested grebe (Figure 7). The analysis of the birds feathers allowed to go back to the middle of the 19th century. Very bad news emerged: mercurial pollution of the seas and oceans has never stopped growing since the beginning of the industrial era. A recent study confirmed these results [8] : average concentrations of a few µg/g are measured in seabird feathers, and if the progression continues, they will reach the estimated danger level of about 20 µg/g in a few decades.

carottes glaciaires wyoming - mercury in wyoming's ice cores
Figure 8. Mercury in Wyoming’s ice cores. [Source: By US government[Public domain], via Wikimedia Commons.]
Other studies have focused on the study of mercury deposits caused by air pollution, in ice, at the poles in particular. One study examined a glacier in the mid-latitude American state of Wyoming [9]. The study of ice cores has largely confirmed human responsibility for this massive mercury pollution of the environment. Figure 8 shows the natural “background noise” in green (naturally occurring deposits), the volcanic activity of this State (in blue) and especially the activity of man, gold seekers (gold colour) and industrial activities (red) in particular. In this study, human activity is responsible for 70% of mercury emissions over the last 100 years. Mercury concentrations have decreased over the past 15 – 20 years as a result of different strategies to reduce mercury emissions.

More recently, it has been shown that permafrost (frozen ground in the northern hemisphere) contains huge amounts of mercury [10]; global warming may raise fears of a gradual release of this mercury.

2.3. A famine in Iraq

A terrible famine appeared in the Iraqi countryside in the 1970s. To help the populations, very large quantities of cereals were then distributed in bags, by the State and also by Associations (which were not yet called NGOs). Quite quickly, various neurological disorders appeared in these farmers and their families. We remember that methyl mercury was then used as a fungicide on cereals. Indeed, cereals had been treated with methyl mercury to use them as seeds but not for immediate consumption. However, on the bags, the inscriptions were labelled in English, a language of which these populations had no knowledge! It was therefore well after the consumption of these treated cereals that these intoxications appeared. Fortunately, almost 20 years after Minamata, the link was quickly established between methyl mercury and the pathologies presented by these populations. The final result was nevertheless dramatic, with nearly 650 deaths and 6,500 patients [11].

This tragedy nevertheless allowed progress to be made. The dose-response relationships of mercury have been better studied and since then hair toxicology has become a standard in the study of chronic heavy metal poisoning.

2.4. The Faroe Islands, Seychelles

In order to improve our understanding of human exposure to organic mercury and its toxicity, numerous studies are being conducted to monitor exposed populations and assess risks. For example, in the Indian Ocean, a monitoring of groups of children from the Faroe Islands and Seychelles was established in 1985 [12]. These populations, which consume a lot of fish, are indeed “good witnesses” of possible chronic exposure to low doses of methyl mercury. Thus, progress can be made thanks to these studies, including the use of fine cognitive tests to detect the smallest signs of toxicity or the determination of mercury in the cord blood from birth.

Nevertheless, it should be noted that these epidemiological studies, known as “cohort” studies, are extremely difficult. Many biases may occur throughout the study. For example, the fact that fish may unfortunately contain other pollutants or that other environmental factors may be present throughout the life of the subjects being monitored. It is therefore difficult to attribute all observations to mercury alone. This is a well-known and common fact in all targeted studies on the effects of the environment on human health.

3. Dental amalgams

carie dentaire - carie dent - dental caries
Figure 9. Amalgam and dental caries. [Source: By DRosenbach (Public domain), via Wikimedia Commons].
Dental amalgams are a sensitive subject that is very difficult to tackle without triggering passions! This property of mercury metal to amalgamate with other metals has long been used to form “fillings“, which have been used for a very long time to fill dental caries (Figure 9). Incidentally, they are misnamed because they do not contain lead but silver, zinc, tin and copper.

The mercury contained in these amalgams is believed to be responsible for various chronic diseases such as Alzheimer’s disease or multiple sclerosis. Mercury vapours can be inhaled and thus enter the body: chewing gum and bruxism [13] increase the risk of mercury vapours being released. To date, no national or international scientific expertise has been able to establish a formal relationship between the presence of amalgams in the mouth and these diseases.

But passions are strong as soon as we talk about it! However, we can regret some of the consequences: the business done in European countries where health professionals claim to cure patients by administering mercury chelating products at a high price. We will see below that it is very difficult to manage this type of risk that is not formally proven.

4. Mercury and gold panners

fleuve maroni guyanne - pollution mercure - maroni river french guiana - mercury pollution
Figure 10. The Maroni River in French Guiana, massively polluted by mercury. [Source: By Maurizio Alì (CC BY-SA 4.0), from Wikimedia Commons]
This is a “remake” of Minamata Bay and takes place in the largest French department, Guyana. Clandestine gold diggers, or “gold panners”, make extensive use of metal mercury to amalgamate gold nuggets that may be present in river water. They then heat the amalgam to recover the gold and each year some deaths occur as a result of the inhalation of mercury vapours.

But above all, the disaster associated with these gold panning practices lies in the fact that all the rivers in this large Amerindian zone are massively polluted by mercury metal (Figure 10). All populations in this area, which covers French Guiana, part of Brazil and Suriname, are exposed to methylmercury, with mercury metal from gold panners being transformed into methylmercury by aquatic micro-organisms. Santé Publique France, the health agency in charge of population monitoring, has long since set up population monitoring measures in this department and regularly communicates with ANSES on the risks of excessive fish consumption (see refs. [1] and [2]).

5. Mercury and risk management

Mercury is an excellent example of the difficulty of managing an environmental health risk. Risk management follows risk assessment.

Risk assessment is carried out by independent scientists: they make proposals based on the current state of knowledge and indicate the health risks of exposure to a particular toxic substance; they also usually propose exposure values that should not be exceeded.

Risk management is the responsibility of the decision-maker: it is the role in France of our health agencies, here the ANSES, and of our government ministers concerned with the subject. These decision-makers may or may not rely on the conclusions of scientific experts. We will take two examples.

  • What are the recommendations for fish consumption?
    The difficulty is compounded by the fact that fish can be contaminated with many pollutants other than mercury, PCBs and dioxins, among others. Risk management will always seek a balance between – you have to eat fish – and – be careful of the toxic substances contained in fish. We know the richness of fish in certain nutrients that are precious for health, such as Omega 3 from fatty fish. We also now know the main contaminants in fish and their health risks (PCBs, dioxins, heavy metals including mercury). The recommendations are then “protective” without being able to formally prove their value. The ANSES thus limits the consumption of fish by young children and pregnant women [14].
  • What about dental amalgams?
    They pose another problem, that of substitutes, in this case the resins most often used in dental surgery. Can it be shown to be completely safe? No, not definitely. Concerning the presence of mercury itself, the recent recommendations are again “protective”, according to the ANSM (Agence nationale de sécurité du médicament et des produits de santé) of the precautionary principle and despite the absence of proven risk according to all recent studies: avoid mercury amalgams in young children and pregnant women [15]. On the other hand, and to be complete, it should be pointed out that the use of mercury in dental offices has been subject to very strict regulations for many years, in particular to avoid the risk of repeated toxic inhalation by the dental surgeon and, more occasionally, by the patient. Recommendations for patients [16] and professionals [17] have been proposed by the ANSM [18].

The mismanaged use of a large number of heavy metals such as mercury, but also lead, arsenic or cadmium, has led to massive and sustainable pollution of the planet for centuries. Unfortunately, these metals all have proven harmful effects on human health.

Mercury represents a real public health issue, in the general population, in its organic form, methyl mercury in particular. As we have seen, it enters the food chain when eating seafood, especially fish. Let us also remember that we must eat fish, but not too much and not every day. Risk management is a difficult exercise when, as in this case, it is necessary to find a balance between what is good and what is bad.

Mercury metal is not to be outdone even if its ingestion does not pose any risk. The identification of the phenomenon of biomethylation in the marine environment has clearly shown that environmental pollution of mercury metal is responsible for the incorporation of organic mercury into the food chain.

The case of dental amalgams is also a good example of the difficulty of managing a risk. Which one exists? Which doesn’t exist? Rightly or wrongly, the precautionary principle will surely find many applications here (see focus The precautionary principle).

Finally, an international convention on mercury has recently been implemented by the United Nations Environment Programme, the Minamata Convention. Adopted in 2013 in Japan, it entered into force on 16 August 2017 [19]. Among its main provisions, the Minamata Convention provides, inter alia, for the prohibition of new mercury mines and the phasing out of existing mines, the elimination and phasing out of the use of mercury in a number of products and processes, the establishment of measures to control emissions of mercury into the atmosphere and its releases to water and land, and the control of the informal artisanal and small-scale gold mining sector. The Convention also addresses the issue of interim storage of mercury and its disposal once it has become waste, contaminated sites and health aspects.

A very interesting video highlights global mercury pollution and puts this convention in perspective [20] :

6. Messages to remember

  • Mercury is an excellent example of the difficulty of managing an environmental health risk that involves two steps:
    • Risk assessment is carried out by independent scientists: their proposals are based on the current state of knowledge; they indicate the health risks of exposure to a particular toxic substance; they also propose exposure values that should not be exceeded.
    • Risk management is the responsibility of the decision-maker: it is the role of the health agencies concerned by the subject. These decision-makers may or may not decide to rely on the conclusions of scientific experts.
  • The toxicity of mercury metal to humans comes from its high volatility at room temperature. Occupational mercury poisoning was registered on the French Occupational Disease Register as early as 1919.
    • Mercury represents a real public health issue, in its organic form, methyl mercury in particular.
    • The identification of the phenomenon of biomethylation in the marine environment has shown that environmental pollution of mercury metal is responsible for the incorporation of organic mercury into the food chain.
    • Mercury is a “cumulative” toxic that accumulates in organisms over time: it is called bioaccumulation.
    • Biomagnification is another important process in environmental health: organic mercury accumulates throughout the food chain to humans: being at the end of the chain, humans receive the maximum dose of organic mercury when they eat swordfish, tuna or halibut, for example.
    • Risk management will always seek a balance between – eating fish is good for your health – and – being careful about the toxic substances in fish.
  • The property of mercury metal to amalgamate with other metals has long been used to form “fillings” made to fill dental caries.
    • To date, no scientific expertise has been able to demonstrate any health risks potentially associated with the presence of dental amalgams.
    • The recommendations are “protective” in application – according to the National Agency for the Safety of Medicines and Health Products – of the precautionary principle.
    • The use of mercury in dental offices has been subject to very strict regulations for many years.
  • Clandestine gold miners use mercury to recover any gold that may be present in river water. As a result, the rivers where this practice exists (French Guiana, for example) are massively polluted by mercury, creating irreparable environmental damage. In addition, there are health risks for populations associated with excessive fish consumption.
  • The mismanaged use of a large number of heavy metals such as mercury, but also lead, arsenic or cadmium, has led to massive and sustainable pollution of the planet for centuries. Unfortunately, these metals all have proven harmful effects on human health.

 


Notes and references

Cover image. [Source: By Arnaud 25[CC BY-SA 3.0 (https://creativecommons.org/licenses/by-sa/3.0)], from Wikimedia Commons]

[1] Bensefa-Colas L, Andujar P, Descatha A (2011). Intoxication au mercure. La revue de Médecine Interne, 32 (7), pp.416-24.

[2] Assembly of heterogeneous elements. The word is most often used in chemistry to refer to a mercury alloy with other metals.

[3] In Environmental Health, a clear distinction is made between the population of professionals exposed to certain risks at the workplace and the general population, i.e. everyone outside the workplace.

[4] Clarkson TW (2002). The three modern faces of mercury. Environment Health Perspectives, 110 Suppl 1: 11-23.

[5] Santé Publique France : www.santepubliquefrance.fr

[6] YEARS. Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement et du travail. : www.anses.fr/fr

[7] Harada M (1995) Minamata Disease: Methylmercury poisoning in Japan caused by environmental pollution, Critical Reviews in Toxicology, 25:1, 1-24

[8] Bond AL, Hobson KA, Branfireun BA. 2015 Rapidly increasing methyl mercury in endangered ivory gull (Pagophila eburnea) feathers over a 130 year record. Procedings of the Royal Society of Biology, 282: 2015

[9] Schuster PF, Krabbenhoft DP, Naftz DL. 2001. Atmospheric mercury deposition during the last 270 years: a glacial ice core record of natural and anthropogenic sources. Environmental Science and Technology, 36, 2303-2310

[10] Shuster PF et al (2018). Permafrost stores a globally significant amount of mercury. Geophysical Research Letters, 45, 1-9

[11] Al-Tikriti K, Al-Mufti AW (1976). An outbreak of organomercury poisoning among Iraqi farmers. World Health Organization Bulletin. 53 Suppl:15-21

[12] Myers GJ, Davidson PW, Cox C and others (1995). Summary of the Seychelles child development study on the relationship of fetal methylmercury exposure to neurodevelopment. Neurotoxicology 16, 711-716.

[13] Repeated and unconscious tooth friction movements

[14] YEARS: Eating fish, benefits and risks. www.anses.fr/fr/content/manger-du-poisson-bénéfices-et-risques

[15] ANSM : Mercury in dental amalgams, data update, April 2015. http://ansm.sante.fr/content/download/76933/976017/version/1/file/ANSM_Report_Mercury-Amalgames-Dentaires_May-2015.pdf

[16] ANSM : http://ansm.sante.fr/var/ansm_site/storage/original/application/0b5892a526480ba401d0ccc3fd4ee0e2.pdf

[17] http://ansm.sante.fr/var/ansm_site/storage/original/original/application/7cacb0593aaa9f8ebd9b176c65ff98890.pdf

[18] ANSM : Agence nationale de sécurité du médicament et des produits de santé: http://ansm.sante.fr/

[19] Minamata Convention on Mercury: http://www.mercuryconvention.org/Portals/11/documents/Booklets/COP1%20version/Minamata-Convention-booklet-fr-full.pdf

[20] Make mercury history: https://youtu.be/guO7RbArWf4


The Encyclopedia of the Environment by the Association des Encyclopédies de l'Environnement et de l'Énergie (www.a3e.fr), contractually linked to the University of Grenoble Alpes and Grenoble INP, and sponsored by the French Academy of Sciences.

To cite this article: DANEL Vincent (August 16, 2019), Mercury, fish and gold miners, Encyclopedia of the Environment, Accessed November 21, 2024 [online ISSN 2555-0950] url : https://www.encyclopedie-environnement.org/en/health/mercury-fish-gold-miners/.

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汞、鱼和金矿

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mercure poissons - poissons - mercury - mercury fish

  汞很能体现评估和管理环境健康风险的难度。这种金属在食物链中的存在已被证实有潜在的风险,这必须与食用某些食物(比如鱼)的好处相权衡。通常以重大事件为标志的汞的历史及其对健康的影响,表明了几十年在环境健康方面取得的进步。

1. 汞

环境百科全书-汞、鱼和金矿-帕拉塞尔苏斯
图1. 帕拉塞尔苏斯(1493-1541),昆汀·梅特西著。
[资料来源: 昆汀·马西斯之后[公共领域], 通过维基共享资源.]

  汞是一种银白色、有光泽、密度大、可流动的金属,因此长期以来也被称为水银。它的化学符号Hg来自其拉丁名“hydrargyrum”;水银中毒这个词有时仍然用来形容汞中毒。“汞”一词出现在17世纪。早在1919年职业汞中毒就被录入法国职业病记录中。在自然界中,汞与硫结合形成硫化汞,即“朱砂”;它在西班牙、阿尔及利亚和中国仍然以这种形式被开采;而在法国,使用的大部分汞来自废料再加工。

  简单来讲,汞以不同形态存在:元素汞金属汞无机汞盐有机汞[1]。长期以来,汞金属的特性使得汞在业界取得了成功。汞的化学性质相对稳定,是唯一在室温下呈液态且易挥发的金属。它能够溶解许多金属来形成汞合金[2]

环境百科全书-汞、鱼和金矿-梅毒:水银药膏
图2. 梅毒:水银药膏在中世纪的应用。
[资料来源: 巴塞洛缪·斯特伯(Bartholomew Steber) [公共领域], 通过维基共享资源.]

  我们不能不把汞和中世纪著名医生和炼金术士——帕拉塞尔苏斯联系起来。自从他公开焚烧希波克拉底和盖伦的著作以来,他就是那个时代的叛逆者(图1)。

  他通过观察矿工的肺部病理开创了职业医学,是第一个将汞引入治疗的人,尤其是在梅毒的治疗中(图2)。当他注意到汞的许多负影响时,他说了这样一句话:“剂量决定毒性”,而这句话在毒理界一直很有名。当时关于梅毒流行这样一种说法——“一夜维纳斯,千夜汞相随”!

1.1. 金属汞

  金属汞对人体的毒性来自于其在室温下的高挥发性,即“蒸汽”风险。这就是为什么1999年法国禁止在“大众”设备(如温度计、气压计等)中使用金属汞。这也是为什么高中生不再看到老师手里滚着几个水银球来上课(图3),年长的学生可能会对此记忆犹新。金属汞被摄入后不会通过消化道屏障,因此不会被身体吸收。换句话说,这种形式的汞不再是公共健康问题,但本文仍然会讨论金属汞。

环境百科全书-汞、鱼和金矿-金属汞球
图3. 一个金属汞球。
[资料来源: A [公共领域], 通过维基共享.]
环境百科全书-汞、鱼和金矿-疯帽匠
图4. 疯帽匠。
[资料来源: 约翰·坦尼尔(John Tenniel) [公共领域], 通过维基共享.]

  毒理学充满了关于金属汞的故事、轶事和参考文献。刘易斯·卡罗尔的《爱丽丝梦游仙境》便是一个例子。你可能知道这个故事中的疯帽匠(图4),也可能知道英语中“疯得像个帽匠”这样的表达。事实上,刘易斯·卡罗尔只是密切观察了19世纪末英国工业时期发生在他周围的事。帽子制造商用加热的水银来制作和抛光帽子上的毛毡。吸入汞蒸汽会导致行为问题,因此刘易斯·卡罗尔决定在这个著名的冒险故事中引入这个疯狂的角色。

1.2. 无机汞

  除个别事故外,无机汞并不存在真正的公共健康问题。在一些实验室或纽扣电池中,仍然存在无机汞盐,但它对人体健康并没有严重的影响。然而,这并不妨碍人们积极寻找某些工业产品(如纽扣电池)的替代品。

1.3. 有机汞

  对于普通人群,汞的问题主要就在于有机汞[3] [4]。人们通过饮食经常接触到的正是有机汞,而人类对此负有不可推卸的责任。1989年之前,人们将有机汞用作为杀真菌剂,来杀灭谷物中微小的真菌(后面我们将看到因此带来的严重后果)。有机汞会使中枢神经系统中毒,因此它在被暴露的个体中引发了严重的神经系统并发症。现在人们已经认识到了这个问题,法国公共卫生部建立了针对暴露人群的监督体系[5],并由法国国家食品环境及劳动卫生署定期发布健康建议[6]

2. 有机汞,一个公共健康问题

  一些重大事件标志着有机汞的历史,同时也帮助我们更好地理解汞的毒性及其进入食物链的途径。

2.1. 水俣湾

  一部真实的刑侦惊悚片发生在20世纪50年代的日本。故事从生活在海湾沿岸的渔民家庭出现严重的神经系统疾病开始。这是一起我们今天所说的“聚集性”病例,即病例都出现在同一区域内。

  成年人有严重的瘫痪、神经精神障碍;许多儿童患有严重畸形,即使不是死胎,也患有严重的神经和心理障碍。这些真实案例持续了很多年,尽管专家给出了许多意见,这个谜团一直没有解开!最终有600人死亡,患病人数达3000人。当时,流行病学还是一门新兴科学,对生物体液(血液、尿液等)的毒理学分析仍然相当不成熟。我们可以想象日本的这个地区几年来一直受到一种神秘疾病的困扰,但病因却无人知晓。

  一些线索渐渐显露,其中有两个特别的地方:一是这些家庭主要以海产品为食,二是当地一家大型化学公司——窒素公司,使用汞作为某些化学合成的催化剂,并定期将废水排放到这片太平洋海湾的水域。

  随着故事的发展,来自苏格兰的毒理学家最终发现了事情的真相。他是怎么发现的呢?首先,他们查看了所有病人的病历,寻找可能的共同点。他们得出的结论是:所描述的病理与当时已知的有机汞的毒性相似。然而,窒素公司的工厂向太平洋大量排放的是金属汞。如我们之前所了解的,只有汞金属蒸汽对人体有毒,且摄入后的汞不会通过消化道屏障。这个谜持续了一段时间。

  专家们最终还是怀疑窒素公司的工厂与这场“流行病”和渔民的病状有关系。

环境百科全书-汞、鱼和金矿-甲基汞和食物链
图5. 甲基汞和食物链。
[资料来源: 拉米奥(Lamiot) (CC BY-SA 3.0), 通过维基共享资源.]
(译者注:volcanoes geysers 火山间歇泉;industry 工业;mines, garbage dumps 矿山、垃圾场;old ammunitions 废旧的军火弹药;methylmercure 甲基汞;food chain 食物链;krill 磷
虾;mercury amount 汞量)

  随后人们发现了有机汞进入食物链的关键一步:存在于水中的金属汞被海洋微生物“甲基化”后变成了甲基汞!也就是说,工厂排放的金属汞被加上了一个甲基自由基[7]。这一被称为“生物甲基化”的现象随后备受关注。金属汞变成了有机汞,一旦被摄入体内,就会被迅速且充分吸收!

  另一个在环境健康领域广为人知的现象是生物累积。汞是一种具有“累积性”的有毒物质,它会随时间推移在生物体内积累:鱼或哺乳动物的年龄越大,其体内累积的有机汞含量越高。人们还发现了另一种现象——生物放大,即大鱼吃小鱼。由于人类处在食物链顶端,有机汞通过食物链最后在人体内积累。所以,当人类食用旗鱼、金枪鱼和大比目鱼时会获取最大剂量的有机汞;食用其它大型鱼类同样如此(图5)。

环境百科全书-汞、鱼和金矿-水俣纪念碑
图6. 水俣纪念碑。
[资料来源: Quirkyjazz via Flickr (CreativeCommons BY-NC-ND 2.0)

  直到半个世纪后的2010年,这一重大事件的幸存者(大多患有严重残疾)才最终得到窒素公司和日本政府的赔偿。水俣县建造了一座纪念碑,还放置了许多金属汞球(图6)。

2.2. 渔民和冰芯

  被水俣湾事件所启发,一些科学家不禁要问自己这样一个问题:这是一起孤立的工业事故吗?还是自19世纪末工业革命以来,海洋已经被汞污染了?首先,值得注意的是,哺乳动物体内的汞会被附属物(如人类的头发和指甲,鸟类的羽毛)部分清除。正如自克劳德·伯纳德以来,科学的推进往往需要实验验证,科学家们提出了一个假设:海洋没有被污染,水俣湾事件是一起孤立的工业事故。

环境百科全书-汞、鱼和金矿-鱼鹰和凤头鸊鷉
图7. 鱼鹰和凤头鸊鷉。关于鱼鹰。
[资料来源: 美国宇航局[公共领域],通过维基共享资源(左图);卢西亚诺·吉萨尼(Luciano
Giussani) (CC BY 2.0),通过维基共享资源(右图)]

  但是如何证明呢?科学家们想出了一个绝妙的主意:他们分析了自然历史博物馆中鸟类标本的羽毛,尤其是捕鱼鸟,如鱼鹰和凤头鸊鷉(图7)。对鸟类羽毛的分析可以回溯到19世纪中叶。坏消息是,自工业时代开始以来,海洋的汞污染从未停止增长。最近的一项研究证实了这些结果[8]:在海鸟羽毛中测得的汞平均浓度为几μg/g。如果继续发展下去,汞浓度将在几十年后达到约20 μg/g的危险水平。

环境百科全书-汞、鱼和金矿-怀俄明州冰芯中的汞
图8. 怀俄明州冰芯中的汞。
[资料来源:美国政府[公共领域],通过维基共享资源]
(译者注:Year (AD) 年(公元);Total Mercury (ng/L) 总汞量(ng/L);Mt St Helens (1980 AD) 圣海伦斯火山(1980 年);industrialization (circa 1880-present) 工业化(约1880年至今);WWII manufacturing(circa 1940-45AD) 第二次世界大战制造业(约1940-1945 年);Krakatau (1883 AD) 喀拉喀托火山(1883 年);Gold Rush(circa 1850-84 AD) 淘金热(约1850-1884 年);”unknown” “未知”;Tambora (1850 AD) 坦博拉火山(1850 年);Pre-industrial 工业化前)

  其他研究集中在由空气污染引起的汞沉积上,特别是在极地冰块中的汞沉积。一项研究调查了一座位于中纬度美国怀俄明州的冰川[9]。这项针对冰芯的研究基本证实了人类对环境中大规模汞污染负有责任。图8 中绿色代表自然的“背景噪音”(自然沉积),蓝色代表该州的火山活动,而金色代表人类活动(如淘金者),红色则代表工业活动。这项研究显示,在过去100年里,70%的汞排放是由人类活动造成的。由于采取了多种减少汞排放的手段,汞浓度在过去15-20年里有所下降。

  最近,有证据表明永冻层中(北半球的冻土)含有大量的汞[10];全球变暖可能会使这类汞逐渐释放,这会引起人们的担忧。

2.3. 伊拉克的饥荒

  20 世纪70年代,伊拉克农村出现了一场可怕的饥荒。为了帮助这些人民,国家和多个协会(尚未被称为非政府组织) 分发了大量袋装谷物。很快,这些农民及其家庭成员出现了各种神经系统疾病。当时甲基汞是被用作谷物的杀真菌剂。事实上,谷物经甲基汞处理后是被用作种子,而不能食用。然而,袋子上的标签是用英语标注的,当地居民对英语一无所知。因此,人们在食用了这些经过处理的谷物之后,出现了中毒症状。幸运的是,在水俣病出现约20年后,人们很快便发现了甲基汞与这些症状之间的关系。然而,最终结果还是令人震惊,近650人死亡,6500人患病[11]

  悲剧的发生使得科学不断进步。汞的剂量-反应关系得到了更好的研究,从那时起,毛发毒理学成为研究慢性重金属中毒的一个标准。

2.4. 法罗群岛和塞舌尔

  为增进我们对人类有机汞暴露及其毒性的认识,大量针对暴露人群及风险评估的研究正在进行当中。例如,在印度洋海域,自1985年设立了一个针对法罗群岛和塞舌尔儿童群体的监测项目[12]。这些儿童食用大量鱼类,是潜在的长期接触低剂量甲基汞的“良好见证者”。这些研究取得了一定进展,包括使用精细的认知测试来检测最微小的毒性迹象,或测定出生时脐带血中的汞含量。

  然而,需要注意的是,这些被称为定群研究的流行病学研究极其困难。在整个研究过程中,可能会出现许多偏差。例如,鱼类可能含有其他污染物,或者被监测对象的生活中可能存在其他环境因素。因此,我们很难将所有的观测结果仅归因于汞。在所有关于环境对人类健康影响的目标性研究中,这是一个众所周知的普遍事实。

3. 牙科汞合金

环境百科全书-汞、鱼和金矿-汞合金和龋齿
图9. 汞合金和龋齿。
[资料来源: 德罗森巴赫(DRosenbach) [公共领域],通过维基共享资源]

  牙科汞合金是一个敏感话题,我们很难平心静气地讨论它。由于金属汞可以与其他金属混合,它长期以来被用作“填充物”来填充龋齿(图9)。顺便说一句,它们之所以被误称,是因为它们不含铅,而含有银、锌、锡和铜。

  这些合金中所含的汞被认为是各种慢性疾病的罪魁祸首,如阿尔茨海默病或多发性硬化症。汞蒸汽可以被吸入,从而进入体内。嚼口香糖和磨牙症[13]增加了汞蒸汽释放的风险。迄今为止,没有任何国内外专家能够明确口腔中的合金与这些疾病之间的关系。

  但是我们一谈论到牙科汞合金,还是会心潮澎湃!然而,后果也是我们不愿看到的: 欧洲国家的卫生从业人员声称可以以高价施用汞螯合产品来治愈患者。下面我们将看到,管理这种未经证实的风险非常困难。

4. 汞和淘金者

环境百科全书-汞、鱼和金矿-马罗尼河
图10. 法属圭亚那的马罗尼河,汞污染严重。
[资料来源: Maurizio Alì (CC BY-SA 4.0),维基共享资源] 

  水俣湾事件的“重演”发生在法国最大的省份圭亚那。秘密淘金者大量使用金属汞来混合可能存在于河水中的金块,然后将汞合金加热以回收黄金,每年都有一些人因吸入汞蒸气而死亡。

  但更严重的是,这些淘金行为使这一大片美洲印第安人地区的所有河流都受到金属汞的严重污染(图10)。来自淘金者的金属汞被水体微生物转化为甲基汞,这使得包括法属圭亚那、巴西和苏里南部分地区在内的所有人口都暴露于甲基汞。负责人口监测的卫生机构——法国卫生组织早就制定了人口监测措施,并定期与法国国家食品环境及劳动卫生署沟通过度食用鱼类的风险(见参考文献[1][2])。

5. 汞和风险管理

  汞很能体现管理环境健康风险的难度。风险管理的难度仅次于风险评估。

  风险评估由独立科学家进行: 他们根据目前的知识状况提出建议,并指出接触某种特定有毒物质的健康风险;通常他们还会建议不应超过的接触剂量。

  风险管理是决策者的责任:法国的卫生机构(法国国家食品环境及劳动卫生署)及相关政府部门的部长就扮演了这一角色。这些决策者可能依据也可能不依据专家们的结论。我们举两个例子。

  • 对于吃鱼有哪些建议?

  除了汞、多氯联苯和二恶英等污染物之外,鱼类还会受到许多其他污染物的影响,这使问题更复杂了。风险管理总是要在“必须吃鱼”和“小心鱼里的有毒物质”之间寻求平衡。我们知道鱼类富含某些对健康非常宝贵的营养物质,比如富含脂肪的鱼类中的欧米伽3。我们还知道鱼类中的主要污染物及其健康风险(多氯联苯、二恶英、包括汞在内的重金属)。这些建议只是“保护性的”,还不能证明其有效性。因此,法国国家食品环境及劳动卫生署仅限制儿童和孕妇食用鱼类[14]

  • 关于牙科汞合金的建议?

  这又带来了另一个问题,即在牙科手术中最常被用作汞合金替代品的树脂。但树脂也不是绝对安全的。根据法国国家药品和保健品安全署的预防原则,尽管最近所有的研究都没有证明汞的存在有风险,但有关部门对此的建议仍然是“保护性的”:避免幼儿和孕妇使用汞合金[15]。另一方面,牙科诊所中汞的使用多年来一直受到非常严格的监管,特别是为了避免牙科医生反复吸入有毒物质的风险和患者偶尔吸入有毒物质的风险。法国国家药品和保健品安全署[18]对患者[16]和专业人士[[17]均提出了建议。

  几个世纪以来,对汞以及铅、砷或镉等大量重金属的不当使用造成了对地球大规模、持续性的污染。不幸的是,这些金属都已被证明对人类健康有害。

  汞对于大众来说是一个真正的公共健康问题,尤其是以有机形式存在的甲基汞。正如我们已经看到的,当我们吃海鲜,尤其是鱼时,它就进入了食物链。但我们也要记住,我们必须吃鱼,但不能吃太多,也不能每天都吃。正如这种情况,当需要权衡利弊时,风险管理是一项困难的工作。

  即使摄入金属汞不会造成任何危险,它也不应过度使用。海洋环境中生物的甲基化现象清楚表明,金属汞的环境污染是有机汞进入食物链的原因。

  牙科汞合金也很好地说明了管理风险的难度。哪种风险存在?哪种不存在?无论对错,我们主要还是要遵循预防原则(详见专题预防原则)。

  联合国环境规划署最近实施了一项关于汞的国际公约,即《水俣公约》。该公约2013年在日本通过,2017年8月16日生效[19]。在其主要条款中,《水俣公约》特别规定禁止开采新的汞矿,逐步淘汰现有汞矿,消除和逐步淘汰汞在一些产品和工艺中的使用,制定措施控制汞向大气、水和陆地的排放,并控制非正规手工和小规模金矿开采。《水俣公约》还涉及汞的临时储存及其成为废物后的处置、污染场地和健康方面的问题。

  一段有趣的视频展示了全球汞污染的问题并正确看待该公约[20]:

6. 需要记住的信息

  • 汞很能体现管理环境健康风险的难度,它涉及到两步:
    • 风险评估是由独立的科学家进行的。他们的建议是基于目前的知识状况;他们提出接触某种特定有毒物质的健康风险,以及不应超过的接触剂量。
    • 风险管理是决策者的责任,相关的健康机构就扮演了这一角色。这些决策者可能会也可能不依据专家的结论来给出建议。
  • 金属汞对人体的毒性来自于其在室温下的高挥发性。早在1919年法国职业病登记册上就记录了职业性汞中毒。
    • 汞是一个真正的公共健康问题,尤其是以有机形式存在的甲基汞。
    • 海洋环境中生物的甲基化现象表明金属汞的环境污染是有机汞进入食物链的原因。
    • 汞是一种具有“累积性”的有毒物质,随着时间推移会在生物体内累积,这就是生物累积。
    • 生物放大是环境健康方面的另一个重要问题:有机汞通过食物链积累,最后进入人体。人类处于食物链的顶端,当我们食用剑鱼、金枪鱼或比目鱼等鱼类时,会接触到最大剂量的有机汞。
    • 风险管理总是在“吃鱼有益健康”和“小心鱼中的有毒物质”之间寻求平衡。
  • 金属汞可以与其他金属混合的特性使其一直被用来制作“填充物”,填补龋齿。
    • 迄今为止,还没有专业知识能够证明牙科汞合金可能带来任何健康风险。
    • 根据国家药品和保健品安全机构的预防性原则,他们给出的很多建议是保护性的。
    • 多年来,牙科诊所对汞的使用一直受到非常严格的监管。
  • 秘密采金者利用水银回收河水中可能存在的任何黄金。因此,这些河流(如法属圭亚那)被汞严重污染,造成了不可挽回的环境损害。此外,过度食用鱼类的人群也存在健康风险。
  • 几个世纪以来,对汞以及铅、砷或镉等大量重金属的不当使用对地球造成了大规模、持续性的污染。不幸的是,这些金属都已被证明对人体健康有害。

参考资料及说明

封面照片:[资料来源:By Arnaud 25 [CC BY-SA 3.0 (https://creativecommons.org/licenses/by-sa/3.0)],来自维基共享]

[1] Bensefa-Colas L, Andujar P, Descatha A (2011). Intoxication au mercure. La revue de Médecine Interne, 32 (7), pp.416-24.

[2] 多种不同元素的组合。这个词在化学中最常用来指汞与其他金属的合金。

[3] 在《环境健康》中,明确区分了在工作场所面临某些风险的专业人员群体和普通人群(即工作场所以外的所有人)。

[4] Clarkson TW (2002). The three modern faces of mercury. Environment Health Perspectives, 110 Suppl 1: 11-23.

[5] 法国公共卫生 : www.santepubliquefrance.fr

[6] YEARS.国家食品、环境和劳动卫生安全局: www.anses.fr/fr

[7] Harada M (1995) Minamata Disease: Methylmercury poisoning in Japan caused by environmental pollution, Critical Reviews in Toxicology, 25:1, 1-24

[8] Bond AL, Hobson KA, Branfireun BA. 2015 Rapidly increasing methyl mercury in endangered ivory gull (Pagophila eburnea) feathers over a 130 year record. Procedings of the Royal Society of Biology, 282: 2015

[9] Schuster PF, Krabbenhoft DP, Naftz DL. 2001. Atmospheric mercury deposition during the last 270 years: a glacial ice core record of natural and anthropogenic sources. Environmental Science and Technology, 36, 2303-2310

[10] Shuster PF et al (2018). Permafrost stores a globally significant amount of mercury. Geophysical Research Letters, 45, 1-9

[11] Al-Tikriti K, Al-Mufti AW (1976). An outbreak of organomercury poisoning among Iraqi farmers. World Health Organization Bulletin. 53 Suppl:15-21

[12] Myers GJ, Davidson PW, Cox C and others (1995). Summary of the Seychelles child development study on the relationship of fetal methylmercury exposure to neurodevelopment. Neurotoxicology 16, 711-716.Encyclopédie de l’environnement 12/12 Généré le 13/08/2021

[13] 反复和无意识的牙齿摩擦

[14] YEARS:吃鱼的好处和风险.www.anses.fr/fr/content/manger-du-poisson-bénéfices-et-risques

[15] ANSM :牙科汞合金中的汞, 数据更新, 2015年4月.
http://ansm.sante.fr/content/download/76933/976017/version/1/file/ANSM_Report_Mercury-Amalgames-Dentaires_May-2015.pdf

[16] ANSM:http://ansm.sante.fr/var/ansm_site/storage/original/application/0b5892a526480ba401d0ccc3fd4ee0e2.pdf

[17] http://ansm.sante.fr/var/ansm_site/storage/original/original/application/7cacb0593aaa9f8ebd9b176c65ff98890.pdf

[18] ANSM :法国国家药品和保健品安全署: http://ansm.sante.fr/

[19] 关于汞的水俣公约:
http://www.mercuryconvention.org/Portals/11/documents/Booklets/COP1%20version/Minamata-Convention-booklet-fr-full.pdf

[20] 创作汞的历史: https://youtu.be/guO7RbArWf4


The Encyclopedia of the Environment by the Association des Encyclopédies de l'Environnement et de l'Énergie (www.a3e.fr), contractually linked to the University of Grenoble Alpes and Grenoble INP, and sponsored by the French Academy of Sciences.

To cite this article: DANEL Vincent (March 9, 2024), 汞、鱼和金矿, Encyclopedia of the Environment, Accessed November 21, 2024 [online ISSN 2555-0950] url : https://www.encyclopedie-environnement.org/zh/sante-zh/mercury-fish-gold-miners/.

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