Environmental pollution and biological effects of trace element vanadium

Zeng Ying [1] Ni Shijun Zhang Chengjiang

(School of Materials and Bioengineering, Chengdu University of Technology, Chengdu 610059, China)

Abstract The relationship between trace elements and human health has received increasing attention in recent years. Vanadium is an essential trace element in animals and humans and exhibits diverse biological activities. In addition to its chemical diversity, the diversity of vanadium biological effects is also affected by the complexity of the environmental ecosystem in which it is involved. The article reviews the work done by researchers at home and abroad in recent years on the environmental pollution and biological effects of vanadium.

Key words trace elements vanadium pollution biological effects

Environmental pollution and biological effect of microelement vanadium Zeng Ying, Ni Shijun, Zhang Chengjang. Institute of Materials and Bioengineering, Chengdu University of Technology, Chengdu, Sichuan, 610059

Abstract: In recent years, the interest of the relationship between microelement and human health increased. Vanadium is an essential trace element for animal and man, and makes varied biological effects. The diversity biological effects of vanadium depend on the diversity chemical properties, and also In this paper, the source of vanadium in environment and biological effect of vanadium were summarized.

Keywords: Microelement Vanadium pollution Biological effect

The relationship between trace elements and human health has received increasing attention in recent years. Due to the influence of environmental conditions in the natural environment, surface elements migrated, dispersed in some areas, and accumulated in other areas, resulting in uneven distribution of some living elements on the surface. This abnormality (deficiency or excess) of living elements in the biogeochemical nutrient chain can cause endemic diseases in plants, animals and even humans.

Vanadium is one of the very widely distributed in nature element, showing a diversity of its chemical properties, such as from the presence of the valence (1) to (+5) price; be the same amino acid, oxalic acid, citric acid, EDTA, phosphorus acid groups A variety of ligands such as ions and hydroxyl groups form polymers [1, 2] . It is the diversity of the chemical properties of vanadium that leads to the diversity of its biological effects. In recent decades, with the understanding of the toxic effects of vanadium in animals and humans, the geochemical cycle, health effects and toxicology of vanadium have attracted widespread attention [3] , and environmental pollution and biotoxicity in vanadium. Progress has been made in terms of rationality and toxicity, and global biogeochemical cycles. This paper focuses on the environmental geochemical cycle of vanadium and its biological effects in plants and plants.

1 Environmental pollution of vanadium

Elemental vanadium is highly chemically mobile and can migrate within the environmental circle of minerals, water, atmosphere, soil and organisms. Present study suggests that the source of vanadium in the Environment There are three main ways [4 ~ 7]: â‘  Natural weathering of rocks; â‘¡ combustion of coal, oil and other fuels; â‘¢ magnet vanadium and titanium vanadium-containing mineral ore mining, smelting.

In the epigenetic zone, after the endogenous vanadium-bearing minerals are subjected to weathering, V 3+ is easily oxidized to a V 5+ -containing (VO 4 3- ) complex anion, whereby the vanadate is formed. A soluble salt that migrates in a solution that varies greatly in acidity and alkalinity and thus enters the ecological circulatory system.

Vanadium is one of the major trace elements in fuels such as coal, heavy oil and petroleum. The combustion of these fuels is the main source of vanadium in the environment. According to statistics [4] , the average vanadium content of coal in the world is 19 ppm, the crude oil is 6-114 ppm, the vanadium that fossil fuel burns into the atmosphere is estimated to be 29,000 tons, and the annual vanadium entering the atmosphere by nature is about 37,000 t. Among them, about 27,000 tons from rocks and soil dust, and about 10,000 tons from volcanic fly ash. In the combustion process of coal, petroleum and other fuels, vanadium in coal enters the atmosphere in the form of particles of volatile organic vanadium or vanadium-containing compounds. At high temperatures, it can participate in various reactions to form vanadium oxides and vanadium. Various compounds, such as chloride or vanadium phosphate, enter the particle phase as the temperature decreases. The particle size distribution depends on the temperature range and coexisting particles in the system [8-10] . Analysis of the particles discharged from the power plant found that vanadium with a particle size between 0.01 and 1.0 um accounted for 88% (mass percent) of the total vanadium [11] , and vanadium in atmospheric particulate matter was mainly soluble in water. Oxides, trioxides, and ammonium vanadate are present in the form of [6] , which is soluble in the atmosphere and enters the ecological cycle. In areas where coal is the main fuel and the technology level is relatively backward, the combustion of fuels such as coal, heavy oil and petroleum is the most important cause of vanadium pollution. In recent years, due to the development of industries such as thermal power generation and petroleum smelting, the resulting vanadium pollution is more serious [12] .

Refining and smelting vanadium alloy vanadium, vanadium pollution of the environment is also an important source. Vanadium is discharged into the environment during a series of processes such as vanadium-titanium magnetite extraction, pulverization, sintering, and steel making. Usually, about 30% of the smelting vanadium is discharged into the environment during the smelting process of vanadium, resulting in pollution. For example, in Panzhihua City, Sichuan Province, during the period from 1973 to 1978, vanadium pentoxide discharged into the Jinsha River was about 2150 t/a, about 2160 t/a was discharged into the atmosphere, and the waste vanadium slag deposited was about 10760 t/a. . The amount of vanadium in the soil around the smelter was 16.5 times that of the control and 6.6 times that of the control [13] . Hope [14] believes that 53% of vanadium in the air is discharged from industrial activities such as smelting and mining of vanadium ore.

Due to the continuous expansion of human production activities, the concentration of vanadium in the environment is still increasing. Vanadium entering the environmental medium can enter the organism and the human body through rainfall action, soil adsorption, plant root function and food chain, thereby affecting the normal physiological activities of organisms and humans.

2 Biological effects of vanadium on humans and animals

The biology and toxicology of vanadium began in 1876 [15] and developed rapidly in the 1970s and 1980s. The study found that [16] , the chemical nature of vanadium is the basis for determining the biological effects of vanadium. The toxicity and life effect of vanadium compounds are related to the total amount of vanadium, and more importantly, they are affected by the chemical characteristics and appearance of vanadium. The toxicity of metal vanadium is very low, but its compounds are moderately toxic to animal and plant, and the toxicity increases with the vanadium compounding state. The toxicity of pentavalent vanadium is the highest [17] ; VO 2+ is biologically ineffective, while VO 3 - It is easy to be absorbed [18] . It can be seen that different chemical forms present different biological effects. In an environmental system, vanadium can exist in the oxidation state of (-1) to (+5) and usually forms a large number of polymers [9,10] . In the extra-tissue fluids and cells, the main forms of vanadium are vanadate (VO 3 - , V 5+ ) and vanadium oxy cations (VO 2+ , V 4+ ). After vanadate enters the cell, it is gluten. Glycopeptide (C 10 H 17 O 6 N 3 S) and other substances are reduced to vanadium oxy cations and are stably present in combination with ligands such as protein, phosphate, citric acid and lactic acid [10] .

Whether it is vanadate or vanadium oxy cation, it can promote the physiological function of the animal at an appropriate amount, such as maintaining the growth of the organism; maintaining the normal work of the cardiovascular system; inhibiting the synthesis of cholesterol; promoting hematopoiesis [4, 19~21] ; affects insulin in tissues, promotes glucose absorption, oxidation and synthesis [22~24] , exhibits insulin-like action [25,26] ; promotes protein tyrosine phosphorylation [27] ; promotes potassium The absorption [23] ; reduces the hydrolysis of triglycerides [28,29] and protein degradation [30] and so on.

Due to the intensification of vanadium environmental pollution in recent years, the research on the biological effects of vanadium is mainly focused on the toxicology of vanadium. Mammalian lung, liver and other organs have a significant accumulation of vanadium [31,32] . For example, the concentration of vanadium in the liver of American Alaskan whale (Cetaceans) increased from 0.1ug/g to 1ug/g, and obvious organisms occurred. Cumulative, cumulative concentration is positively correlated with animal age and size [31] . This result was also verified in the rat kidney test [33] . The accumulation of vanadium has moderate to high toxicity to animals, which can cause damage to the respiratory system, nervous system, gastrointestinal system, hematopoietic system, and metabolic changes [4,19-21,34] , reducing food intake and causing diarrhea. Reduce weight [35] ; change metabolism and biochemical function [36] ; inhibit reproductive capacity and growth [11] ; reduce animal's ability to resist external stress, toxins and carcinogens [37] ; even death. For example, the toxicity test of rats showed that the concentration of vanadium in rats was 0.25 mg/L and the lethal concentration was 6 mg/L [38] .

In the early 1970s, vanadium was identified as an indispensable trace element in animals such as chickens and mice [39,40] , and it also led to the question of whether vanadium is also an indispensable trace element in humans. Nielsen [41] believes that vanadium is an essential element in higher animals and humans, but the possible effects on high levels of vanadium (1 or 2 ug/g) are still unknown, so it is still considered that the human essential to vanadium is not available. solve.

Studies have shown that normal adults contain about 25 mg of vanadium, and the blood vanadium content is very small, about 0.00078 mol / L. There are two main ways for vanadium to enter the human body: one is daily dietary intake, which is the main way for many other trace elements to enter the human body. The amount of vanadium ingested by the diet is 10-20 ug/d [42] , and the most needed vanadium in humans and animals is about 20 ug/d [43] , but it has been reported [44] that vanadium in the United States has been invaded by diet. It reaches 10~60 ug/d. Second, the vanadium in the environment is absorbed into the body through the skin and absorbed into the body. This pathway is rare among most other essential elements.

Vanadium entering the human body is mainly accumulated in the stomach, kidney, liver and lung [3 , 45 , 46] , and can also be stored in fat and plasma lipids [3] . At this time, although there is an important understanding of the biochemical effects and functions of vanadium [9,47,48] , there is still a lack of understanding of the metabolic process of vanadium, and there is no data to illustrate [3] . To this end, Sabbioni et al. [49] measured the concentration of vanadium in human blood, serum and urine by RNAA method. The content of vanadium in blood and serum was about 1 nmol/L, and the content of vanadium in urine was about 10 nmol/L, and the amount of vanadium is not related to gender. However, it is also considered that the above data is only normal values ​​under the test conditions because the appropriate literature reference values ​​are still missing.

The study also showed that [40,50,51] , when the accumulation of elemental vanadium in the human body reaches a certain concentration, it will have toxic effects on the human body. Vanadium can irritate the eyes, nose, throat, and respiratory tract, causing cough; competition with calcium makes calcium free, and decalcification is prone to occur; vanadium is also a poison that can be absorbed by the body, affecting the gastrointestinal, nervous system and heart, poisoning When the kidney, spleen, and intestines appear severe vasospasm, gastrointestinal hypermotility and other symptoms.

3 Biological effects of vanadium on plants

For plants, although it has not been determined that vanadium is an essential nutrient for plant growth, studies have found that vanadium plays an important role and influence on the growth and development of plants, especially legumes [4, 52] . Appropriate amount of vanadium promotes crop growth and promotes nitrogen fixation and chlorine fixation of plants. However, when the vanadium compound is excessive, it is also toxic to higher plants. Rice seedlings had a good effect on growth when applied with 150 ppm ammonium metavanadate. Poisoning at 500 ppm and seedling death at 1000 ppm [53] ; yield of soybean treated with 25 mg/kg vanadium began to decrease, and vanadium treatment reached 50 mg. Soybean yield decreased significantly when /kg was above [54] . At the same time, excessive vanadium can strongly inhibit various ATPases on the cell membrane of plant roots, causing plant dwarfing and yield reduction [41] , reducing the absorption of calcium, phosphate and other nutrients by plants [54, 55] ; reducing sorghum root tip The absorption of calcium [55] ; reduced the extraction of phosphate from corn roots [56] ; inhibited the growth and development of soybean seedlings [57] .

Zou Baofang et al [54] believed that plants have a strong ability to control the transport of vanadium to the aboveground part. Most of the vanadium is enriched in the roots of plants, so soil vanadium is less likely to cause direct damage to the aerial parts of plants, and vanadium treatment causes plant dwarfs. The decrease in growth and above-ground growth is the result of vanadium seriously affecting root growth.

So far, a large amount of research has been done on the effective vanadium of plants. However, since vanadium in plants is mainly derived from soil, vanadium dissolved in 2.5% (pH 2.5) in the soil is regarded as an effective vanadium of plants. The existence of vanadium in soil is extremely complicated. It is affected by many factors such as vanadium content in soil and migration and transformation characteristics of vanadium. Therefore, when using dissolved vanadium in soil as effective vanadium of plants, soil type and pH of soil solution must be considered. The effect of conditions such as values. Wang Jinhang [57] investigated the relationship between the toxicity of vanadium to soybean seedlings and soil properties. The study found that in the fluvo-aquic soil, the vanadium content is higher than 30 mg/kg, and the dry matter quality of the aboveground and underground parts of soybean seedlings is significantly reduced. In the red soil, the vanadium content is as high as 75 mg/kg, which is not obvious for the growth of soybean seedlings. influences. The mechanism of uranium-producing vanadium poisoning may be due to the small adsorption capacity of vanadium, the maintenance of a large amount of effective vanadium in the soil solution for soybean seedlings, and the high adsorption capacity and supply of vanadium when the soil pH changes. ability. It can be seen that the soluble vanadium in the soil cannot be simply used as the effective vanadium of the plant.

4 Conclusion

In summary, vanadium has a diverse biological effect on both animal and plant and human body. The diversity of vanadium biological effects is inseparable from the diversity of its chemical properties, mainly depending on the chemical properties of the three aspects [58] :(1) VO 4 3- /VO 2+ electrical pair and Fe 3+ /Fe 2+ electricity The similarity of the pair, ie, the one-electron redox system, promotes the formation and transformation of free radicals; (2) the similarity between VO 4 3- and PO 4 3- , the interaction of vanadate as an analogue of phosphate and the intervention of phosphate (3) Coordination chemistry of VO 2+ . In addition, the diversity of vanadium biological effects is also affected by the complexity of the environmental ecosystem in which it is involved.

Although a series of achievements have been made in the environmental geochemical cycle of vanadium and its biological effects, especially toxicology research, most of the research work remains in the local environmental regions and qualitative research of individual species. The mechanism of physiological metabolism in animals, such as the mechanism in cell biological reactions, is not fully understood; there is no standard for the classification of vanadium in environmental media; there is still no quantitative study on the toxic concentration region of vanadium in humans, animals and plants.

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[1] first author: Zeng Ying, female, born in 1968, Ph.D., associate professor, mainly engaged in chemical thermodynamics and kinetics.

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