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Ординатура / Хирургия / Библиотека им академика М.И. Перельмана / Книга_5217_Библиотеки_им_академика_М_И_Перельмана.pdf
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Phytovolatilization
Phytoaccumulation/
phytoextraction
Phytodegradation
Rhizodegradation
Methods Used in Organic
Pollutants
Phytodegradation
Rhizodegradation
Phytovolatilization
Contaminants uptake
Phytostabilization
Phytoextraction
Methods Used in Metal
Contaminants
Rhizofiltration
Phytostabilization
PHYTOROMEDIATION TYPES
Figure 7.8: Uptake mechanisms by plants with phytoremediation technology [77].
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 283
Hyperaccumulation is a process in which certain plants absorb significant amounts of heavy metals and store them within their tissues [77]. This mechanism is particularly effective for plant species thriving in metal-contaminated soils. Studies have identi­fied plants such as Brassica juncea, Helianthus annuus, and Thlaspi caerulescens as highly efficient at extracting heavy metals from the soil and accumulating them within their tissues [78]. These species play a crucial role in remediating soils polluted with metals like cadmium, lead, zinc, and copper.
nated soils involves the application of soil amendments. These substances help re­duce the mobility and bioavailability of heavy metals in the soil. For example, add­ing organic materials such as compost and biofertilizers assists in stabilizing heavy metals and limiting their movement. Likewise, using mineral amendments like lime and gypsum can alter soil pH levels, thereby decreasing heavy metal availability to plants [79].
Beyond phytoremediation, another effective method for detoxifying contami-
Figure 7.9: Flower spike of Lavandula angustifolia.
284 Negar Valizadeh and Gülen Özyazıcı

7.11 Selection of heavy metal-resistant plants

An effective approach to mitigating the adverse effects of heavy metals is the selection of plant species that exhibit natural resistance to these contaminants. Such plants have evolved specialized mechanisms to cope with heavy metal stress, either by ab­sorbing and isolating these metals within their tissues or by preventing their uptake at the cellular level. Among medicinal and aromatic plants, species such as Lavandula angustifolia (lavender), Mentha piperita (peppermint), and Ocimum basilicum (basil) have shown significant resilience to heavy metal exposure. These plants are capable of growing and adapting even in environments with contaminated soils (Figure 7.9).
Plants employ various mechanisms to resist heavy metal stress, including the produc­tion of antioxidant compounds, alterations in metal transport pathways, and the syn­thesis of chemical substances that confine heavy metals within specific tissues. For ex­ample, certain medicinal plants can limit heavy metal absorption or stabilize these contaminants in the soil by secreting compounds such as organic acids and phosphates [80, 81].
A study by Pandey et al. [81] investigated the adaptation mechanisms of clary sage (Salvia sclarea L.) when exposed to high zinc concentrations (900 micromoles of Zn) over an eight-day period in a hydroponic system. The research aimed to understand the plant’s zinc tolerance strategies by assessing factors such as nutrient absorption, leaf pigmenta­tion, phenolic compound content, photosynthetic efficiency, and structural changes in the leaves. To analyze zinc distribution and essential element levels – including calcium, mag­nesium, iron, manganese, and copper – the study utilized inductively coupled plasma mass spectrometry (ICP-MS). Findings revealed that S. sclarea, as a zinc-accumulating spe­cies, counteracts toxic zinc levels by increasing the concentrations of iron, calcium, and manganese ions in its leaves. This adjustment helps sustain photosynthetic efficiency and supports the functionality of photosystems I (PSI) and II (PSII).
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 285
Furthermore, increased zinc levels notably boosted the synthesis of phenolic com­pounds and anthocyanins in the leaves, which play a vital role in detoxifying zinc and reducing oxidative stress. Although the plants were exposed to high zinc concentra­tions, indicators of damage, including lipid peroxidation and electrolyte leakage, ex­hibited only slight elevations. These results suggest that S. sclarea could be a practical and cost-efficient option for phytoextraction or phytostabilization of zinc-polluted soils. Moreover, genetic engineering holds great promise for enhancing plant toler­ance to heavy metals. The incorporation of specific genes that aid in detoxifying heavy metals can strengthen a plant’s capacity to absorb and neutralize these contam­inants. For instance, introducing MT and HMA genes into medicinal plants has been found to improve their resistance to heavy metals such as cadmium and lead [74, 82].

7.12 Case studies

Extensive research has explored the impact of heavy metals like cadmium, lead, and cop­per, which are major contaminants in agricultural soils. For example, Es-Sabihi et al. [83] studied the role of SA in alleviating copper toxicity in Salvia officinalis L. Their findings indicated that copper stress significantly hindered both stem and root growth while also depleting calcium, phosphorus, and potassium levels in leaves and roots. Interestingly, exposure to copper stress increased essential oil yield by 16.66% compared to control plants. However, the application of SA enhanced plant growth and replenished calcium, phosphorus, and potassium content in leaves and roots. Notably, treatment with 0.5 mM SA led to a 116.66% increase in essential oil content relative to untreated plants under copper stress. In terms of essential oil composition, copper stress resulted in a 19% de­cline in oxygenated monoterpenes, particularly α-thujone, camphor, and 1,8-cineole. However, SA application effectively restored these compounds to levels observed in non­stressed plants. These findings indicate that SA, especially at 0.5 mM concentration, can effectively mitigate copper-induced stress while enhancing growth, yield, and essential oil quality in S. officinalis L.
A study by Pirooz et al. [84] examined the effects of nitric oxide and silicon, both separately and together, on rosmarinic acid and essential oil production in S. officinalis leaves under normal and copper-stressed conditions. The findings revealed that high copper levels led to a decline in biomass and polyphenol content. However, moderate copper concentrations, particularly at 200 µM, were associated with an increase in poly­phenol levels, essential oil production, and antioxidant activity in the leaves.Similarly, research by Elzaawely et al. [85] found that treating shell ginger (Alpinia zerumbet (Pers.) B.L. Burtt & R.M. Sm.) with 500 mM copper sulfate resulted in a reduction in total essential oil yield. Interestingly, despite the overall decrease, certain essential oil compo­nents, including 1,8-cineole, linalool, camphor, borneol, and cumin aldehyde, showed in­creased concentrations.
286 Negar Valizadeh and Gülen Özyazıcı
Lajayer et al. [86] investigated the impact of different copper and zinc concentra­tions on the growth, nutrient composition, and essential oil production of Mentha pu- legium L. Their study revealed that the best growth outcomes, including plant height, shoot dry weight, essential oil content, and yield, were observed when 5 mg/kg copper and 10 mg/kg zinc were applied. The combined use of these metals at these concentra­tions enhanced the uptake of essential nutrients such as potassium, manganese, iron, copper, and zinc in the aerial parts of the plants. Moreover, notable increases were recorded in essential oil constituents, including pulegone, cis-isopulegone, α-pinene, sabinene, 1,8-cineole, and thymol. These findings suggest that appropriate levels of copper and zinc not only promote plant growth and nutrient absorption but also boost essential oil yield and quality in M. pulegium L.
Babashpour-Asl et al. [87] examined the impact of selenium nanoparticles on Cor- iandrum sativum L. under cadmium-induced stress. Cadmium was introduced at concen­trations of 0, 4, and 8 mg/L, while selenium nanoparticles were applied as a foliar spray at 0, 20, 40, and 60 mg/L. The findings revealed that cadmium stress led to increased cadmium accumulation in both roots and shoots of coriander; however, the application of selenium nanoparticles significantly reduced this uptake. Exposure to the highest cad­mium concentration resulted in decreased root and shoot biomass, chlorophyll content, and relative water content (RWC), whereas selenium nanoparticles improved these pa­rameters. Additionally, cadmium stress elevated proline and malondialdehyde (MDA) levels, while selenium nanoparticle treatment lowered MDA levels, thereby reducing lipid peroxidation. Changes in essential oil composition were also observed, particularly in compounds such as n-decanal, 2E-dodecanal, 2E-decanal, and n-nonane, in response to cadmium stress and selenium supplementation. The study concluded that selenium nanoparticles alleviated cadmium-induced stress by enhancing growth, biochemical properties, and essential oil quality in coriander plants.
Farajzadeh Memari-Tabrizi et al. [88] investigated the effects of silicon nanopar­ticles on Satureja hortensis L. cultivated in cadmium-contaminated soil. Cadmium stress significantly reduced root and shoot biomass, along with RWC, while increasing cadmium accumulation in plant tissues and proline levels. Interestingly, moderate cadmium stress led to an increase in total phenolic content (TPC), total flavonoid con­tent (TFC), and essential oil production. Foliar application of silicon nanoparticles (1.5 and 2.25 mM) under cadmium stress improved plant growth and boosted essential oil yield. Key essential oil components, including carvacrol, γ-terpinene, p-cymene, and thymol, were influenced by both cadmium stress and silicon nanoparticle treatments. Overall, the study suggested that applying silicon nanoparticles at concentrations of
1.5–2.25 mM mitigated cadmium-induced stress by enhancing physiological and bio­chemical characteristics in S. hortensis L.
A study examined the effects of cadmium and lead on seed germination, growth characteristics, and essential oil composition in Ocimum basilicum L [89]. Soil was treated with cadmium (0, 5, 10, and 20 mg/kg) and lead (0, 100, 200, and 400 mg/kg) over a 2-month period. The findings indicated that exposure to these heavy metals adversely
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 287
impacted seed germination, flowering, stem growth, leaf area, and dry biomass. Gas chromatography-mass spectrometry (GC-MS) analysis identified 38 compounds in the essential oil, with major constituents including estragole, 2,6-octadienal, caryophyllene oxide, caryophyllene, phthalic acid, and geranial. Although cadmium and lead stress negatively affected plant growth and morphology, they also enhanced essential oil yield and modified its composition. These results suggest that O. basilicum may hold promise for phytoremediation in contaminated soils.
Poursaeid et al. [90] also reported that cadmium exposure stimulated essential oil production in basil. Their study found that different cadmium concentrations in­creased the synthesis of key compounds such as geranial, linalool, and estragole in a dose-dependent manner. These findings indicate that cadmium stress, at specific lev­els, can influence the biosynthesis of active metabolites in basil plants.
Similarly, Mohammed et al. [91] investigated the effects of cadmium-contaminated irrigation on two mint species: spearmint (Mentha × piperita L.) and mint (M. spicata var. crispa L.). Their research revealed significant phytotoxic effects, including abnor­mal growth patterns and a decline in total chlorophyll levels due to cadmium exposure.
Youssef [92] also observed that applying cadmium (5, 10, 15, 20, and 25 ppm) and lead (100, 350, 750, 1,000, and 1,500 ppm) to Ocimum basilicum L. (basil) increased es­sential oil yield. However, a separate study on Melissa officinalis L. (lemon balm) found that soil contamination with cadmium at concentrations of 10, 20, and 30 mg/kg over 3 months led to a significant decrease in essential oil production [93]. This de­cline was likely attributed to structural and functional damage that interfered with essential oil biosynthesis.
Another study assessed the essential oil yield of vetiver grass cultivated in Bot­swana’s mine tailings and explored the effects of chelating agents such as ethylenedia­minetetraacetic acid (EDTA) and arbuscular mycorrhizal fungi (AMF) on oil produc­tion. The findings revealed that vetiver grass grown in mine tailings produced a higher quantity of essential oil compared to those in uncontaminated soils. In steril­ized soil, the oil yield was only 0.26%, whereas it increased to 0.86% in mine tailings. Further enhancements were observed with the addition of EDTA or AMF, raising the yield to 0.95% and 0.89%, respectively. These improvements were attributed to greater heavy metal uptake, which induced stress in the plants and stimulated the production of secondary metabolites, including essential oils. Notably, despite the elevated heavy metal concentrations in mine tailings, the extracted essential oils contained negligible amounts of these metals, highlighting the suitability of vetiver grass for thriving in polluted environments while producing high-quality essential oils [94].
Amirmoradi et al. [95] examined how different concentrations of cadmium (10, 20, 40, 60, 80, and 100 ppm) and lead (100, 300, 600, 900, 1,200, and 1,500 ppm) in irri­gation water affected peppermint (M. piperita). Their study demonstrated that as cad­mium and lead levels increased, essential oil content decreased significantly, accom­panied by visible symptoms of phytotoxicity. Likewise, Azimychetabi et al. [96] investigated the impact of cadmium on peppermint and found that it altered the com-
288 Negar Valizadeh and Gülen Özyazıcı
position of essential oils. Specifically, pulegone and menthofuran concentrations rose, whereas menthol levels declined.
Kunwar et al. [65] investigated the effects of lead (500, 600, 750, and 900 ppm), cop­per (270, 300, 500, and 700 ppm), and cadmium (6, 10, 20, and 30 ppm) on M. spicata and O. basilicum. Their findings indicated that in O. basilicum, total essential oil yield, partic­ularly its main component linalool, increased, whereas methyl chavicol levels declined. In contrast, M. spicata exhibited no significant alterations in either essential oil content or composition.
Additionally, Sulastri and Tampubolon [97] examined cadmium’s influence on various plant species, including Vetiveria zizanioides, Cymbopogon citratus, C. nardus, Curcuma xanthorrhiza, Pogostemon cablin, and Alpinia galanga. The study highlighted species-specific variations, with essential oil production in V. zizanioides doubling, while other species showed minimal or no significant changes.
Sa et al. [98] investigated how different lead concentrations in soil influenced the growth of Mentha crispa. Their findings showed that increased lead contamination significantly enhanced essential oil production and modified its chemical profile. No­tably, the proportion of carvone, the dominant component of mint essential oil, in­creased to 90% in lead-contaminated soils. Prasad et al. [99] carried out a pot culture experiment to assess how increasing chromium and lead levels (30.0 and 60.0 mg/kg of soil) influenced yield, essential oil composition, and heavy metal accumulation in three mint species: M. piperita, M. arvensis, and M. citrata. The study found that while M. arvensis exhibited no significant changes in fresh weight yield under chromium and lead exposure, its essential oil yield declined considerably compared to the con­trol. Conversely, M. piperita demonstrated increased fresh weight yield, root biomass, and essential oil production under higher heavy metal concentrations, whereas M. citrata experienced reductions in these parameters.
The application of chromium and lead also led to significant alterations in essen­tial oil composition. In M. arvensis and M. piperita, levels of α-pinene, β-pinene, sabi­nene, β-myrcene, limonene, menthone, and isomenthone changed notably, while in M. citrata, sabinene, pinene, and linalyl acetate concentrations were affected. Addi­tionally, heavy metal accumulation in both the aerial parts and roots increased across all three mint species, with the highest levels observed in the roots. Based on these results, M. piperita was identified as the most suitable species for cultivation in chro­mium- and lead-contaminated soils, followed by M. arvensis and M. citrata.
Zheljazkov et al. [100] examined how cadmium, lead, copper, and their combina­tions affected Anethum graveolens L. (dill), Mentha × piperita L. (mint), and Ocimum basilicum L. (basil). Their findings indicated that exposure to these heavy metals led to a reduction in menthol content within mint essential oil and a decline in total oil yield in basil. Likewise, at the highest tested copper concentration (150 mg/L), a signif­icant decrease in dill oil content was observed.
In a separate study, Nabi et al. [101] explored the impact of nickel on menthol mint (Mentha arvensis L.) by growing seedlings in soils treated with nickel at concen-
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 289
trations of 20, 40, 60, 80, and 100 mg/kg. The results revealed a biphasic response, where lower nickel levels (20 mg/kg) stimulated essential oil production, while higher concentrations led to a decline. Interestingly, at 20 mg/kg, menthol content decreased, whereas menthone and menthyl acetate levels increased.
Biswas et al. [102] investigated the effects of arsenic exposure using disodium hy­drogen arsenate [Na₂HAsO₄•7 H₂O] at soil concentrations of 10, 50, and 150 ppm. Their study on basil (Ocimum basilicum) demonstrated a dose-dependent effect on essential oil production. While lower arsenic concentrations (10 and 50 ppm) increased oil yield, a higher level (150 ppm) resulted in a decline. Additionally, arsenic exposure influenced oil composition, with linalool levels rising and 1,8-cineole and methyl euge­nol concentrations decreasing.
Several studies have investigated the impact of soils contaminated with complex heavy metal mixtures on essential oil content. For example, Scora and Chang [103] found that the composition of peppermint (Mentha piperita) essential oil remained unchanged when the plant was cultivated in soils containing cadmium, chromium, copper, nickel, lead, and zinc. Similarly, Pandey et al. [104] studied Cymbopogon mar- tinii (palmarosa) grown in soil contaminated with tannery effluent, which contained substantial amounts of chromium, nickel, lead, and cadmium. Their results indicated that despite the presence of these heavy metals, palmarosa’s essential oil yield re­mained unaffected.
In another study, Gautam and Agrawal [105] examined Cymbopogon citratus (lem­ongrass) cultivated in soil mixed with sludge containing heavy metals and supplemented with wastewater effluent at different concentrations (5%, 10%, and 15% by weight). The findings suggested that lower concentrations (5% and 10%) enhanced total essential oil production, while the effects of higher concentrations were not specified.
Additionally, Gharib et al. [106] conducted a comparative analysis of wild mint (Mentha longifolia) collected from both polluted and non-polluted areas along the Nile River in Egypt. Their study revealed that plants from polluted regions produced higher essential oil yields. Furthermore, antioxidant activity, assessed using the DPPH (2,2-diphenyl-1-picrylhydrazyl) free radical scavenging assay, was significantly greater in oils from polluted sites. However, the oil composition varied, with menthone levels increasing and pulegone concentrations decreasing in plants exposed to pollution.
Givianrad and Hashemi [107] analyzed the chemical makeup of Tanacetum poly- cephalum Sch.Bip., a species belonging to the Asteraceae family. The plant samples were collected from different distances around the Veshnavah mine in Qom, Iran. Their study found that the concentration of chemical compounds increased as the dis­tance from the mine increased. The primary heavy metals detected in the soil samples from these regions were copper and silver. The research suggests that heavy metals significantly impact essential oil production and composition, depending on factors such as the type and concentration of the metal, the plant species, and surrounding environmental conditions. At lower concentrations, certain metals, including copper, cadmium, and lead have been shown to enhance both the total yield of essential oils
290 Negar Valizadeh and Gülen Özyazıcı
and the presence of specific components within them. For instance, increased essen­tial oil production has been noted in plants such as sage, coriander, and wild mint when exposed to minimal levels of heavy metals.
On the other hand, when present in higher concentrations, these metals exhibit phy­totoxic effects, leading to inhibited growth, disruptions in essential oil biosynthesis, and undesirable changes in the oils’ chemical composition. Additional negative effects include reduced chlorophyll content and indications of cellular toxicity. For example, in plants like shell ginger (Alpinia zerumbet) and basil (Ocimum basilicum), excessive heavy metal exposure resulted in lower essential oil yields, although certain compounds showed an increase under these conditions. Studies also indicate that plant responses to heavy met­als vary considerably between species. Some, such as Mentha piperita and Vetiveria ziza- nioides, display greater tolerance or even utilize heavy metals to enhance essential oil production. In contrast, species like Melissa officinalis experience a significant decline in essential oil yield when exposed to the same conditions. In summary, while low levels of heavy metals can enhance essential oil production, excessive amounts generally lead to reduced yields and alterations in chemical composition. These findings emphasize the im­portance of evaluating environmental conditions, metal concentrations, and plant species when dealing with contaminated soils. Furthermore, although low levels of heavy metals may offer benefits, their potential risks to both the environment and human health must be carefully considered.

7.13 Conclusions

Plants exhibit various responses to heavy metal-induced stress, ranging from inhib­ited growth to biochemical adjustments, such as changes in antioxidant enzyme activ­ity. Secondary metabolites, including essential oils, play a vital role in shielding plants from harmful substances and are notably influenced by these stressors. Research sug­gests that exposure to heavy metals, known for their toxicity, can impact both the quantity and composition of essential oils. However, the results remain inconsistent, with no definitive patterns identified. The fluctuations in essential oil yield and com­position in medicinal plants under heavy metal stress are influenced by multiple fac­tors, such as the plant species, the type of essential oil, and the concentration of heavy metals. Studies indicate that while low levels of heavy metals may promote essential oil production, higher concentrations generally have an inhibitory effect.
This decline is linked to disruptions in the metabolic pathways responsible for essential oil synthesis, which may arise from factors such as altered enzymatic activ­ity, increased free radical production, or direct effects on genes regulating these pro­cesses. Due to the limited scope of research and the small number of species studied, two important aspects require further investigation. Firstly, heavy metals impact gene expression, particularly those involved in essential oil biosynthesis, leading to
Chapter 7 Impact of heavy metal on the medicinal and aromatic plants’ biochemistry 291
either upregulation or downregulation and modifications in associated biochemical pathways. Secondly, recent studies have explored the feasibility of growing medicinal plants in heavy metal-contaminated soils as an alternative to food crops. Research on heavy metal bioaccumulation indicates that many medicinal plants can absorb sub­stantial amounts of these metals; however, this contamination typically does not ex­tend to their essential oils. Despite this, cultivating or harvesting plants in polluted environments poses challenges, as it may lead to unpredictable variations in essential oil yield and composition, potentially affecting their quality and therapeutic proper­ties. The limited research available and the narrow focus on specific plant species hin­der the broader applicability of findings, highlighting significant knowledge gaps.
To overcome these limitations, future studies should explore the effects of heavy metals on a wider variety of medicinal plant species and further examine the underly­ing mechanisms driving these impacts. A deeper understanding of this subject could aid in developing strategies to sustainably cultivate medicinal plants in contaminated environments while ensuring the preservation of their beneficial properties.

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