Perchlorate – Properties, Toxicity and Human Health Effects
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Rev Environ Health 2021; 36(2): 199–222 Review Article Przemysław Niziński*, Anna Błażewicz, Joanna Kończyk and Rajmund Michalski Perchlorate – properties, toxicity and human health effects: an updated review https://doi.org/10.1515/reveh-2020-0006 Introduction Received January 14, 2020; accepted July 28, 2020; published online September 4, 2020 Perchlorate has been identified as an environmental pollutant. Interest in perchlorate as potential substance Abstract: Interest in perchlorate as environmental affecting human health has increased since 1997, when pollutant has increased since 1997, when high concentra- large amounts of them have been detected in water sam- tions have been found in the waters of the Colorado River, ples from western states of the USA [1]. Sources of USA. Perchlorate is very persistent in nature and it is slowly perchlorate in the environment may include those related degraded. Although harmful effects of large doses of to human activity and natural formation. Naturally occur- perchlorate on thyroid function have been proven, the ring perchlorate were found in samples of Chilean nitrate, environmental effects are still unclear. The primary used on a large scale in agriculture as a fertilizer, probably objective of the present review is to collect prevailing data also formed during reactions occurring in the upper re- of perchlorate exposure and to discuss its impact on hu- gions of atmosphere. The sources related to human activity man health. The results show that more than 50% of should involve applications in military purposes, space reviewed works found significant associations of perchlo- exploration, fireworks and other industries [2]. In the past rate exposure and human health. This review consists of years perchlorate was used as a hyperthyroidism treating the following sections: general information of perchlorate agent, although it was withdrawn from medical usage due sources, its properties and determination methods, role to its grave adverse effects [3]. Perchlorate has been clas- and sources in human body including food and water sified as goitrogen (i.e., substance inhibiting iodine uptake intake, overview of the scientific literature on the research by thyroid cells), which disturbs the metabolism of thyroid on the effect of perchlorate on human health from 2010 to hormones and consequently can lead to serious health is- 2020. Finally, conclusions and recommendations on future sues [4, 5]. Many studies were conducted to examine the perchlorate studies concerning human exposure are effects of perchlorate on thyroid activity, while influence presented. on other tissues and organs is still unknown. There are few Keywords: endocrine disruptors; environmental hazard; papers describing the effect of perchlorate depending on goitrogens; perchlorate; risk assessment; thyroid. the route of administration other than oral (inhalation, transdermal) and on other tissues and systems of the hu- man body [6, 7]. Although the results of animal studies are available (mainly in rats) and significantly broaden the knowledge of perchlorate mode of action, their findings certainly require confirmation in humans [8]. Epidemio- *Corresponding author: Przemysław Niziński, Chair of Chemistry, logical research was mainly conducted in the US, partly Department of Analytical Chemistry, Medical University of Lublin, also in China, but so far in other regions of the world have + + Lublin, Poland, Phone: 48 534780270, Fax: 48 81 448 7181, been carried out on a very small scale [8, 9]. The review of E-mail: [email protected] perchlorate toxicity in humans was published in 2010 in Anna Błażewicz, Chair of Chemistry, Department of Analytical Chemistry, Medical University of Lublin, Lublin, Poland which the authors presented the outcomes of population Joanna Kończyk, Institute of Chemistry, Health and Food Sciences, exposure studies, multiple regression analyses of sodium- Faculty of Mathematics and Natural Sciences, Jan Dlugosz University iodine symporter (NIS) inhibitors in urine and thyroid in Czestochowa, Czestochowa, Poland hormone concentration. Some of the occupational studies Institute of Chemistry, Health and Food Sciences, Rajmund Michalski, were included and the impact of gestational perchlorate Faculty of Mathematics and Natural Sciences, Jan Dlugosz University in Czestochowa, Czestochowa, Poland; Institute of Environmental exposure of newborn thyroid function were investigated. Engineering, Polish Academy of Sciences, Zabrze, Poland Conclusion of the aforementioned review indicates that Open Access. © 2020 Przemysław Niziński et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0 International License. 200 Niziński et al.: Perchlorate: an updated review there is no strong evidence between abnormal thyroid inherently incomplete and consequently far from being function and environmental perchlorate exposure, but actual. It is estimated that the annual global production of there are some weaknesses of this study. Reviewed works perchlorate is about several hundred thousand tons and were mainly conducted in the US and very few were from the largest production plants are placed in the USA, different geographical regions, such as East Asia or France, Germany, Italy, China and Brazil [16–17]. Europe. The investigated outcomes were focused directly Anthropogenic sources include the import and use of on thyroid hormones or TSH levels and ignored many other Chilean nitrate as a fertilizer exploited from deposits in the serious health effects [10]. In the past decade many of new Atacama desert in Chile. The fertilizer produced on the facts about perchlorate toxicity, involving non-thyroidal basis of Chilean nitrate contains approximately 98% outcomes were acknowledged. A new mechanisms of NaNO3 and, according to various studies, from 0.05 to − perchlorate impact on NIS were proposed [11], so a novel 0.4% ClO4 [18]. In the 1830–1980 period, the estimated approach on environmental perchlorate toxicity was taken volume of imports of Chilean saltpeter ore to the USA and in our review. The review focuses on the period of 2010– Europe amounted to approximately 23 million tons in 2020 to investigate into the most recent directions of terms of nitrogen, with the highest value being reported in perchlorate studies. 1930s [19]. In US commercial production of sodium nitrate In this review we present the most actual knowledge of began in 1915 and in the following years domestic pro- perchlorate chemistry, its environmental occurrence and duction increased its share in total US nitrate consumption. human toxicity. The new data about perchlorate occur- In 1994 over 11 million tons of sodium nitrate were used in rence and health effect still reveals and there is essential US agriculture and only approximately 30,000 tons were need to re-evaluate periodically the state of knowledge on from imported Chilean nitrate [2]. According to United these compounds [12]. The main purpose of this work is to Nations Trade Statistics Branch the volume of sodium ni- discuss findings of the human population studies from the trate import from Chile was about 19,000 tons in 2018 [20]. peer-reviewed literature published in last 10 years which A material evidence of increasing man-made perchlorate assessed potential risk of exposure and health effects. We contamination has been disclosed in shallow ice core in − also present the chemistry and some routes of exposure in Thienshan, East Asia, where concentration of ClO4 was order to facilitate the environmental perchlorate pollution. still increasing during 1980s’ to 2004 [21]. This review seeks to indicate the gaps of knowledge on perchlorate and attempts to outline new directions of prospective perchlorate studies. Natural The largest known perchlorate reservoir in the world are Sources in the environment the aforementioned Chilean saltpeter deposits. The presence of natural perchlorate has also been demon- Anthropogenic strated in snow samples from Arctic, waters of the Great Lakes (USA and Canada), soil samples from Death Valley Perchlorate was described for the first time by Count Frie- (USA)andDryValley(Antarctica)[1,22–25]. In 2015, the drich von Stadion in the work “Von den Verbindungen des results of determination of perchlorate content in surface Chlorine mit dem Sauerstoff” in 1816 [13]. Significant in- and underground waters as well as soil samples from crease in worldwide production of perchlorate was semi-arid areas and deserts (Atacama Desert in Chile, observed during World War II. In 1940 global production of Mojave Desert in the USA, deserts in western regions of − −1 ammonium perchlorate was about 2,000 tons per year, Africa), showed the presence of ClO4 in range from 10 then in 1945 it was approximately 20,000 tons [14]. In this to 106 μg/kg [26]. The mechanism of formation of period perchlorate were mainly used for the production of perchlorate in nature is not fully understood. Several explosives for war industry. After 1945, the production of paths of a possible perchlorate natural formation have perchlorate continued to grow especially for military ap- been proposed [2, 26–31], mainly in photochemical pro- plications, as their interesting properties were discovered cesses, with the participation of chloride ions and ozone as a valuable component of rocket fuel [15]. In conjunction in the troposphere and stratosphere [32]. The theory with the current use of perchlorate in military installations, indicating the possibility of perchlorate