Sources of HM Contamination in Arable Lands: Comparison
Please note this is a comparison between Version 2 by Conner Chen and Version 1 by Abdur Rashid.

Heavy metals and metalloids (HMs) are environmental pollutants, most notably cadmium, lead, arsenic, mercury, and chromium. When HMs accumulate to toxic levels in agricultural soils, these non-biodegradable elements adversely affect crop health and productivity. The toxicity of HMs on crops depends upon factors including crop type, growth condition, and developmental stage; nature of toxicity of the specific elements involved; soil physical and chemical properties; occurrence and bioavailability of HM ions in the soil solution; and soil rhizosphere chemistry. HMs can disrupt the normal structure and function of cellular components and impede various metabolic and developmental processes. 

  • heavy metals
  • arable lands
  • agricultural practices

1. Introduction

Metals, including potentially toxic elements, are inorganic elements containing atomic densities (g·cm−3) several times higher than H2O (1 g·cm−3) and broadly classified into heavy and light metals, and semi-metals (Figure 1). Based on physical, physiological, and chemical properties, metals have been classified under several sub-groups, namely: transition metals: e.g., chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and molybdenum (Mo); post-transition metals: e.g., aluminum (Al), zinc (Zn), cadmium (Cd), mercury (Hg), and lead (Pb); alkaline earth metals: e.g., calcium (Ca), magnesium (Mg), beryllium (Be), and barium (Ba); alkali metals: e.g., lithium (Li), sodium (Na), potassium (K), and cesium (Cs); and metalloids, which are also referred to as semi-metals because of their metallic and non-metallic properties: e.g., boron (B), silicon (Si), arsenic (As), and antimony (Sb) [1].
Figure 1. Classification of metallic and non-metallic elements frequently found in agricultural soils. Mg (magnesium), Ca (calcium), Fe (iron), B (boron), Mn (manganese), Zn (zinc), Mo (molybdenum), Cu (copper), Pb (lead), Ni (nickel), Cr (chromium), As (arsenic), Hg (mercury), Cd (cadmium), Al (aluminum), Li (lithium), K (potassium), Na (sodium), Si (silicon).
Heavy metals and metalloids (HMs) are environmental pollutants. They are also agricultural soil contaminants, because if present at elevated levels in the soil, HMs can negatively impact crop health and productivity [2,3][2][3]. HMs are recalcitrant to degradation, and if not taken up by plants or removed by leaching, they can accumulate in the soil and persist for long periods [4,5,6][4][5][6]. The elements that are frequently found to contaminate agricultural soils and cause toxic effects at elevated levels on plants include Cd, Pb, Cr, As, Hg, Ni, Cu, and Zn [4,7][4][7]. Among them, Cd, Pb, As, Hg, and Cr are highly toxic and detrimental to plant health at almost all levels of contamination [8,9,10][8][9][10].
Several elements are classified as essential mineral nutrients for plant growth and productivity (Figure 1). Examples include Cu, Zn, Fe, Mn, Mo, Ni, Mg, Ca, and B. At relatively low concentrations, these elements can enhance specific cellular functions in plants including ion homeostasis, pigment biosynthesis, photosynthesis, respiration, enzyme activities, gene regulation, sugar metabolism, nitrogen fixation, etc. [3,8,11][3][8][11]. However, when accumulated at concentrations above optimum, these same essential elements can adversely affect plant growth, development, and reproduction [2,3][2][3]. Conversely, if the concentration falls below certain threshold levels, they also produce mineral deficiency symptoms in plants [11].
HM contamination in agricultural soil is a global issue. In addition to certain geogenic and climatic factors, specific circumstances such as rapid urbanization, and increased industrial, municipal, agricultural, domestic, medical, and technological applications appear to be the major causes of HM pollution in the environment at the present time. However, the problem is more prominent in many developing countries, partly because of the above reasons, and perhaps partly due to a lack of proper awareness about the toxic consequences of these elements not only to human health but also to crop health [12,13,14,15,16][12][13][14][15][16].

2. Sources of HM Contamination in Arable Lands

Agricultural soil is an important non-renewable natural resource. It can be contaminated with toxic HM elements such as Cd, Pb, Cr, As, Hg, Cu, Ni, Zn, Al, and several others due to natural causes as well as anthropogenic activities. Natural causes include, among many others, weathering of metal-bearing rocks by rainwater and atmospheric deposition. Anthropogenic activities include industrial activities (e.g., mining, leather tanning, textile, and petrol-chemical), disposal of metal-containing wastes, vehicle exhausts, and agricultural practices [4,15,17,18,19,20][4][15][17][18][19][20]. However, irrespective of the source of contamination, continued addition of HMs to arable lands can result in soils that can be too toxic to support plant growth and productivity.

2.1. Application of Chemical Fertilizers

Chemical fertilizers, particularly inorganic fertilizers, are a crucial input for crop production. Consequently, large quantities of inorganic fertilizers, including nitrogen (N), phosphorus (P), potassium (K), and compound/mixed fertilizers are routinely added to agricultural lands to supply adequate quantities of these macronutrients. For instance, it was estimated that in 2019, more than 220 million tons of commercial fertilizers and liming materials were applied worldwide, mostly to agricultural fields [21]. Among these fertilizers, P fertilizers contain the highest level of HM contaminants [4,22,23,24][4][22][23][24]. For example, superphosphate fertilizers can contain Cd, Co, Cu, Pb, Zn, Cr, and Ni as contaminants. In a study that assessed soil with and without P fertilizer amendments, the concentration of Zn was higher not only in the amended soil, but also in the plants grown in that soil [25]. Cadmium content in the soil has been shown to increase persistently due to the application of P fertilizers [12,23,26][12][23][26]. Cadmium is extremely toxic to plants because of its high solubility and mobility in soil solution. The concentration of Cd present as an impurity in several P fertilizers evaluated in a study is shown in Table 1.
Table 1.
Cadmium concentrations in several phosphate fertilizers (adapted from [27]).
In addition to P fertilizers, copper sulphate, iron sulphate, and zinc sulphate fertilizers can also contain HM contaminants, including Pb [22,27,28][22][27][28]. A study reported from greenhouse experiments that repeated application of chemical fertilizers significantly increased the accumulation of several HM elements in the soil (Table 2). Experiments carried out with soil samples collected from multiple locations in agricultural lands of peninsular Malaysia and Guangdong Province of China show that the concentrations of different HM elements (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Zn) were severalfold higher as compared to control soil samples (refer to Table S2). These HM elements have originated from suspected agricultural practices, including fertilizer applications. Sources of HM contamination in fertilizers include the raw materials used in the manufacture of inorganic fertilizers. For instance, phosphate rock, also known as phosphorite, is utilized in the production of P fertilizers [29,30][29][30]. Over 90% of potash extracted from mines is used in the manufacture of K fertilizer [31]. Based on the level of HM impurities, chemical fertilizers can be ranked as follows: P fertilizers ≥ compound fertilizers> K fertilizers> N fertilizer [32,33][32][33].
Table 2. Heavy metal concentrations in greenhouse soil because of repeated application of inorganic fertilizers (adapted from [24]).

2.2. Pesticide Application

Pesticides play an important role in global agriculture. It has been estimated that without pesticides, the world’s food production could be reduced by close to ~40% [34]. Another study estimated a 78% loss of fruit production, 54% loss of vegetable production, and 32% loss of cereal production without pesticide use [35]. Pesticides such as insecticides, fungicides, rodenticides, nematicides, and herbicides are composed of either organic or inorganic compounds that are toxic to the targeted organisms. Analysis of these compounds shows that some of them contain HM elements either as active ingredients (Table 3) or as impurities in the formulations (Table 4).
Table 3. Pesticides containing different HM elements in their active ingredients (adapted from [36,37]).
Pesticides containing different HM elements in their active ingredients (adapted from [36][37]).
Table 4.
Pesticide products containing HM elements as impurities.

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