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Original Article
2025
:18;
642025
doi:
10.25259/AJC_64_2025

Investigation of major, toxic, and trace element contents and mineral safety index (MSI) of parts of Elaeagnus angustifolia L. and total element contents in the soil using the ICP OES technique

GAP İnternational Agricultural Research and Training Center, Quality and Technology Laboratory Unit, Diyarbakır, Türkiye

* Corresponding author: E-mail address: mehmetdzgn@ymail.com (M. Düzgün)

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This is an open-access article distributed under the terms of the Creative Commons Attribution-Non Commercial-Share Alike 4.0 License, which allows others to remix, transform, and build upon the work non-commercially, as long as the author is credited and the new creations are licensed under the identical terms.

Abstract

Alternative medicine, perfumery, animal feed, and beverages use Elaeagnus angustifolia L. (Russian olive). Therefore, it is essential to determine the major, trace, and potentially toxic element (PTE) contents of the leaves and fruits of this plant. Moreover, the mineral composition of the soil may influence its elemental distribution. In this study, the content of major, essential trace, and potentially toxic elements (PTEs) in the leaf and fruit components (skin, pulp, and seed) of Russian olives and soil minerals was determined. Inductively coupled plasma optical emission spectroscopy (ICP OES) was used to measure the concentrations of major elements (Ca, K, Mg, Na, and P), essential trace elements (Fe, Cu, Mn, Zn, Cr, Co, Ni, Se, Sn, and V), and potentially toxic trace elements (Ag, As, Ba, Cd, and Pb) in Russian olive parts and soil samples. For the solubilization process, the microwave-assisted wet digestion technique was used on plant and soil samples. Additionally, the mineral ratio and mineral safety index (MSI) of these parts were calculated. Regarding mineral ratios and MSI, all plant parts were satisfactory in Ca/P but very low in Na/K. Furthermore, while leaf and pulp [K/Ca+Mg] were greater than the ideal value (2.2), the seed was found to be below this value. All samples were above 1.0 for Ca/Mg and below 500 for Zn/Cd. Moreover, Mg and Fe were overloaded in all parts of the plant. On the other hand, the findings show that the quantified plant parts have different concentrations of major, trace, and toxic elements. The components of Russian olive contained higher amounts of Mg, Ca, Na, and P compared to other elements. The seed contained only As, while the pulp was the only source of Se. However, Ag values were found to be well above the limit values in plant parts. ICP OES precisely measured element concentrations in plant and soil samples. This study provides important details about the different parts of E. angustifolia in terms of elements that will help to understand their pharmacological, toxicological, and nutritional uses.

Keywords

Elaeagnus angustifolia L
ICP OES
Mineral safety index
Toxic elements
Trace elements

1. Introduction

Belonging to the Elaeagnaceae family, Elaeagnus angustifolia L. is widely distributed in cold and arid parts of Asia, temperate regions of Europe, and one part of North America [1]. Elaeagnus boasts over 90 species worldwide [2]. The branches, leaves, flowers, and fruits of E. angustifolia have high economic value and are known as the “treasure tree” in the saline-alkali land. Pharmaceuticals, the perfume industry, and wood production have utilized different parts of E. angustifolia [1]. As a fruit, the Russian olive has a higher content of nutrients in terms of carbohydrates, protein, organic substances, amino acids, and vitamins, which provides a significant contribution to wildlife [3]. Moreover, it finds widespread use in medicine and pharmaceuticals across Asia and Europe. Several components were proven to have anti-inflammatory[4], muscle relaxant, anti-ulcerogenic, antimicrobial, antinociceptive [5], antitumor [6], and antioxidant effects [7]. Furthermore, the whole fruit and medulla powder of E. angustifolia showed a positive effect on relieving pain, stiffness, and physical function in women with osteoarthritis of the knee [8, 4]. It is also stated that its leaves can be used as tea and animal feed, while its fruit is used as pulp, seed pulp, jams, and drinks.

Food safety has emerged as a significant global public concern in recent decades owing to the widespread occurrence of metal contamination in plant-based meals [9, 10]. The different parts of E. angustifolia also contain variable concentrations of minerals. Branches, stem bark, leaves, and fruits contain Fe, Cu, Cd, Zn, Cr, Ni, and Co [11], whereas the most abundant mineral found in E. angustifolia fruit is potassium (8504 mg/kg), followed by sodium (1732 mg/kg) and phosphorus (635 mg/kg) [12]. Potentially toxic elements (PTEs) include those with more than 60 metals, including Pb, Cd, Cr, Ba, As, and Hg. Studies that looked at how much of them built up in plant tissues and organs showed that they might be phytotoxic substances that stop plants from growing or even kill them [13]. External sources, such as agricultural and anthropogenic activities, can introduce metals into the food chain. Trace metals can be toxic even at low concentrations. They are highly stable, persistent in the environment, and bioaccumulate in the food chain. The recognized adverse effects encompass fatal and chronic diseases, including neurological symptoms, Alzheimer’s disease, dementia, hepatic syndrome, cardiovascular disorders, dermatological issues, systemic ailments, and renal failure. Additional illnesses include hepatic ailments, developmental difficulties, autism spectrum disorders, cerebral palsy, and skeletal disorders. At the cellular level, increased trace metal concentrations can disrupt cellular functions, impair damage-repair mechanisms, and induce apoptosis [1416]. The United States Environmental Protection Agency (USEPA) has identified priority pollutant trace metals for monitoring in food products due to their potential harm to human health. The enumeration comprises Cd, Cu, Co, Fe, Ni, Pb, and Mn. Particular trace metals accumulate more swiftly in certain organs, resulting in more significant health effects on those organs than on others. For example, Cr and Ni significantly impact respiratory organs, Cd specifically affects the kidneys and intestines, Pb is linked to neurotoxicity and nephrotoxicity, while As consumption via drinking water can induce urinary bladder cancer. Group 1 human carcinogens include compounds of Cr, Cd, and Ni [17, 18]. Industrial, municipal, and agricultural activities, like the use of fertilizers, are the primary contributors to soil contamination, introducing PTEs to plants. These elements may accumulate in greater quantities in the leaves of plants following their uptake from the soil. Consequently, regular oversight of these components is essential. When essential elements for nutritional requirements and toxic elements in food items exceeded the standards set by the World Health Organization (WHO), the European Food Safety Agency’s (EFSA) became problematic due to their negative impact on human health. If food contains potentially hazardous elements (PTEs: Cr, Fe, Mn, Ni, Co, Cu, Zn, Al, Cd, and Pb) over WHO and EFSA limits, public health is at risk in developing nations [19]. Soil is the source that ensures the continuity of fertility for mankind. Research has shown that plants’ element uptake from the soil is greatly affected by the soil’s pH, texture, lime, and similar physicochemical properties. The uptake of metals into root cells and the entry point into living cells constitute one of the important steps for the phytoextraction process. In addition, Liu et al. [20] stated in their study that soil stoichiometry is affected by the C/P and N/P ratio of the soil. Soil C:N:P ratios govern biogeochemical processes in soil, such as mineralization/immobilization, nitrification/denitrification, and plant uptake/release, which affect the transformation direction and efficiency of organic and inorganic forms of soil nitrogen and phosphorus. However, for phytoextraction to occur, metals must be transferred from the root to the shoot. Two recognized processes control the movement of metal-containing sap from roots to shoots. These are root pressure and leaf transpiration. Silver, Cr, Pb, Sn, and V are more abundant in shoots (leaves and stems) than in roots and rhizomes. Cadmium, Co, Cu, Fe, and Mo accumulate more in roots, rhizomes, and shoots (leaves and stems) than in Ni. Nickel, Mn, and Zn are less uniformly distributed in the roots and shoots of the plant [21]. Salt [22] reported that the maximum amount of some heavy metals that are harmful to plants and other living things that can be found in the soil should be between 10 and 50 mg/kg for Ni, 1 to 20 mg/kg for Co, and 10 to 80 mg/kg for Cr. However, these amounts vary depending on the plant.

Many different techniques have been used to find out the amounts of elements present, such as graphite furnace atomic absorption spectrometry (GFAAS) [23], inductively coupled plasma-optical emission spectroscopy (ICP OES) [24], inductively coupled plasma- mass spectroscopy (ICP MS) [25], polarography and voltammetry [26], and flame atomic absorption spectrometry (FAAS) [27]. Among these techniques, ICP OES offers a wide dynamic linear range.

The objective of this study is to analyze a valuable plant with such a wide area of use in terms of essential and non-essential elements, to determine their amounts and to calculate the important mineral ratios, to determine the safety indices of the important elements, and to estimate the health effects of these plant parts. Therefore, it examined major, trace, and toxic elements in E. angustifolia grown along the Tigris River in Diyarbakır, Türkiye, and compared them to soil element levels. Major elements such as Ca, Mg, K, Na, and P are abundant in plants and foodstuffs and are essential for both nutrition and health, as well as good plant growth. Essential trace elements, such as Fe, Mn, Zn, Cu, Cr, Ni, Co, Se, and V in certain ratios, are critical for the enzyme and hormonal systems of the body’s mechanisms. High amounts of these can have toxic effects on organisms. The determination of the concentrations of PTEs, such as As, Pb, Cd, Ba, and Ag, which can show side effects even in low amounts without a certain benefit in plants, animals, and humans, is important for the literature and food codexes in general. Therefore, these elements were selected and evaluated in this study. Additionally, mineral ratio and MSI of plant parts are computed to assess trace and toxic elements above acceptable limits in plant parts to provide element concentration data for future pharmacological, toxicological, and nutritional studies of E. angustifolia.

2. Materials and Methods

2.1. Materials

The samples were collected in November 2018 at the stage of ripening; leaves and fruit were collected from different trees, and soil samples were taken from 30, 60, and 90 cm depths from the coordinates (37.947359, 40.265342) of Sur, a district of Diyarbakır, Türkiye. It is assumed that tree roots at depths of 30, 60, and 90 cm take up plant nutrients and that micro, macro, and toxic elements are transported to the plant through the roots at these depths. Therefore, generally, when analyzing the soil of fruit trees, the soils at these depths are analyzed separately. The collected fruits were divided into the skin, pulp, and seeds. To remove moisture, the pulp, skin, seed, and leaves were dried in the oven (Mipro) at 65°C for 24 hrs and then ground into small particles with the mill (Perten 3303). Furthermore, soil samples were prepared for elemental and physical analysis. A microwave digestion unit (Milestone Start D, Italy) was used for the digestion of the samples, and ICP OES (Thermo Fisher Scientific ICAP 6000, England) was used for elemental determination.

2.2. Methods

2.2.1. Microwave digestion procedure

To dissolve, 0.25 g of plant parts like pulp, skin, leaf, and seed were put into Tetrafluoroethylene (TFM) containers, and 2 mL of 30% H₂O₂ (Merck No. 1.08600.2500) and 8 mL of 65% HNO₃ (Merck No. 1.00456.2500) were added. Furthermore, 0.3 g soil samples were put into TFM containers, and 6 mL of 65% HNO₃, 1 mL of 30% H₂O₂, and 3 mL of 40% HF (Merck No. 1.00337.2500) were added. Blank samples were also prepared for both plant and soil samples and analyzed on the instrument according to the same procedure. For dissolving plant parts, HNO3 was used, and the microwave program was set at 1200 watts of energy and 180°C, depending on the number of samples. For better dissolving silica in soil samples, HF was used, and 600 watts of energy were used, also depending on the number of samples. Table 1 presents the solubilization program. After solubilization, the samples were allowed to cool, and they were filtered with blue-band filter papers and completed with 50 mL of ultrapure Milli-QTM water (Millipore Corporation, USA). Samples were kept in polypropylene containers until the day of analysis.

Table 1. Microwave digestion program for Russian olive parts and soil samples.
Step (plant samples) Time (mins) T (oC) Power (W)
1 20:00 180 1200
2 15:00 180 1200
Step (soil samples)
1 20.00 180 600
2 20:00 180 600

2.2.2. Validation procedures for analytical methods

For ICP OES calibration, standard concentrations of all elements were prepared with ICP Multielement Stock Solution (HIGH-PURITY, ICV-4, 1408726, Charleston, SC); appropriate wavelengths were selected for each element in the method, and a radial view type was selected for soft elements and an axial view was selected for strong elements. Conditioning of the plasma was done for 30 mins, and the certified reference material (CRM) material prepared according to the same procedure was analyzed. After determining the accuracy and validity of the analysis, the real samples were analyzed. Table 2 presents the operating conditions of ICP OES. Table 3 displays the standard concentration ranges of the elements. Reference standards validated analytical procedures in terms of linearity, limit of detection (LOD), and quantification (LOQ). Linearity was assessed by means of calibration curves of each analyte, and the obtained correlation coefficients were comprised between 0.9971 and 0.9999 for inorganic elements (Table 3). LOD and LOQ were determined as 3 and 10 times, respectively, the blank standard deviation (n=10) divided by the slope of the analyte calibration curve. For inorganic elements, LODs ranged from 0.00062 mg/kg to 0.44100 mg/kg, and, accordingly, LOQs were between 0.00206 mg/kg and 1.47000 mg/kg, respectively, for Zn and P (Table 3). This study chose the best spectral lines and view types for each element based on how strong they were and how little interference they caused.

Table 2. Instrumental operating conditions for Thermo ICAP 6300 ICP-OES.
Parameter Property

Polychromator

Detector

Echelle based polychromator, UV region (166 – 847 nm)

High performance CID86 chip, Charge Injection Device (CID), 50,000 analytical wavelengths

Ultrasonic nebulizer

RF plasma generator

Spray chamber

Ultrasonic, concentric glass

27.12 MHz solid state, 750-1350 watt

Glass cyclonic

Normal Hydride System
RF Power 1100 W 1300 W
Flush pump rate 100 rpm -
Pump speed 50 rpm 30 rpm
Purge gas Argon Argon
Pump tubing type Tygon Orange/white -
Coolant gas Normal Hydride System
Flow 12 L/min. 16 L/min.
Auxiliary gas Normal Hydride System
Nebulizer flow 0.6 L/min. 0.3 L/min.
Auxiliary gas flow 0.5 L/min. 0.5 L/min.
View Mode Axial, Radial Axial
Auto sampler Cetac ASX-260 -
Table 3. Standard range, wavelengths, view, R2, LOD and LOQ values of the elements.
Elements Standard solution ranges (mg/L) Wavelengths (λ nm) View R2 LOD LOQ
As (Arsenic) 0.05-0.4 189.0 Axial 0.9996 0.01060 0.03500
Ba (Barium) 5-100 455.4 Radial 0.9999 0.03100 0.09300
B (Boron) 0.05-1 249.7 Radial 0.9997 0.00600 0.02000
Ca (Calcium) 50-400 317.9 Radial 0.9997 0.00078 0.00260
Mg (Magnesium) 50-400 279.5 Radial 0.9938 0.00105 0.00350
Na (Sodium) 50-400 589.5 Radial 0.9988 0.07300 0.24400
K (Potassium) 50-400 766.4 Radial 0.9999 0.18700 0.62400
Cd (Cadmium) 0.05-1 214.4 Axial 0.9999 0.00029 0.00095
Co (Cobalt) 0.05-1 228.6 Axial 0.9987 0.05700 0.19200
Cr (Chromium) 0.05-1 283.5 Radial 0.9999 0.01520 0.05070
Cu (Copper) 0.05-1 324.7 Radial 0.9999 0.02030 0.06700
Fe (Iron) 5-100 238.2 Radial 0.9999 0.02300 0.07600
Mn (Manganese) 0.05-1 257.6 Radial 0.9998 0.00280 0.00950
Ni (Nickel) 0.05-1 232.0 Axial 0.9999 0.00135 0.00450
Pb (Lead) 0.05-1 220.3 Axial 0.9981 0.00640 0.02140
P (Phosphorus) 5-100 178.2 Axial 0.9995 0.44100 1.47000
Sn (Tin) 0.05-1 189.9 Axial 0.9971 0.00156 0.00520
Se (Selenium) 0.05-0.4 196.0 Axial 0.9996 0.01900 0.06600
V (Vanadium) 0.05-1 310.2 Radial 0.9999 0.00300 0.01000
Zn (Zinc) 0.05-1 213.8 Axial 0.9993 0.00062 0.00206

The validation of the method was tested with certified standard reference material NCS DC 73350 (Poplar Leaves). Table 4 displays the results in terms of percentage recoveries. The recovery figures demonstrated the extraction efficiency of the different metals. The recovery percentages varied between 74% and 122% for Sr and Pb. (Table 4) and reproducibility (n = 3). The element contents of the samples were determined according to the program optimized by ICP OES.

Table 4. Element content of certified reference material (NCS DC 73350, Poplar Leaves) and recovery of elements by method.
Elements Found value (mg/kg) Certified value (mg/kg) Recovery (%)
As 0.34±0.2 0.37±0.09 92
B 51.8±0.6 53±5 97.7
Ca 13949±78 13506±161 83
Cd 0.32±0.006 0.32±0.07 100
Co 0.43±0.006 0.42±0.03 102.3
Cr 0.55±0.46 0.55±0.007 100
Cu 7.20±0.07 9.3±1 77.4
Fe 275±2.4 274±17 100.3
K 10253±93 13800±70 74.2
Mg 4836±15 6500±50 74.4
Mn 36±0.25 45±4 80
Ni 2±0.2 1.9±0.3 105.2
P 1820±6.8 2435±15 108.3
Pb 1.83±0.76 1.5±0.3 122
Sr 114±1 154±9 74
Zn 32.2±0.25 37±3 87

2.2.3. Physicochemical analyses in the soil

To examine the growing media of the plants, soil analysis was performed with the usage of some methods. The TS 8333 method TSE [28] was used to find the saturation percentage. In saturated mud, pH and EC (electrical conductivity) were also measured [29]. The Walkley-Black wet combustion method was used to measure the amount of organic carbon in the soil samples. The results were then turned into organic matter values by multiplying them by 1.72, which is known as the organic conversion coefficient [30]. The calimetric method by Allison and Moodie [31] determines the amount of lime, while the Olsen [32] method determines the phosphorus level. According to soil analysis results presented in Table 5, the soil texture taken from a 30 cm depth was clayey, and the soil taken from 60 and 90 cm depths was in a clayey-loam texture. On the other hand, soil samples were less calcareous in terms of lime, alkaline in terms of pH, and low in phosphorus and organic matter.

Table 5. Some physical and chemical properties of soil samples.
Depth (cm) Saturation (%) Texture Salinity (%) pH (sm) CaCO3 (%) (P) P2O5 (kg/da) Organic matter (%)
0-30 75.9 C 0.011 8.34 4.72 0.86 0.99
30-60 69.3 CL 0.006 8.28 4.72 1.20 0.49
60-90 66 CL 0.002 8.29 4.88 0.52 0.42

sm: Saturation mud, C: Clay, CL: Clay-loam

3. Results and Discussion

Major elements are minerals often present in substantial quantities in living beings and soil. Their substantial presence typically does not result in harmful effects for living creatures. Below is some information regarding them.

3.1. Major elements

Calcium: Russian olive’s seed had the highest Ca concentration among the plant parts, followed by the skin and pulp. It is clear that the ground Russian olive seed and fruit can be a beneficial source of Ca, and on average, plants contain 1000 to 10000 mg/kg of Ca, according to WHO [33]. Furthermore, soil samples and leaves were unable to identify Ca content, leading to no evaluation. Table 6 and Figure 1 show Ca values.

Table 6. Element contents of Russian olive components and soil samples (n=3, mean±sd, mg/kg, dry weight).
Elements Leaf Pulp Skin Seed Soil-30cm Soil-60cm Soil-90cm
Ag 16.46±1.1 22.25±1.2 14.75±3 19.5±2.1 13.35±3.4 10.24±0.9 6.12±0.2
As <LOD <LOD <LOD 0.62±0.1 3.4±0.05 3.81±0.7 3.67±0.4
Ba 22.01±4.1 1.73±0.02 3.08±0.03 5.58±0.2 161.7±11 190.3±13 149.8±5
Ca ND 1687±96 2790±56 4566±107 ND ND ND
Cd 0.186±0.12 0.271±0.09 0.228±0.13 0.183±0.04 0.0025 <LOD 0.0039
Co 0.028±0.003 ND 0.081±0.002 0.074±0.05 28.25±6.1 33.04±2.1 26.56±3.3
Cr 1.57±0.06 0.80±0.04 1.79±0.08 2.24±0.17 169±0.9 206.3±16 166±24
Cu 3.065±0.3 4.77±0.9 6.82±0.25 6.87±1.2 49.4±9 52.36±6 46.3±5.4
Fe 336.5±2.2 69.8±3.2 394±44 557.6±32 50301±156 63685±43 44344±52
K 5516±13 8793±25 8847±82 6344±61 5416±54 8374±12 6723±44
Mg 6231±15 519.2±41 662±23 1631±51 28403±112 36450±142 26280±111
Mn 209±16 9.50±8 14.51±9 37.5±11 1087±25 1290±38 1094±31
Na 987.5±2.3 496.3±5.4 542.4±7.1 370.8±5.2 408±8.6 570.6±6.1 451.5±2.5
Ni 2.74±0.09 1.10±0.2 0.72±0.08 1.29±0.12 32.6±2.1 34.9±9.1 30.4±3.3
Pb 1.42±0.07 0.82±0.12 0.92±0.18 2.06±0.09 1.64±0.14 1.84±0.45 0.97±0.04
Se <LOD 0.22 <LOD <LOD <LOD <LOD <LOD
Sn 19.91±2 24.3±2.2 29.7±3.4 9.17±0.6 14.3±0.17 15.5±0.6 15±0.23
V 2.55±0.3 2.66±0.9 2.26±0.8 3.93±0.9 141.9±21 162.6±17 133.9±34
Zn 19±0.5 12±0.3 8.36±0.2 23.17±0.4 95.9±1.2 99±2.6 80.4±1.4
P ND 1882±76 1903±65 2416±45 868±9 870±22 821±24

ND: Not detected, sd: Standard deviation

Radar graphic representation of major element distribution in plant and soil.
Figure 1.
Radar graphic representation of major element distribution in plant and soil.

Magnesium: When looking at the Mg results, it was found that they were mostly in the soil that was taken at a depth of 60 cm. The soils taken from 30 and 90 cm depths also showed high concentrations and proximity to each other. The leaves and seeds were the most commonly found plant parts, followed by the skin and pulp. Moreover, FAO/WHO [34] reports that plants contain an average of 1000 to 4000 mg/kg of Mg.

Sodium: The plant’s leaves had the highest Na values, but the soil, pulp, skin, and seed had similar ones.

Potassium: The K levels in the pulp and skin were similar to the K levels in the 60-cm-deep soil sample. The K level in the leaf was very similar to the value in the 30 cm depth soil sample, and the K level in the skin was similar to the value in the 90 cm depth soil sample. According to WHO [33], the average K level in plants is between 10,000 and 50,000 mg/kg.

Phosphorus: P wasn’t found in the leaves, but the seeds had the highest P value of all the plant parts. The P values in the soil were similar but still very low compared to the plant parts. Table 6 displays the results. Figures 1-3 provide examples of radar graphics that clearly show the prominent elements in plant and soil samples.

Radar graphic representation of essential trace element distribution in plant and soil.
Figure 2.
Radar graphic representation of essential trace element distribution in plant and soil.
Radar graphic representation of potentially toxic trace elements in plant parts and soil.
Figure 3.
Radar graphic representation of potentially toxic trace elements in plant parts and soil.

Humans and other species require heavy metals in specific quantities. Nevertheless, elevated exposures to heavy metals might potentially harm living organisms. The primary heavy metals that can induce toxicity include Zn, Cu, Ni, As, Cd, Pb, and Cr. Heavy metals in soil and water are frequently detrimental as they are assimilated by organisms and enter the food chain. They can exhibit bioaccumulation at that level. A significant quantity of hazardous chemicals accumulates inside the food chain. Life may be adversely impacted. In addition to living situations, hereditary factors, food habits, and environmental contaminants contribute to the development of numerous diseases. Details regarding several metals have been provided below.

3.2. Essential trace elements

Iron: Plant parts contain less iron than the soil, despite the soil’s abundance. Iron is a very prominent element because it is an essential trace element that plays a significant role in many metabolic activities, especially in anemia. According to WHO [33], the maximum permissible concentration of iron in soils is 5000 mg/kg, and in plants, it is 1000 mg/kg. Excessive Fe levels can lead to liver failure, dizziness, and gastrointestinal disorders [35].

Copper: Approximately 10 times more Cu was found in the soil parts than in the plant parts, and it was identified mostly in the seed and skin parts of the plant, followed by the leaves. Cu is also an important trace element for metabolism; the maximum permissible value of Cu in soils is 36 mg/kg, while the maximum permissible value in plants is 10 mg/kg [33]. Copper is essential for hair, skin, bone, and some internal organs, promoting significant growth. However, it serves as a fundamental building component and may lead to gradual development, greying of hair, reduced body warmth, and potential brain damage [36].

Manganese: Total Mn content in the soil was close to each other and very high compared to the plant, whereas in the plant’s parts, Mn was detected in leaves more than in other parts, followed by seeds, skin, and pulp. Mn is an important essential trace element. The maximum permissible value of Mn in soils is 1000 mg/kg, while in plants it is 100 mg/kg [34]. Elevated levels of Mn are associated with Alzheimer’s disease [37]. Manganese has been associated with mitochondrial disruption and is significant in the death of central nervous system cells, as described [38].

Zinc: While soil samples contained much more Zn, seeds and leaves exhibited the highest concentration, followed by pulp and skin. Zinc is a crucial trace element for hormonal balance and metabolism, and the maximum permissible value for Zn in soils is 300 mg/kg, while in plants it is 100 mg/kg [34]. Zinc concentrations over 3 mg/L in water result in numerous health issues [39]. Zinc, ulcers, pulmonary edema, and irritation of mucosal membranes and respiratory pathways induce airway irritation [40]. Additionally, experimental mice were utilized to assess the impact of Zn in a study examining its carcinogenicity and effects on patient behavior [41].

Chromium: The pulp contained the least Cr, while the seed contained the most. On the other hand, the soil samples showed very high Cr levels compared to the plant parts. In addition, it is stated that Cr is involved in the insulin mechanism, and the maximum permissible value for Cr in soils is 100 mg/kg, while in the plants it is 1.3 mg/kg [33]. Chromium poses a health risk when consumed within the established daily dosage limits. Excessive inhalation of Cr can lead to upper respiratory tract diseases, asthma, and hemorrhages resulting from nasal damage reported [42].

Cobalt: It was not detected in pulp but was found in the skin, seeds, and leaves in tiny amounts compared to soil. The maximum permissible Co value in plants is 0.5 mg/kg, whereas the soil has a value of 10 mg/kg [33]. Cobalt dissolves in the lungs and subsequently enters the bloodstream and urine [43]. Inhalation of Co absorbed into the body induces lung cancer and detrimental effects on DNA structure [44].

Nickel: The leaves exhibited the highest concentration of nickel, while the skin showed the least amount. However, concentrations were close to each other and higher than the plant in soil samples. The maximum permissible Ni value in plants is 10 mg/kg, while in the soil it is 80 mg/kg [33]. Excessive Ni consumption beyond the threshold can lead to diarrhea, vomiting, respiratory constriction, liver and kidney damage, and chronic Ni toxicity, perhaps resulting in allergic reactions [45].

Selenium: Se was not detected in soil samples, but in plant parts, it was only detected in pulp (0.22 mg/kg). Moreover, Se plays an important role in many metabolic events, and the maximum Se content in soils and plants generally varies between 0.1 and 2 ppm. On average, the Se content in soils was 0.31 ppm. Although Se is a micronutrient that can be beneficial for plants at low concentrations, high doses can lead to toxic effects. Therefore, it is important to carefully monitor the selenium content in plants and soils [46].

Tin: It was found to be higher in all plant parts than in soil samples, except for the seeds, and close values were detected in the soil. The Turkish Food Codex determined that the maximum residue amount for Sn is 50-200 mg/kg [47].

Vanadium: The plant’s seed contained the highest amount of V, while leaves, pulp, and skin also showed similar levels. In soil samples, it was detected at quite high levels and close to each other compared to the plant. Table 6 and Figure 2 display the results. The average V content of soils around the world ranges from 18 mg/kg to 115 mg/kg, while the V content of plants ranges from 0.06 mg/kg to 3 mg/kg [48].

3.3. Potentially toxic trace elements

Silver: Silver content was higher in all plant parts than in the soil samples. The pulp of the plant contained the highest concentration of silver, while the soil at a depth of 90 cm had the lowest. While there is no universally accepted maximum concentration for silver in plants from FAO or WHO, concentrations above 0.1 to 1 mg/kg are generally considered harmful [49]. Accordingly, Ag values were found to be well above the limit values in plant parts. Due to anthropogenic activity, Ag is progressively functioning as a pollutant, resulting in the contamination of ecosystems and soils with numerous silver compounds (nanoparticles, oxides, sulfides, etc.). As agricultural crops absorb trace elements from irrigation water and soil, direct contact between Ag nanoparticles and plant roots may result in their uptake and translocation to shoots, stems, and leaves. Silver nanoparticles can infiltrate plant organs from the soil through various mechanisms. The initial method involves diffusion into seeds, followed by absorption into the root, and ultimately translocation to various plant organs. The other method involves absorption by plant roots, followed by migration to other organs. The third method involves direct migration to plant organs and localization inside the epidermal or xylem cells. The pathways for Ag nanoparticles to enter plant cells from soil or water are contingent upon their size, concentration, and physicochemical properties, in addition to the features of the crops and soil structure. Nevertheless, insufficient research exists to evaluate the impact of Ag and its nanoparticles on plants, as most studies are undertaken during the early stages of plant development.

Arsenic: Only the seed contained 0.62 mg/kg of the substance. Furthermore, in the soil samples, the highest value was 3.81 mg/kg. According to FAO, the maximum permissible value in soils is 20 mg/kg, whereas the average amount of As that can be found in foods is 0.1–2.0 mg/kg [50], and the maximum permissible value in foods is 0.02 mg/kg [51]. Arsenic induces hepatomegaly, anemia, and the development of brown spots on the skin, along with several dermatological conditions. Elevated As concentrations have been demonstrated to impact bone health and have been associated with respiratory system malignancies [45].

Barium: Plant parts primarily involved leaves, with seed, skin, and pulp following closely behind. Furthermore, the soil samples revealed high levels of Ba. To sum up, regulatory bodies have not set a clear maximum concentration for Ba in plants. However, concentrations above 200 mg/kg are usually thought to be harmful, while lower levels are typically okay and don’t cause any problems [52].

Cadmium: Although the soil contained very little cadmium, plant parts contained more of it. Pulp had the highest amount, followed by skin, leaves, and seeds. According to FAO/WHO [34], the maximum permissible value for Cd in soil is 3 mg/kg, whereas it is 0.2 mg/kg in foods. Table 6 and Figure 3 present the results. Cadmium, osteoporosis, and tooth problems are the primary sources [53]. Research indicates that persistent Cd poisoning can lead to lung and prostate cancer associated with the condition [54].

Lead: The seed contained the highest amount of lead, followed by leaves, skin, and pulp. The maximum permissible value for lead in soils is 100 mg/kg, while for plants it is 2 mg/kg [33]. Despite Pb being the first metal utilized since antiquity, it has been assimilated into human metabolism. Lead is a significant heavy metal that is extremely detrimental [55]. Excessive Pb levels in the human body that disseminate to bones and other organs result in harm to the kidneys, brain, and nervous systems [56].

Russian olive parts and soil samples were analyzed, and the results were tabulated in Table 6. The study looked at the differences in element concentrations between different parts of the plant. The leaf had higher concentrations of Mg, Ba, Mn, Na, and Ni than the other parts. Khan et al. [57] studied the leaves of Russian olives and found that the amounts of Cu, Ni, Cr, Pb, Cd, Zn, and Co were 0.072±0.0009, 0.016±0.001, 0.002±0.0011, 0.006±0.0007, 0.009±0.0004, 0.780±0.0011, and 0.008±0.0034 mg/kg, respectively. These values are significantly lower than those found in the present study. The study by Hambaba et al. [58], on the other hand, discovered that the leaves of E. angustifolia had Pb levels ranging from 1.05 ± 0.22 to 5.47 ± 4.65 mg/kg, Cd levels ranging from 0.01 ± 0.01 to 0.24 ± 0.23 mg/kg, Ni levels ranging from 2.13 ± 0.59 to 6.61 ± 3.75 mg/kg, Fe levels ranging from 30.8 ± 11.84 to 237 ± 76.62 mg/kg, Cu levels ranging from 4.18 ± 0.49 to 19.42 ± 15.89 mg/kg, Zn levels ranging from 45.0 ± 7.50 mg/kg to 58.5 ± 17.91 mg/kg, and Mn levels ranging from 162.35 ± 30.81 mg/kg to 253.3 ± 14.83 mg/kg. On the other hand, the element concentrations that Khan et al. [57] observed were different from their values. To clearly identify these differences would require a huge amount of work. However, to summarize briefly, soil structure, texture, and other physicochemical properties of the countries may explain these differences, as well as the methods of analysis, chemicals, and equipment used. On the other hand, climate and environmental factors (such as applied fertilizers, pesticides, vehicle exhaust, industrial chimneys, and waste) may cause these differences. Moreover, in the study of Yildirim et al. [59] on E. angustifolia, Cu, Fe, and Mn amounts in leaf samples were determined by atomic absorption spectrophotometer (AAS), and the values found for Cu, Fe, and Mn were 25.39, 26.37, and 11.70 mg/kg, respectively. It was observed that Cu contents were considerably higher than the values of the current study, but Fe and Mn contents were significantly lower than the values of the present study. According to Noreen et al. [60], the amounts of N, P, K, Ca, and Mg in dry Russian olive leaves were 37,500, 5580, 43,700, 24590, and 7690 mg/kg, respectively. Whereas Motsara and Roy [61] reported that optimal N, P, K, Ca, and Mg ranges in plants were for N between 20000-50000, for P between 2000-5000, for K between 10000-50000, for Ca between 1000-10000, and for Mg between 1000-4000 mg/kg. The study found that the skin part had higher concentrations of Co, K, and Sn elements than other components (Table 6). The seed, on the other hand, had more As, Ca, Cr, Cu, Fe, Pb, V, Zn, and P than the other parts of the plant. This finding suggests that different parts of the plant accumulate different elements in different ways, with some elements being more concentrated in certain parts of the plant. These findings have implications for understanding the distribution of essential and non-essential elements in plants and their potential impact on human health. These results suggest that the leaf samples of Russian olives have sufficient levels of macro and trace elements for healthy growth.

3.4. The mineral ratio and mineral safety index of Russian olive parts

Mineral ratios are more important than minerals alone. These important ratios play an important role in the balance of metabolism and in the prevention and detection of certain diseases. In contrast, overloading some body elements can disrupt the uptake and mechanism of others. Therefore, these important element ratios and safety indices were tabulated (Tables 7 and 8) and evaluated. Ca/K, Ca/P, Na/K, Ca/Mg, Na/Mg, Zn/Cu, Fe/Cu, Ca/Pb, Fe/Pb, Zn/Cd, Fe/Co, K/Co, and the milliequivalent ratio of [K/(Ca + Mg)]; the mineral safety index (MSI) of Na, Mg, P, Ca, Fe, Cu, Zn, and Se was also calculated according to Eq. (1) [62-65].

Table 7. Calculated mineral safety index (MSI), RAI and standard MSI values of minerals.
Mineral RAI (mg) Leaf
Pulp
TV CV D %D TV CV D %D
Ca 1200 10 null null null 10 14.05 -4.05 -40.50
Na 500 4.8 9.48 -4.68 -97.50 4.8 4.76 0.04 0.83
Mg 400 15 233.60 -218.60 -1457 15 19.47 -4.47 -29.80
P 1200 10 null null null 10 15.70 -5.70 -57.00
Fe 15 6.7 150.30 -143.60 -2143 6.7 31.20 -24.50 -365.60
Cu 33 33 3.07 29.93 90.70 33 4.77 28.23 85.54
Zn 15 33 41.80 -8.80 -26.60 33 26.40 6.60 20.00
Se 0.07 14 null null null 14 44.00 30.00 214.30
Mineral RAI (mg) Skin Seed
TV CV D %D TV CV D %D
Ca 1200 10 23.25 -13.25 -132.5 10 38 -28 -280
Na 500 4.8 5.2 -0.4 -8.33 4.8 3.55 1.25 26.04
Mg 400 15 24.8 -9.8 -65.3 15 61.2 -46.2 -308
P 1200 10 15.85 -5.85 -58.5 10 20.13 -10.3 -103
Fe 15 6.7 175.9 -169.2 -2525 6.7 249.06 -242.36 -3617
Cu 33 33 6.82 26.18 79.2 33 6.87 26.13 79.2
Zn 15 33 18.4 14.6 44.2 33 50.97 -17.97 -54.45
Se 0.07 14 null null null 14 null null null

CV: Calculated value, TV: Table value, D: Difference, RAI: Recommended adult intake, No MSI: Standard for other elements.

Table 8. Calculated mineral ratio of plant parts.
Leaf Pulp Skin Seed Standart value Acceptable value
Ca/K null 0.19 0.32 0.72 4 4.2
Ca/P null 0.89 1.46 1.88 >0.50 2.6
Na/K 0.18 0.06 0.06 0.06 0.60 2.4
Ca/Mg null 3.25 4.21 2.78 1 7
[K/Ca+Mg]* null 3.98 2,56 0.77 <2.2 2.2
Na/Mg 0.16 0.95 0.82 0.23 4.17 4
Zn/Cu 6.19 2.51 1.22 3.37 8 8
Fe/Cu 109.78 14.6 57.7 81.2 0.90 0.90
Ca/Pb null 2057 3032 2216 84 84
Fe/Pb 236.9 85.12 428.2 270.6 4.4 4,4
Zn/Cd 102.1 44.2 36.6 126.6 500 500
Fe/Co 12017 null 4864 7535 440 440
K/Co 197000 null 109222 85729 440 2000
Milliequivalent ratio

To calculate MSI,

(1)
Calculated&nbsp;MSI = MSI&nbsp; ( standard ) / RAI&nbsp; ( standard ) × Data&nbsp; ( research ) &nbsp;or&nbsp;result

RAI is the recommended adult intake, while CV in the table will represent the calculated value of the calculated MSI from research results. The differences between the standard MSI and the MSI of the samples were also calculated [62].

Table 7 depicts the MSI of the Russian olive part samples. Table 7 also presents the standard MSI values for the elements. Na (4.80), Ca (10.0), Mg (15.0), Zn (33.0), Fe (6.70), Cu (33.0), P (10.0), and Se (14.0) [65].

The calculated MSI for Na ranged in plant parts from 3.55 to 9.48, with discrepancies between the table values (TV) and the calculated values (CV) ranging from 0.04 to -4.68. The zinc pulp (26.4) and skin (18.4) were below the standard value. Nonetheless, the output exceeding the acceptable value in the leaf (41.8) and seed (50.97) indicates a substantial uptake that could interfere with the Cu and Mn content necessary for metabolism. Elevated Zn levels are detrimental as they can impede the absorption of other metals, such as Cu and Fe. Iron is crucial for optimal growth, healthy blood cell formation, and hemoglobin production; its lack is linked to diminished cognitive performance [62]. A 2143% Fe excess was detected in the leaf. The finding indicates a potential risk of excessive indebtedness. Conversely, all plant components contain elevated levels of Fe compared to the usual value. Calcium, P, and Se values could not be available in the leaf and could not be calculated. On the other hand, there were positive differences in Na, Cu, Zn, and Se in the pulp, while negative differences were observed in Ca, Mg, P, and Fe. In addition, in pulp and skin, negative differences were observed in other elements except Cu and Zn, but Se could not be measured. In the seed, negative changes were observed in elements other than Na and Cu; also, Se could not be measured. The fact that Cu is positive differences in plant parts is a beneficial result for Fe, Mn, and Zn metabolism. However, high amounts of Cu can disrupt Fe, Mn, and Zn metabolism. On the other hand, the fact that Mg shows negative differences in all plant parts meant that it could overload the consumer by 1457% in leaves, 29.8% in pulp, 65.3% in skin, and 308% in seeds.

The minerals’ ratios are sometimes considered more important than their absolute levels. The chosen mineral ratios showed a satisfactory balance between these elements and provided information about what might happen if the connections between them are messed up. This disruption may affect disease conditions and physiological and developmental factors, along with the effects of nutrition and pharmaceutical drugs [63].

Table 8 shows the mineral ratios. The 6th and 7th columns of the table displays the ideal ratio and the acceptable ratio, respectively. The leaf did not have a Ca/K ratio, but the pulp, skin, and seed ratios were significantly lower than the standard ratio (4.0). Furthermore, the Ca/P ratio could not be determined in the leaf, but it was found that it was above 0.50 and below the acceptable value (2.6) in other plant parts. When it comes to optimal calcium absorption in the intestine and bone formation, higher Ca/P ratios would lead to faster bone growth because they allow for better absorption. Numerous animals have demonstrated that the Ca/P ratio influences blood calcium levels [66]. Na and K are needed to keep the osmotic balance in body fluids, keep the pH level stable, control the absorption of glucose, and help cells keep the right amount of protein as they grow [62]. All plant parts have a Na/K ratio well below the standard, which favors the non-enhancement of high blood pressure. Additionally, the Na/K ratio in food sources should be approximately 0.6. The WHO [67] recommended a Na/K ratio of less than 1 as an advantageous strategy for hypertension management. The Ca/Mg ratios in plant parts ranged between 2.78 and 4.21, exceeding the threshold of 1.0 but below the acceptable value of 7.0; the Ca/Mg ratio could not be measured in leaves. The Ca/Mg ratio aids in the regulation of blood glucose levels. Mg deficiency and an elevated Ca/Mg ratio cause excessive insulin release, resulting in a decrease in blood sugar levels. The [K/Ca+Mg]* milliequivalent ratio could not be determined in the leaf but was above the standard value (2.2) in pulp and skin and well below the standard value in seed. The report of Marton and Andersen [68] showed that the milliequivalent of [K(Ca+Mg)] must be less than 2.2 to prevent hypomagnesaemia. On the other hand, all plant parts showed a Na/Mg ratio significantly lower than the standard value (4.17). The Zn/Cu ratio was below the standard value in all plant parts. The Fe/Cu ratio was much higher than the standard value in all plant parts. The Fe/Cu ratios surpassed the advised threshold of 0.9. The elevated Fe/Cu ratio is due to the higher concentration of Fe compared to the lower amount of Cu. The ratios of Ca/Pb and Fe/Pb exceeded the acceptable ranges. Ca/Pb value could not be determined in leaves, but it was found to be much higher than the standard (84) in other plant parts. Likewise, the Fe/Pb ratio was well above the standard (4.4) in all plant parts. However, the Zn/Cd ratio was much lower than the standard value in all plant parts. This is not a desired situation either. On the other hand, Fe/Co and K/Co ratios could not be determined in the pulp but were found to be much higher than the standard value in other plant parts. This result is a desired situation.

4. Conclusions

Russian olive fruit minerals are rarely discussed in the literature. There are a few references on this topic. Most researchers believe Russian olive trees are ideal biological environmental monitors due to their hazardous compounds and heavy elements in their leaves. This study discovered no correlation between plant element quantities and soil element averages from 30, 60, and 90 cm depths. According to the results, Ag, Cd, K, Na, Pb, and P were identified in modest concentrations in the soil but more in the plant. It is thought that they may have accumulated in excess in the plant due to anthropogenic (fertilizer, pesticides, and car exhaust) reasons. Other elements such as Ba, Co, Cr, Cu, Mg, Ni, V, Zn, and Fe were found to be more abundant in the soil than in the plants. This result demonstrates that the accumulation of component elements is not solely dependent on the availability or scarcity of soil elements. Many variables may contribute to this condition. For instance, plant physiology, root nutrient absorption, and soil pH may also affect element accumulation. The impact of heavy metals on soil is contingent upon soil features; thus, a comprehensive study of the soil is essential to grasp the characteristics and interactions between heavy metals and soil. Consequently, it is imperative that comprehensive investigations be conducted, and that research and literature be enhanced. Additionally, in the study, plant components’ mineral ratio and MSI were calculated. Based on the difference between the calculated MSI and standard MSI values, the following conclusions were drawn: Fe was 2143% higher in leaf, 365.6% in pulp, 2525% in skin, and 3617% in seed. As determined in the study, the high Fe content in the soil and the low calcareous content of the soil samples may explain the high Fe MSI values calculated in the plant parts, because Fe uptake by plants is easier in low calcareous soils. Similarly, the study found that Mg was 1457% higher in the leaf, 29.8% higher in the pulp, 65.3% higher in the skin, and 308% higher in the seed. Moreover, Zn was found to be below the standard value in pulp and skin, whereas it was found to be above this value in leaf and seed. Furthermore, Na, Cu, Zn, and Se were found to be positively different in pulp, while Ca, Mg, P, and Fe were found to be negatively distinct. On the other hand, Ca/K, Na/K, and Na/Mg were found to be below the standard value in all plant parts, while Ca/Mg and Fe/Cu were found to be above the standard value in all plant parts. This ratio is believed to be associated with the plant’s physiology and the physicochemical composition of the soil. Moreover, the [K/Mg+Ca] ratio exceeded the optimal range in both pulp and skin, signifying elevated K absorption. Generally, it is preferable for these ratios to remain within an acceptable range, with lower element ratios being favored over excessively high ones. In a similar vein, a lower calculated MSI value is preferred over one that greatly exceeds the standard MSI values. The lacking ingredient can be substituted with another food source. Conversely, the Zn/Cd ratio was determined to be below the standard value, which is unfavorable. On the other hand, the MSI values revealed an excess of Mg and Fe in all plant components. This result indicates that the plant is abundant in Fe and Mg, and it is advisable for consumers to ingest it in specific proportions to mitigate Fe and Mg-related ailments. In addition, the study found significant levels of macroelements like K, Ca, Mg, Na, and Fe in plant components, which are essential for human and animal nutrition. However, Ag values were found to be well above the limit values in plant parts according to WHO or FAO results. These findings indicate that a regulatory evaluation for Ag would be advantageous, and additional research on the possible bioaccumulation dangers of Ag is necessary. Consequently, the impacts of heavy metals on plant physiology and the defensive mechanisms of plants against heavy metals must be comprehensively explored. In addition, the ICP OES method was safe, effective, and quick for analyzing macro, trace, and hazardous elements in plant and soil samples at the same time.

CRediT authorship contribution statement

Mehmet Düzgün: Writing – original draft, Visualization, Methodology, Investigation, Formal analysis, review & editing, Supervision, Data curation, Validation, Software, Resources

Declaration of competing interest

No potential conflict of interest was reported by the author(s).

Declaration of Generative AI and AI-assisted technologies in the writing process

The authors confirm that there was no use of artificial intelligence (AI)-assisted technology for assisting in the writing or editing of the manuscript and no images were manipulated using AI.

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