Trace Determination of Cr(VI) and Total Cr in Fruit and Vegetable Samples: Utilizing Monte Carlo Simulation for Risk Assessment in an Iranian Mining Area

doi:10.21203/rs.3.rs-3909058/v1

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Trace Determination of Cr(VI) and Total Cr in Fruit and Vegetable Samples: Utilizing Monte Carlo Simulation for Risk Assessment in an Iranian Mining Area

https://doi.org/10.21203/rs.3.rs-3909058/v1

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In light of food safety concerns, accurately determining Chromium (VI) concentrations in fruits and vegetables is imperative. Due to their complex matrices, achieving precise and efficient Cr(VI) measurement remains challenging, leading to uncertainty in dietary intake data. This study aimed to assess the Cr(VI) concentration in apples, grapes cultivated in farmlands and carrots available in local markets. An alkaline extraction method was employed at 80°C for 5 minutes, utilizing a solution containing 50 mM EDTA and dispersive liquid-liquid microextraction (DLLME). Apples and grapes were collected from two distinct case studies: Case Study A, located near Lead and Zinc factories, and Case Study B, situated at a significant distance from mining sites. The average total Cr and Cr(VI) concentrations in apples from the contaminated Case Study A were 438.4 ± 157 µg kg⁻¹ and < LOD, respectively. For grapes, were 450.265 ± 65.530 µg kg⁻¹ and 70.303 ± 18.208 µg kg⁻¹.

Conversely, the lowest average concentrations of Cr and Cr(VI) were observed in grapes, with values of 314.27 ± 14.41 µg kg⁻¹ and 52.06 ± 2.79 µg kg⁻¹, respectively, attributed to Case Study B. In the case of apples, the values were 241.65 ± 11.466 µg kg⁻¹ for Cr and < LOD for Cr(VI). For carrots available in the markets, the total Cr and Cr(VI) concentrations were found to be 2493.159 ± 280.57 µg kg⁻¹ and 326.32 ± 65.89 µg kg⁻¹, respectively. The assessment of potential health risks indicated that the intake of carrots and grapes increases the local population's carcinogenic Cr(VI) risks.

Cr(VI)

DLLME

Spectrophotometric Assay

Fruit and Vegetable Contamination

Risk Assessment

Mining Area

Chromium is a nutritionally hazardous heavy metal, primarily due to daily exposure to Cr(VI), a carcinogenic oxidized state of chromium. This element can adversely impact the safety and quality of agricultural products, especially in mining areas and industrial sites [1–4]; Due to daily exposure, the accurate and precise determination of Cr(VI) and understanding of the associated health risks in fruits and vegetables are of utmost importance[2].

Chromium concentration in foodstuffs has been the subject of numerous studies, particularly those related to crops grown around mining, industrial, and waste deposit sites, given the health risks posed by Cr(VI) in the most commonly consumed fruits and vegetables[5–8]. Most of the adverse effects of chromium revolve around the harmful effects of Cr(VI). Evidence suggests that oral exposure to Cr(VI) compounds can lead to liver, gastrointestinal tract, and respiratory system toxicity. Additionally, Cr(VI) toxicity is associated with immune toxicity, adverse effects on the male reproductive system, and hematologic effects in humans. Cr(VI) in food is likely carcinogenic when ingested through the human gastrointestinal tract[9].

Considering the safety and quality of fruits and vegetables as vital agricultural products, this study focuses on apples, carrots, and grapes grown in soil contaminated with Cr(VI) in mining areas. Due to the medium's complexity, accurately determining Cr(VI) in organic media presents a significant challenge[10, 11]. Given the limited data on chromium speciation in food, information regarding oral exposure to Cr(VI) remains uncertain. Most studies suggest that effective extraction of Cr(VI) in complex media can be achieved using a modified USEPA 3060A method[12] .This method creates an alkaline condition by adding Na₂CO₃ and EDTA at 80°C for 5 minutes. Cr(VI) is the only ion in this alkaline solution. Furthermore, the formation of the Cr(EDTA) complex is enhanced, which stabilizes Cr(III) and reduces ion reduction[13] .

Currently, the DLLME (Dispersive Liquid-Liquid Microextraction) technique is a well-known pre-separation, microextraction, and preconcentration technique used for effective determination of Cr(VI) in water, and it is compatible with most available instruments such as UV-visible spectrophotometry [14]. To achieve high extraction efficiency and miniaturize the Cr(VI) preparation process, DLLME employs n-butanol, tetrabutylammonium bromide, and diphenylcarbazide. In this method, tetrabutylammonium bromide acts as an ion-pair agent, enhancing the concentration of Cr(VI) in the organic phase due to the salting-out effect[15, 16]. The reaction between Cr(VI) and diphenylcarbazide produces a violet color in an acidic medium, which can be measured using the UV-Vis spectrophotometric method at 540 nm[15] .

Zanjan, located northwest of Iran, is home to farmland, several heavy metal mines, and related welding factories[17]. Grapes and apples are widely cultivated in this region and constitute the primary fruits and vegetables used in juice products. They are also consumed as syrups, fresh fruits, raisins, and marmalades by the residents of Zanjan. Information regarding the health risk assessment of Cr(VI), including carcinogenic and non-carcinogenic risks associated with the daily consumption of fruits and vegetables, is quite limited. Therefore, this study aims to 1) quantify the amount of Cr(VI) in apples, carrots, and grapes using DLLME; 2) determine the total chromium content in fruits and vegetables; 3) assess the carcinogenic and non-carcinogenic health risks of Cr(VI) in adults and children.

2.1. Experimental Sites

The experimental sites are located in the mining area of Zanjan province, Iran, which is considered an agricultural region. Zanjan is situated at a latitude and longitude of 36.6830°N and 48.5087°E and includes a Pb-Zn mining site and abandoned welding factories. Two sites were selected as Case Study A, and Case Study B. Case Study A encompasses farmlands near mining activities and welding factories contaminated by heavy metals. In contrast, Case Study B comprises farmland with low heavy metal-contaminated soil, selected as a comparison site.

2.2. Chemicals and Reagents:

All primary chemicals including 1,5-diphenylcarbazide and tetrabutylammonium bromide Potassium chromate, nitric acid(65%), n-butanol, Na₂CO₃ and EDTA used in this study were analytical grade reagents purchased from Sigma-Aldrich Company (St. Louis, MO, USA). A stock solution of Cr (VI) (500 mg L^− 1) was prepared by dissolving K₂CrO₄ in ultra-pure water. Working solutions of Cr (VI) were prepared by dilution of the stock solution. 0.5% (w/v) of tetrabuthylammonium bromide (TBAB, Sigma), Na₂CO₃(0.28M), EDTA (0.05M) and acidic diphenylcarbazide (0.05M, HNO3) was prepared. Before the experiment, all glassware and polyethylene bottles were acid washed (10 (v/v) % HNO₃, 24 h).

2.3. Experimental Section

2.3. Fruit and Vegetable Sampling and Analysis

Samples of apples and grapes were collected from the two distinct experimental sites, A and B. To ensure similarity in factors such as distance from factories and soil watering sources, which significantly influence the distribution, bioavailability, transportation, and accumulation of Cr(VI), 26 farmlands were selected for apple and grape sampling. Carrots were obtained from grocery stores. Approximately 1 kg of apples and grapes was collected from each farmland at 10-meter intervals, and 10 carrots were sourced from groceries. The edible parts of the samples were washed, cut, and grated to prevent changes in the color of the vegetables. Subsequently, the samples were dried at 45°C in triplicates. The dried samples were then finely powdered, passed through a 2-mm mesh sieve, and refrigerated. To determine Cr and Cr(VI), 35 representative samples of apples, grapes, and carrots were sent to laboratories. To determine the total Chromium concentration, half of the samples were digested using a mixture of H₂O₂ and HNO₃, following the microwave digestion method (SINEO-MDS-10, Shanghai, China).

2.4. Total Chromium Concentration

The chromium content in the apple, carrot, and grape samples was determined using a Graphite Furnace Atomic Absorption Spectrophotometer (GFAA) (Varian Model GTA120 atomic absorption spectrometer). The instrumental conditions for GFAA spectrometry were as follows: equipped with an auto-sampler, deuterium background correction, and the conditions were set to a wavelength of 357.9 nm and a slit width of 0.7 nm (Varian GTA120, Australia).

2.5. Cr(VI) Determination in Fruit and Vegetable Samples

To quantify Cr(VI) in the fruit and vegetable samples, a modified method 3060A designed for complex matrices was employed to enhance the extraction recovery. Additionally, spiking tests were conducted to identify matrix effects, as described in previous studies[13, 16, 18].

2.5.1 Calibration Standard

Stock solutions of Cr(VI) (500 mg L⁻¹) were freshly prepared from an appropriate amount of K₂CrO₄ (Merck). Six calibration standard Cr(VI) solutions ranging from 6.25 to 75 µg kg⁻¹ were used for method calibration. DLLME Matrix-matched Cr(VI) calibration curves were established by spiking calibration solutions and blank samples following the microextraction and preconcentration procedure.

2.5.2 Alkaline Digestion Procedure

Samples and blanks were subjected to alkaline extraction. A 0.1g sample of dried apples, carrots, and grapes was weighed into a 100 mL glass beaker, adding 50.0 mL of Na₂CO₃ (0.28 M) and EDTA (0.05 M). The mixture solution (pH > 10) was heated for 5 minutes at 80°C to initiate the extraction process. The resulting solutions were then diluted to 100 mL with distilled water. To reduce Cr(VI) to a lower oxidation state, the solutions were filtered and centrifuged at 4500 rpm for 5 minutes[13]. A corresponding blank was prepared following the same alkaline digestion procedure. The solution was neutralized with HNO₃; the microextraction procedure was applied to 4 mL of the alkaline extraction solution.

2.5.3 Microextraction and Preconcentration Procedure

For the analysis of Cr(VI), the DLLME (Dispersive Liquid-Liquid Microextraction) procedure followed by UV-Vis spectrophotometry using diphenylcarbazide reagent and n-butanol was employed, as described by Shishov, Terno et al. in 2020. In the microextraction and preconcentration step, 4 mL aliquots of an alkaline extraction solution containing Cr(VI) concentrations ranging from 6.25 to 25 µg L⁻¹ of Cr(VI) were used. The pH of the solution was adjusted to 2 using an HNO₃ solution. Subsequently, 2 mL of a 0.5% (w/v) TBAB (Tetrabutylammonium Bromide) solution was added, and the mixture was vortexed for 2 minutes at 3000 rpm. This resulted in the formation of fine microdroplets of TBAB and the Cr complex, forming a cloudy solution of droplets. 700 µL of n-butanol as the disperser solvent, containing acidic diphenylcarbazide, was introduced, and the solution was vortexed again for 2 minutes at 3000 rpm. The n-butanol phase was separated by centrifugation for 5 minutes at 4000 rpm, and the organic phase containing Cr(VI) was collected using a syringe. To quantify Cr(VI), spectrophotometric detection at 540 nm was carried out using a Diar 5000 spectrophotometer. The tests were conducted four times, and the results were averaged. Additionally, a blank sample underwent the same procedure. In this study, the determination of Cr(VI) in apple, carrot, and grape samples was performed using the standard addition method to mitigate matrix effects and obtain accurate results ranging from 12.5 to 50 µg kg − 1. The efficiency of microextraction was evaluated through spiking tests.

2.6. Estimating Target Hazard Quotient (THQ)

2.6.1 Assessment of Cr(VI) Non-Carcinogenic Risk

Estimated Cr(VI) risk (both carcinogenic and non-carcinogenic) for apples, carrots, and grapes in two case studies were performed considering adult and children groups, utilizing the US EPA method. The assessment involved the calculation of Target Hazard Quotients (THQ) and Carcinogenic Risk, employing the methodology for health risk assessment based on average daily consumption (kg/person/day). A THQ value of less than 1 indicates a chronic intake level of chromium that poses no significant health risk to consumers. Conversely, if the THQ value is greater than or equal to 1, there is a potential for non-carcinogenic health effects. The models for estimating THQs are as follows [19]:

$$THQ= V\times Con\left(Cr\right)\times ED\times EF/AT\times W\times ORFD$$

Here, V represents the average daily consumption of vegetables (kg/person/day), which is 0.3 kg for the inhabitants. Con(Cr) denotes the chromium concentration in fruit and vegetables (mg kg⁻¹ ). EF is the exposure frequency (365 days) for 70 and 7 years (for adults and children, respectively) through the consumption of fruit and vegetables. ORFD is the Cr(VI) oral intake reference dose (mg/kg/day). W, for both adults and children, represents the average body weight (70 kg for adults and 20 kg for children), while AT signifies the duration of exposure[19] .

2.6.2. Assessment of Cr(VI) Carcinogenic Risk

Cancer risk (CR) assessment is based on human intake values, specifically the CR associated with carrots and grapes' chromium(VI) content. The calculation for cancer risk is as follows [19] .

$$CR= D\left(ing\right) \times OSF$$

Here, D represents the estimated chronic intake of carcinogenic Chromium(VI) by ingestion (mg/day), and OSF (mg.kg^− 1 BW.day) is the ingestion slope factor, given as 0.5 (mg.kg^− 1 BW.day). For cancer risk (CR), a threshold of 10 − 4 is utilized, where values lower than 10^− 6 indicate no cancer risk, while values between 10^− 4 and 10^− 6 fall into an intermediate range and are considered acceptable.

2.6.3. Monte Carlo Simulation (MCS) Method

This study employed a probabilistic Monte Carlo Simulation (MCS) method to estimate cumulative health risks. Rather than relying on a single-point value, the MCS was performed with repeated trials (100,000 trials). Two age groups of children and adults were considered variables in the MCS. The results were estimated with 5% and 95% confidence using Crystal Ball software 212 (version 11.1.2.4, Oracle, Inc., USA) with 100,000 trials. Furthermore, the 95th percentile (95%) of THQ and CR (Carcinogenic Risk) in the cumulative MCS method was determined for groups at risk in mining areas[20].

2.10. Statistical Analyses

This research utilized statistical methods, including mean value, standard deviation, maximum and minimum values, and non-parametric T-test for statistical analysis. The Prism software (Graph Pad Prism 8.4) was employed for analysis (p-value < 0.05). All figures and tables were generated using Microsoft Excel 2016.

3.1. Method Validation

3.1.2. Limits of Detection (LODs) and Limits of Quantification (LOQs)

The detection and quantification limits of the method (LOD) were determined based on the slope of the matrix match calibration curve and the standard deviation of 10 repeated analyses of a blank sample. The method validation parameters, the LOD and LOQ for Cr(VI) detection, were found to be 0.6 and 2.4 µg kg⁻¹, respectively.

3.1.3. Recovery Test

The method validation was analyzed by spiking blank samples with 12.5, 25, and 50 µg kg⁻¹ of Cr(VI) solutions. The recoveries were in the range of 89.1–120.8% for Cr(VI). The accuracy of the DLLME procedure, as demonstrated by spiking recoveries, yielded satisfying results based on four replicate measurements. The microextraction procedure's relative standard deviation (RSD) was studied for 10 replicate analyses of standard solutions for precision within the concentration range of 10–50 µg kg⁻¹ of Cr(VI). In all cases, the RSDs for Cr(VI) microextraction were calculated to be less than 2.9% respectively.

3.2. Cr and Cr(VI) Concentration in Apple, Carrot, and Grapes Samples

The average total Cr and Cr(VI) concentrations (µg kg⁻¹) in apple and grapes samples from farmlands in case studies A and B and carrots from groceries are shown in Table 1. Total chromium was detected in apple and grape samples, with apple samples ranging from 301.6 to 648.2 µg kg⁻¹ (A1-A9) and grape samples from 331.5 to 534.3 µg kg⁻¹ (A1-A9). The maximum mean of total Chromium was found in apples and grapes (mean ± sd; 438.4 ± 157.85 µg kg⁻¹), (mean ± sd; 450.265 ± 65.530 µg kg⁻¹), and in carrots (mean ± sd; 2449.3.159 ± 280.571 µg kg⁻¹), respectively. The Cr(VI) concentration for carrots ranged from 223.4 to 452.547 µg kg⁻¹ (mean ± sd 326.332 ± 65.89µg kg⁻¹), and for grapes between 40.2 to 99.247 µg kg⁻¹ (mean ± sd 70.303 ± 18.208 µg kg⁻¹), with apple samples being below the limit of detection (LOD).

Table 1

Cr(VI) and total Cr concentration (µgkg^− 1) of carrot, apple, and grapes samples at Case study A and B
Sample	Cr(Total)	Cr(VI)	Sample	Cr(Total)	Cr(VI)
A1Carrot	2542.97	277.6842
A2Carrot	2416.98	347.1325
A3 Carrot	3140.01	452.68
A4 Carrot	2430.41	297.5476
A5 Carrot	2471.23	314.5
A6 Carrot	2391.14	285.7
A7 Carrot	2408.00	337.9
A8 Carrot	2517.1	351.8
A9 Carrot	2170.4	223.4
Mean ± sd	2493.159± 280.5719	326.3325± 65.89321
A1grape	442.5	50.6	B1grape	313.1	52.8
A2grape	483.56	58.59398	B2grape	328.5	56.65
A3grape	331.5	99.247	B3grape	322.5	51.8
A4grape	534.3	75.18	B4grape	298.31	49.43
A5grape	436.5	73.5	B5grape	319.32	48.43
A6grape	461.4	40.2	B6grape	330.7	52.2
A7grape	412.5	67.1	B7grape	304.5	50.1
A8grape	492.1	78.3	B8grape	296.1	55.1
mean ± sd	450.2657±	70.303±	mean±	314.2757±	52.06±
	65.530	18.208	sd	14.4106	2.79
A1apple	428.55	<LOD	B1apple	285.3	<LOD
A2apple	648.2	<LOD	B2apple	249.1	<LOD
A3apple	333.5	<LOD	B3apple	225.4	<LOD
A4apple	470.3	<LOD	B4apple	241.8	<LOD
A5apple	301.6	<LOD	B5apple	250.3	<LOD
mean ± sd	438.4±			241.65±
	157.85			11.466
Permissible level(FAO,WHO,2011)	2.3mg kg^− 1	-

In case study B, the minimum level of total chromium concentration in B1-B5 apple samples ranged from 225.4 to 285.3 µg kg⁻¹(mean ± sd; 241.65 ± 11.46µg kg⁻¹),, and B1-B6 grape samples ranged from 296.1 to 330.7 µg kg⁻¹(mean ± sd; 314.276 ± 14.41µg kg⁻¹). The Cr(VI) amounts in apple were below the detection limit and in grapes ranged from 48.43 to 56.65 µg kg⁻¹ in grapes (mean ± sd; 52.06 ± 2.79µg kg⁻¹), respectively. As shown in Table 1, there was a significant difference in the total Cr and Cr(VI) concentration in the grapes of case studies A and B (p-value < 0.001). Moreover, a significant difference (p-value < 0.05) was observed in the total chromium concentration between apple samples from case studies A and B. Cr(VI) concentration in apples grown in both case studies A and B were below the detection limit. However, as shown in Table 1, in case study A, the levels of Cr in carrots exceeded the standard limits for Cr (2.3 mg kg⁻¹) set by WHO/FAO in 2011.

The results were slightly comparable with previously conducted research, such as Mohsen Mirzaei et al. (2020), which showed Cr concentrations in grapes in Chaharmahal and Bakhtiari provinces of Iran, with Cr concentration in grapes being as high as 9.5 mg kg⁻¹. Yousaf et al. (2016) reported total Cr levels in carrot samples from urban-industrial areas ranging from 0.51 to 2.18 mg kg⁻¹, below the recommended safety limit[21]. A study by Shaheen (2016) in Bangladesh showed that the Cr concentration in carrots was 0.296 mg kg⁻¹, also below the standard limit[22]. Amer et al. (2019) reported various Cr concentrations in grape samples collected from different sites, ranging between ND to 1.06 mg kg⁻¹[23]. The concentration of Cr in grape samples from South Africa ranged from 0.51 to 0.87 (mg kg⁻¹), while in apple samples, it was 0.75 (mg kg⁻¹), and all samples were below the defined limit by WHO (2.3 mg kg⁻¹)[24]. Fan et al. (2017) showed that in greenhouse fruit, leaf, and tuber types, Cr concentrations ranged from 1.59 in tubers to 2.83 (mg kg⁻¹) in fruit types[25].

The results of this study show that in carrots, the amount of Cr(VI) significantly increases with the total Cr content (r = 0.516). However, it represents about 9–29% of the total Cr concentration (Table 1, 2). Therefore, Cr content in apples, carrots, and grapes is primarily present as Cr(III), the less toxic, essential element and immobile Cr species. To estimate the health risks of Cr and its oxidation state, such as Cr(VI), the focus should be on the daily consumption of vegetables and processed products in the contaminated area. The apple, carrot, and grapes from fruit and vegetable samples were selected from the most consumed foodstuff groups, such as raisins in dried form, fresh fruit, and fruit juice.

Table 2

Estimated daily intake (mg day^− 1 kg^− 1), THQ, and CR of Cr and Cr(VI) related to carrot, apple,grapes consumption
	Case study A				Case study B
	THQ Cr		THQ Cr(VI)		THQ Cr		THQ Cr(VI)
	Children	Adult	Children	Adult	Children	Adult	Children	Adult
THQ carrot	0.249	0.076	1.63	0.465
CR (log CR)			0.0024 (-2.6)	0.00069 (-3.16)
THQ grape	0.045	0.0128	0.36	0. 142	0.03	0.0004	0.26	0.074
CR (log CR)			0.0005 (-3.3)	0.00015 (-3.82)			0.0039 (-2.408)	0.00011 (-3.95)
THQ apple	0.043	0.012	-	-	0.02	0.006	-	-
EDI: Estimated Daily intake (mg/kg body weight/day), Oral Reference dose (0.15) for Cr, and (0.003) for
Cr (VI) (mg kg body weight^− 1 day^− 1).

Furthermore, the Target Hazard Quotients (THQs) of Cr and Cr(VI) through the consumption of apples, carrots, and grapes by the local inhabitants in the northwest of Iran were derived based on the methodology described by the US EPA and Monte Carlo simulation techniques were used for assessing health risks. THQ of Cr(VI) for carrots was calculated as 0.465 and 1.6 for adults and children, respectively, and for grapes in case study A, it was 0.142 and 0.36, respectively, while for children in site B, it was calculated as 0.26 with 95% assurance. Therefore, THQ values higher than 1 for Cr(VI) in carrots for children indicate that the consumer population is at significant non-carcinogenic health risk (Table 2). For carrots, carcinogenic risk due to Cr(VI) was obtained for adults and children as 6.9E-4 and 2.4E-3, and for grapes in case study A, it was 5E-5 and 1.5E-4, respectively. Cumulative carcinogenic and noncarcinogenic risk assessment in adult and children were simulated by Monte Carlo simulation indicated there is a significant possibility of risk in mining-contaminated area inhabitants (Fig. 1).

Fruits and vegetables cultivated in contaminated fields, especially those with heavy metal contamination, may accumulate higher concentrations of heavy metals. Cr(VI) is a mobile and bioavailable form of Chromium with carcinogenic effects. This study demonstrated that alkaline extraction followed by DLLME is an accurate and precise method for Cr(VI) determination, and the amount of Cr(VI) in carrots significantly increases with the total Cr content. Apples showed no detectable Cr(VI) levels. To estimate the health risks of Cr(VI), the focus should be on vegetables and fruits in contaminated areas, especially those processed into juice and dried products for fresh consumption. Determining Chromium and Cr(VI) in carrots and grapes, as well as root vegetables and bush fruits, revealed that Cr(VI) in vegetables may be associated with additional health risks for the local population in mining areas. Therefore, it is necessary to strengthen the monitoring of Cr and Cr(VI) levels in highly consumed fruits and vegetables, and agricultural advisories on substitute products should be issued.

AAS-GF; (graphite furnace atomic absorption spectrometry), DES; (Deep eutectic solvent); DLLME;(dispersive liquid-liquid microextraction),

Funding: The current study was financially supported by the research deputy of Zanjan University of medical science (Grant NO.A-12-1400-3).

Declaration of Competing Interest

The authors declare that they have no known competing financial interests that could have appeared to influence the work reported in this paper.

Authors’ contributions: “R.D. Conceptualization, Methodology, and conducted the study, analyzing and writing, M. M contributed to the review, Kh. A and K. k. contributed to the editing. All authors reviewed the manuscript. “

Data availability Not applicable.

Ethics approval Not applicable.

Consent to participate Not applicable.

Consent for publication Not applicable.

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Trace Determination of Cr(VI) and Total Cr in Fruit and Vegetable Samples: Utilizing Monte Carlo Simulation for Risk Assessment in an Iranian Mining Area

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Abstract

Figures

1. Introduction

2. Material and Methods

2.1. Experimental Sites

2.2. Chemicals and Reagents:

2.3. Experimental Section

2.3. Fruit and Vegetable Sampling and Analysis

2.4. Total Chromium Concentration

2.5. Cr(VI) Determination in Fruit and Vegetable Samples

2.5.1 Calibration Standard

2.5.2 Alkaline Digestion Procedure

2.5.3 Microextraction and Preconcentration Procedure

2.6. Estimating Target Hazard Quotient (THQ)

2.6.1 Assessment of Cr(VI) Non-Carcinogenic Risk

2.6.2. Assessment of Cr(VI) Carcinogenic Risk

2.6.3. Monte Carlo Simulation (MCS) Method

2.10. Statistical Analyses

3. Result and Discussion

3.1. Method Validation

3.1.2. Limits of Detection (LODs) and Limits of Quantification (LOQs)

3.1.3. Recovery Test

3.2. Cr and Cr(VI) Concentration in Apple, Carrot, and Grapes Samples

Conclusion

Abbreviations

Declarations

References

Additional Declarations

Status:

Version 1