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Figure 7.3: Leaves of Mentha piperita and Urtica dioica.
Figure 7.4: Leaves and flowers of Mentha spicata.
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 273
and roots, where it can degrade plant quality and overall performance. Arsenic expo­sure can trigger oxidative stress and cause severe cellular damage, ultimately leading to stunted growth and lower yields [41]. Studies from Poland indicate that arsenic lev­els in Mentha × piperita range between 0.05 and 0.13 mg/kg, while in Urtica dioica, con­centrations vary from 0.09 to 0.24 mg/kg (Figure 7.3) [42].
In Austria, a study analyzing plant samples grown in chernozem soil – a fertile, humus-rich black soil – found that arsenic concentrations in the leaves and branches ranged from 1.2 to 2.0 mg/kg, while the soil itself contained 18 mg/kg of arsenic [43]. Similarly, for Mentha spicata (spearmint), the reported average arsenic content is ap­proximately 0.2 mg/kg (Figure 7.4) [44].
Furthermore, analyses of fennel seed samples from India have detected arsenic con­centrations ranging from 0.51 to 0.59 mg/kg [45]. Research conducted in Bulgaria has revealed that commonly consumed tea bags contain arsenic levels between 0.02 and
0.25 mg/kg [46]. Additionally, significant arsenic accumulation has been reported in macroalgae and sea moss, with concentrations varying from 20 to 100 mg/kg [47]. These results underscore the need for stringent monitoring of arsenic levels in food and medicinal products, particularly in edible and therapeutic plants.
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Although nickel is an essential micronutrient for certain plants, excessive amounts can be harmful. At high concentrations, it interferes with protein and enzyme struc­tures, disrupting vital metabolic activities such as respiration and photosynthesis. More­over, nickel exposure can induce genetic and structural alterations in plants, potentially leading to long-term damage. Such effects are particularly concerning for medicinal and aromatic plants, as their bioactive compound composition must remain stable and of high quality [18]. Consequently, identifying sources of contamination and mitigating heavy metal levels in the environment is crucial.
7.3 Mechanisms of heavy metal uptake
and accumulation in plants
The soil solution, which serves as the medium for plant mineral absorption, consists of a complex blend of elements. Consequently, interactions between these elements frequently occur in plants. Due to the chemical resemblance between cadmium and zinc, their interactions have been widely observed in various plant species. Research on plants cultivated in different soil types has shown that higher zinc levels in flax seeds (Linum usitatissimum) lead to a significant decrease in cadmium accumulation [48]. A pot experiment conducted in North Dakota, USA, further confirmed that soil enrichment with zinc can lower cadmium content in flax seeds. However, when cad­mium and zinc were applied together, cadmium concentration in the seeds increased compared to when cadmium was added alone [49]. The application of monoammo­nium phosphate in flax seeds has been found to elevate cadmium concentrations while decreasing zinc levels [48]. Chizzola and Mitteregger [50] explored cadmium­zinc interactions in chamomile plants, revealing that soil enrichment with zinc signifi­cantly lowered cadmium accumulation in the aerial parts. However, this reduction was insufficient for plants in contaminated areas to match the cadmium levels of those in uncontaminated regions. In the case of Achillea millefolium (yarrow), the con­current addition of cadmium and zinc did not significantly influence cadmium accu­mulation [51].
Cadmium-manganese interactions have also been documented in lettuce, where an increase in cadmium concentration within the nutrient solution led to greater manganese absorption and translocation to the aerial parts [52]. Similarly, nutrient solution studies indicated that introducing a small amount of cadmium enhanced iron uptake in sorghum [24]. In Picea abies (Norway spruce), elevated calcium levels reduced cadmium and zinc accumulation, whereas the presence of cadmium or cop­per hindered calcium uptake [53]. Additionally, interactions between phosphorus and zinc at both the plant and soil levels have been reported [54].
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 275

7.4 Processes of heavy metal uptake by roots

Roots serve as the primary interface between plants and soil, playing a crucial role in the absorption of heavy metals. This process occurs through two main mechanisms: active and passive uptake. Active uptake involves the transport of heavy metal ions into root cells via specialized membrane proteins, such as H energy-driven mechanism enables plants to absorb heavy metals efficiently from the soil. In contrast, passive uptake depends on diffusion or nonspecific ion channels, al­lowing heavy metals to enter the plant without energy expenditure [55].
Several factors influence the efficiency of heavy metal absorption by roots. Soil pH is a major determinant, as it affects the availability of heavy metals for uptake. In acidic conditions, heavy metals are more likely to exist in their ionic forms, making them more accessible to plants. Additionally, soil characteristics such as organic mat­ter content and cation exchange capacity also play a role in regulating heavy metal absorption [7].
Dinu et al. [12] examined how peppermint (Mentha piperita) responds to soil con­tamination by heavy metals such as cadmium, lead, nickel, and arsenic. The study as­sessed the movement of these metals from the soil into different plant parts, including roots, stems, and leaves, and compared the findings with a control group grown in uncontaminated soil. Peppermint seedlings were exposed for 3 months to two metal mixtures with similar concentrations. The first mixture contained arsenic and cad­mium, while the second included arsenic, cadmium, nickel, and lead. The metal con­centrations were 23.7 mg/kg for arsenic, 5 mg/kg for cadmium, 136 mg/kg for nickel, and 95 mg/kg for lead.
The results showed that cadmium, nickel, and lead accumulated in different plant tissues, with arsenic remaining undetectable. The accumulation pattern followed the order: roots > stems > leaves. During the first month, no significant differences in growth, development, or chlorophyll content were observed when compared to the control plants. However, after 3 months, signs of phytotoxicity began to appear. Anal­ysis of metal translocation and transfer factors yielded values below 1, indicating that M. piperita primarily retained metals within its root system. These findings suggest that peppermint can effectively stabilize heavy metals in its roots during short-term exposure, demonstrating its tolerance to contaminated conditions when grown in nu­trient-rich garden soil. This research highlights peppermint’s potential as a metal­resistant plant, particularly for applications where root-based metal stabilization is needed.
+
ions and H+-ATPase. This
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7.5 Transport and accumulation in various plant tissues

Once absorbed by the roots, heavy metals are transported to different plant tissues via the vascular system. In flowering plants, this movement primarily occurs through the xylem, which carries metals from roots to stems and leaves, and the phloem, which facilitates transport between stems and leaves. During this process, heavy met­als accumulate in various plant parts. While roots, stems, and leaves serve as the pri­mary sites of accumulation, their specific distribution varies based on plant species, metal type, and environmental conditions. For instance, cadmium predominantly ac­cumulates in roots, whereas lead and zinc are more commonly found in stems and leaves [6].
A study conducted in 2021, titled Hysteresis of Heavy Metal Uptake in Dandelions, examined how heavy metals are absorbed and distributed within dandelion plants. The results indicated that these metals could accumulate in different plant tissues, po­tentially affecting the plant’s medicinal properties [56].
7.6 The effect of soil type and environmental
conditions on heavy metal uptake
Soil composition and environmental conditions are key factors influencing the uptake and accumulation of heavy metals in plants. Various physical and chemical character­istics of the soil, such as pH, moisture content, organic matter, mobile cation concen­trations, and microbial activity, significantly affect the extent to which plants absorb these metals. For example, in acidic soils, heavy metal ions are more readily available, facilitating their uptake by plants. Conversely, in alkaline soils, heavy metals tend to form mineral complexes or insoluble precipitates, reducing their bioavailability.
In addition to soil properties, environmental factors like temperature, light, and moisture play a crucial role in heavy metal absorption and transport within plants. Higher temperatures can stimulate enzymatic activity and metabolic processes, thereby enhancing metal uptake. Similarly, moisture levels influence metal bioavail­ability, with heavy metals being more accessible to plants in wetter soil conditions [13, 57].
A study investigated the effects of different exposure durations to thiram on the uptake of manganese, cobalt, nickel, copper, zinc, cadmium, and lead in basil (Oci- mum basilicum L.). In addition, the research assessed various physiological parame­ters of the plants. The experiment was conducted using two common agricultural soil types found in rural areas of Poland. The methodology included soil analysis to deter­mine bioavailable and total metal forms, measurements of chlorophyll content, and
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 277
evaluations of gas exchange in plants. Metal concentrations were quantified using atomic absorption spectroscopy.
Analysis of variance indicated that thiram treatment significantly affected metal transfer from the soil to basil plants, influencing metal concentrations in both the roots and aerial parts. These effects were most pronounced on the 14th day after fun­gicide application. Thiram altered metal uptake and distribution within basil by modi­fying the microbial composition of the rhizosphere. The impact was more noticeable in plants grown in mineral soils than in organic soils, which have a higher buffering capacity [58].
7.7 The effects of heavy metals on physiology,
metabolism, and secondary metabolites in medicinal and aromatic plants
Heavy metals have a significant impact on various plant physiological functions, in­cluding growth, photosynthesis, respiration, and metabolic activities. One of the pri­mary effects is their disruption of the photosynthetic process. Metals such as cad­mium, lead, and zinc can inhibit key photosynthetic enzymes, including RuBisCO (ribulose-1,5-bisphosphate carboxylase/oxygenase), and interfere with chlorophyll production. This disruption reduces photosynthetic efficiency, limiting the energy available for plant growth [59].
Additionally, heavy metals influence plant respiration by altering mitochondrial structure and function, thereby reducing energy efficiency during the respiratory pro­cess [55]. These changes lead to decreased ATP production and an accumulation of free radicals, which can damage cellular membranes, proteins, and DNA. Heavy metal exposure also negatively affects plant growth, particularly in the early stages of devel­opment, leading to lower germination rates, reduced root and shoot elongation, and decreased dry weight [60, 61].
The adverse effects of heavy metals are particularly concerning for medicinal and aromatic plants, as their optimal growth is essential for synthesizing bioactive compounds used in pharmaceutical and aromatic industries. These plants are known for producing secondary metabolites with therapeutic and aromatic properties. Heavy metal exposure can interfere with the production of these metabolites by af­fecting enzyme activity and disrupting metabolic pathways. Key affected compounds include alkaloids (e.g., morphine, atropine, and papaverine), flavonoids (e.g., querce­tin, apigenin, and luteolin), terpenoids (e.g., menthol, thymol, and linalool), and antho­cyanins (Figures 7.5–7.7).
For instance, in aromatic plants such as mint and lemon, heavy metals can impair the biosynthesis of terpenoid compounds, which contribute to their characteristic aro-
Figure 7.5: Alkaloids’ chemical structures.
Figure 7.6: Flavonoids’ chemical structures.
Figure 7.7: Terpenoids’ chemical structures.
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mas. Metals like cadmium and lead inhibit the activity of enzymes involved in terpe­noid production, leading to a reduction in these vital compounds [62, 63].
Heavy metals can significantly influence the biochemical composition of medicinal and aromatic plants, leading to notable reductions in anthocyanins, flavonoids, and terpenoids. Anthocyanins and flavonoids, which belong to the phenolic compound group, play a crucial role in protecting plants from environmental stress while also providing antioxidant benefits to counteract free radical damage. Research suggests that heavy metal exposure leads to decreased anthocyanin and flavonoid concentra­tions in plants such as thyme, basil, and sage. This reduction is likely attributed to dis­ruptions in their biosynthetic pathways, triggered by oxidative stress resulting from heavy metal accumulation [64].
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 279
Similarly, terpenoid production in aromatic plants, including basil, mint, and pen­nyroyal, can be significantly impaired by heavy metals. These compounds are essen­tial not only for the characteristic scent of these plants but also for their medicinal properties, such as anti-inflammatory and anticancer activities. A decline in terpenoid biosynthesis negatively affects both the therapeutic efficacy and aromatic qualities of these plants, diminishing their overall value in medicinal and aromatic applica­tions [65].
Antioxidant activity is a fundamental medicinal property of plants, playing a vital role in shielding them from damage caused by free radicals. When exposed to heavy metal contamination, plants experience elevated levels of free radicals, placing con­siderable stress on their antioxidant defense systems. While some plants may tempo­rarily enhance their antioxidant responses to counteract the damage, excessive heavy metal accumulation can overwhelm these systems, ultimately reducing their effective­ness and making plants more vulnerable to oxidative stress [55].
In addition to affecting antioxidant properties, heavy metals also influence the antibacterial activity of medicinal and aromatic plants. These plants naturally pro­duce antibacterial compounds that help them resist harmful bacteria and microorgan­isms. However, exposure to heavy metals can alter the composition of these bioactive substances, leading to a decline in antibacterial potency and a subsequent reduction in the plants’ therapeutic value. Studies have demonstrated that heavy metals such as cadmium and lead can impair the antibacterial properties of plants, thereby diminish­ing their medicinal efficacy [7].
Furthermore, bioactive compounds – including alkaloids, glycosides, and essen­tial oils – are critical components of medicinal and aromatic plants, contributing to their therapeutic benefits. These compounds not only offer health-promoting effects but also define the unique characteristics of each plant. Heavy metal contamination disrupts the biosynthetic pathways responsible for producing these bioactive substan­ces. For instance, alkaloids present in plants like Datura and Peganum harmala de­crease under heavy metal stress due to the inhibited activity of key enzymes, such as alkaloid synthase, which are essential for their synthesis [8].
Likewise, glycosides, which are found in plants such as ginseng and thyme, are adversely affected by heavy metal stress. Alterations in the plant’s internal environ­ment due to metal exposure result in decreased glycoside production [7]. Essential oils, primarily composed of terpenoid compounds, are particularly vulnerable to heavy metal contamination. Plants like mint and pennyroyal experience a significant reduction in essential oil synthesis when exposed to metals such as cadmium and lead. This decline negatively affects both the aromatic properties and medicinal effi­cacy of these plants [65].
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7.8 Plant defense mechanisms against heavy metals

Plants utilize various defense strategies to withstand stress caused by heavy metal ex­posure. These adaptive mechanisms involve alterations in their antioxidant systems and the production of signaling molecules to mitigate heavy metal toxicity. The plant’s response to heavy metals is highly complex and depends on factors such as contami­nation levels and the specific type of metal involved. One of the most notable re­sponses to heavy metal stress is the increased activity of antioxidant defense systems.
Heavy metal exposure leads to the generation of free radicals within plant tissues, which can harm cellular membranes, proteins, and DNA. To counteract this damage, plants enhance their antioxidant defenses. Key antioxidant enzymes, including SOD, CAT, and peroxidase (POD), play a crucial role in neutralizing free radicals and mini­mizing oxidative harm. Research indicates that plants such as wheat and maize ex­hibit a significant rise in antioxidant enzyme activity, particularly SOD and CAT, when subjected to heavy metal stress as a means of reducing oxidative damage [66, 67].
Under extreme heavy metal contamination, the efficiency of antioxidant defense systems may decline significantly, compromising the plant’s ability to neutralize free radicals and mitigate oxidative stress. In such conditions, cellular membranes, pro­teins, and DNA become increasingly vulnerable to damage, leading to the breakdown of cellular structures and disruption of essential physiological processes. The weak­ened defense mechanisms can manifest as cellular stress symptoms, inhibited growth, decreased synthesis of vital biochemical compounds, and, in severe cases, cell death.
Beyond enzymatic antioxidants, nonenzymatic compounds also play a vital role in plant defense. These include flavonoids, phenols, and vitamin C, which help coun­teract heavy metal-induced oxidative stress through their antioxidant properties. Re­search suggests that exposure to heavy metals such as cadmium and lead can trigger an increase in the levels of these antioxidant compounds in certain plants, including beans and sainfoin, as part of their adaptive response to stress [67].
Plants synthesize specific signaling compounds to adapt to heavy metal stress. These molecules function as internal messengers, enabling plants to regulate their re­sponses to adverse conditions. Among these compounds are plant hormones such as auxins, cytokinins, salicylic acid (SA), and ethylene. SA is a key signaling molecule in­volved in plant responses to environmental stress, including heavy metal exposure. This hormone plays a vital role in strengthening plant defense mechanisms against metal toxicity. Research indicates that elevated levels of SA can enhance the activity of antioxidant enzymes, thereby alleviating the harmful effects of heavy metals on plant health [68, 69]. Ethylene is another essential hormone produced in response to heavy metal stress. It contributes to stress adaptation by regulating critical physiologi­cal processes, such as root development and tissue growth, which help plants better withstand unfavorable conditions [70].
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 281

7.9 Molecular and genetic responses to heavy metal contamination

Plants adapt to heavy metal stress through various molecular and genetic modifica­tions. These adaptations involve changes in gene expression, activation of genetic resis­tance pathways, and, in some cases, genetic engineering techniques aimed at enhancing tolerance. Heavy metals such as cadmium, lead, zinc, and copper influence multiple sig­naling pathways, leading to alterations in the expression of specific genes that regulate plant defense responses.
One of the primary responses to heavy metal exposure is the increased expres­sion of genes involved in the production of antioxidants and protective enzymes. For example, exposure to heavy metals can stimulate the upregulation of genes responsi­ble for synthesizing SOD, CAT, and POD. These enzymes are critical in neutralizing free radicals, reducing oxidative stress, and safeguarding plant cells from heavy metal toxicity [71, 72].
Additionally, heavy metals can activate genes associated with hormonal signaling pathways, including those governing ethylene, SA, and auxins. These hormones play an essential role in regulating plant defense responses to heavy metal stress [68]. To sur­vive in polluted environments, plants employ complex genetic mechanisms that regu­late the uptake, transport, storage, and detoxification of heavy metals within their cells and tissues.
A crucial component of the plant defense system against heavy metal stress is the role of transporter proteins, which regulate the movement of heavy metals within the plant. These proteins help transfer metals from the roots to other tissues or confine them within specific compartments for safe storage. For instance, metallothionein (MT) proteins and heavy metal ATPases (HMA) play a significant role in absorbing heavy metals and isolating them within designated plant structures.
Additionally, plants can minimize heavy metal uptake by stabilizing these con­taminants in the soil. This process involves the secretion of chemical compounds, such as organic acids and amino acids, which bind with heavy metals to reduce their mobility. One such mechanism, known as phytostabilization, allows plants to release these substances into the surrounding soil, thereby preventing further absorption of heavy metals [73].
Another way plants resist heavy metal stress is by making structural and func­tional adjustments to their cell membranes. Some plants reinforce their membranes to block heavy metal entry, while others modify their structure to reduce metal ab­sorption. Given the significant role of medicinal and aromatic plants, genetic engi­neering has emerged as a promising strategy to enhance their ability to tolerate heavy metals. This approach involves introducing genetic modifications that strengthen plant defense mechanisms and improve their capacity for metal uptake and detoxifi­cation.
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One genetic engineering technique involves incorporating genes that encode MT proteins and heavy metal transporters into medicinal plants. These genes help plants effectively sequester heavy metals in specific tissues or expel them altogether. For exam­ple, transferring HMA or MT genes into medicinal plants has been found to enhance their resistance to metals such as cadmium and lead. Additionally, genetic modifications can target hormonal signaling pathways to improve stress resilience. Enhancing the ac­tivity of SA and ethylene signaling pathways, for instance, enables plants to better man­age the adverse effects of heavy metals. Research has shown that increasing the produc­tion of these hormones through genetic engineering significantly improves the tolerance of medicinal and aromatic plants to heavy metal contamination.
Furthermore, cutting-edge technologies like CRISPR/Cas9 offer precise gene-editing tools to enhance plant resistance. This method allows for the targeted modification of genes responsible for heavy metal detoxification, thereby strengthening the plant’s abil­ity to tolerate and manage these contaminants more effectively [74].
7.10 Management and control of heavy metal
contamination in medicinal and aromatic plants
To mitigate the effects of heavy metals on plants, various agricultural and manage­ment strategies can be employed. One crucial approach is reducing soil contamination by addressing pollution sources. Effective management of industrial and agricultural waste plays a vital role in preventing heavy metals from entering the soil, thereby minimizing long-term environmental damage.
Additionally, techniques such as cover cropping and crop rotation help limit heavy metal exposure. Cover crops assist in immobilizing heavy metals within the soil, reducing their uptake by medicinal and aromatic plants. Likewise, crop rotation and diversifying plant cultivation in a given area can prevent excessive accumulation of heavy metals in the soil. For instance, planting crops that absorb and retain heavy metals in their root systems can act as a protective barrier, shielding medicinal plants from contamination [75, 76]. Effective soil and water remediation techniques play a vital role in managing heavy metal contamination in affected regions. One commonly applied approach is phytoremediation, which utilizes plants to cleanse environments polluted with heavy metals. This method encompasses various processes, including phytostabilization, hyperaccumulation, and phytodetoxification. Among these, phytos­tabilization is particularly significant, as it involves the use of plants to restrict heavy metals within the soil, thereby preventing their dispersion and minimizing environ­mental hazards (Figure 7.8).