Needle trap device technique: From fabrication to sampling.

Needle Trap Device (NTD) as a novel, versatile, and eco-friendly technique has played an important role in analytical and environmental chemistry. The distinctive role of this interdisciplinary technique can be defended through the sampling and analysis of biological samples and industrial pollutants in gaseous and liquid environments. In recent years, significant efforts have been made to enhance the performance of the needle trap device resulting in the development of novel extraction routes by various packing materials with improved selectivity and enhanced adsorption characteristics. These achievements can lead to the facilitated pre-concentration of desired analytes. This review tries to have a comparative and comprehensive survey of the three important areas of NTD technique: I) Fabrication and preparation procedures of NTDs; II) Sampling techniques of pollutants using NTDs; and III) Employed materials as adsorbents in NTDs. In the packing-material section, the commercial and synthetic adsorbents such as carbon materials, metal-organic frameworks, aerogel, and polymers are considered. Furthermore, the limitations and potential areas for future development of the NTD technique are presented.

Synthesis and characterization of Fe3O4@SiO2 -supported metal-organic framework PAEDTC@MIL-101 (Fe) for degradation of chlorpyrifos and diazinon pesticides.

In this study, a new core-shell Fe3O4@SiO2/PAEDTC@MIL-101 (Fe) photocatalyst was prepared by sol-gel method and used to degrade diazinon (DZN) and chlorpyrifos (CPS) from aqueous solutions. The characteristics analyzed by various techniques indicate that the core-shell photocatalyst with a specific surface area of 992 m2/g, pore size of 1.35 nm and saturation magnetization of nanocomposite was 12 emu/g has been successfully synthesized and can be separated from the reaction solution by a magnetic field. The maximum efficiencies of DZN (98.8%) and CPS (99.9%) were provided at pH of 5, photocatalyst dosage of 0.6 g/L, pollutant concentration of 25 mg/L, radiation intensity of 15 W, and time of 60 min. The presence of anions such as sulfate, nitrate, bicarbonate, phosphate, and chloride had a negative effect on the performance of the photocatalysis system. Compared to the adsorption and photolysis systems alone, the photocatalytic process based on Fe3O4@SiO2/PAEDTC@MIL-101 (Fe) under two UV and visible light sources showed a high efficiency of 90% in the reaction time of 60 min. The BOD5/COD ratio improved after 50 min to above 0.4 with TOC and COD removal rates >80%. Scavenging tests showed that •OH radical, hole (h+), electron (e-), and O2•- anion were produced in the reaction reactor, and the •OH radical was the dominant species in the degradation of DZN and CPS. The stability tests confirmed the recyclability of the photocatalyst in 360 min of reactions, with a minimum reduction of 7%. Energy consumption for the present system during different reactions was between 15.61 and 25.06 kWh/m3 for DZN degradation and 10-22.87 kWh/m3 for CPS degradation.

Biological exposure indices of occupational exposure to benzene: A systematic review.

The current study aimed to systematically review the studies concerning the biological monitoring of benzene exposure in occupational settings. A systematic literature review was conducted in Scopus, EMBASE, Web of Science, and Medline from 1985 through July 2021. We included peer-reviewed original articles that investigated the association between occupational exposure to benzene and biological monitoring. We identified 4786 unique citations, of which 64 cross-sectional, one case-control, and one cohort study met our inclusion criteria. The most studied biomarkers were urinary trans-trans muconic acid, S- phenyl mercapturic acid, and urinary benzene, respectively. We found the airborne concentration of benzene as a key indicator for choosing a suitable biomarker. We suggest considering urinary benzene at low (0.5-5.0 TLV), urinary SPMA and TTMA at medium (5.0-25 and 25-50 TLV, respectively), and urinary phenol and hydroquinone and catechol at very high concentrations (500 and 1000 TLV ≤, respectively). Genetic polymorphism of glutathione S-transferase and oral intake of sorbic acid have confounding effects on the level of U-SPMA and U-TTMA, respectively. The airborne concentration, smoking habit, oral consumption of sorbic acid, and genetic polymorphism of workers should be considered in order to choose the appropriate indicator for biological monitoring of benzene exposure.

Application of a novel composite of Fe3O4@SiO2/PAEDTC surrounded by MIL-101(Fe) for photocatalytic degradation of penicillin G under visible light.

The novel photocatalyst of Fe3O4@SiO2/PAEDTC@MIL-101(Fe) was prepared based on the sol-gel method, and its structure and morphology were determined by SEM mapping, TEM, XRD, FTIR, and N2 adsorption-desorption analyses. The photocatalytic activity of nanocomposite was evaluated in comparison with other particles as well as adsorption and photolysis processes. The effect of operating parameters showed that the complete degradation of penicillin G (PNG) can be provided at a photocatalyst dosage of 0.6 g/L, radiation intensity of 36 W, pH of 5, and time of 60 min. In the optimum condition, 84% TOC removal was attained and the BOD5/COD rate for the treated effluent was above 0.4, which was representative of the high biodegradability of the treated effluent compared to the raw sample. The findings of energy consumption showed that PNG can be easily and effectively treated by the photocatalytic process based on magnetic MIL-101(Fe) with electrical energy per order between 10 and 20.87 kWh/m3. Due to the excellent interaction between the MIL-101(Fe) and Fe3O4@SiO2/PAEDTC, the photocatalyst stability test showed a recyclability of the particles for 5 consecutive reaction cycles with a minimum reduction of 7%. Solution treated with photocatalyst under UV and visible light sources explained that the toxicity of the effluent after treatment is significantly reduced with the growth of Escherichia coli. Scavenging experiments showed that •OH radical and hole (h+) are the main agents in degrading PNG to CO2, H2O, and biodegradable and low-toxicity products. Finally, the findings of the diagnostic analysis and comparative experiments proved that with the interaction of Fe3O4@SiO2, NH2, and MIL-101(Fe), a lower band gap can be prepared for more absorption of photons and pollutant and also more and faster production of active radicals.

Magnetic layered double hydroxides for the sensitive dispersive solid phase microextraction of hippuric acid in urine samples prior to HPLC-UV analysis.

The core- shell structural layered double hydroxide (Fe3O4-SiO2-EN@Zn-Al-LDH) was successfully synthesized and applied as a solid sorbent in the magnetic dispersive micro solid-phase-extraction (M-DµSPE) method. It was combined with high-performance liquid chromatography for the trace analysis of hippuric acid (HA) from urine samples. The obtained magnetic layered double hydroxides (LDHs) were characterized by XRD, FT-IR, VSM, FE-SEM, and BET techniques. The characterization analysis indicated that Fe3O4- SiO2- EN@ Zn-Al-LDH has a sufficient surface area and good saturation magnetism. The affecting variables on the extraction of HA by the proposed method were optimized. Excellent adsorption capacity (127.8 mg g-1), wide linearity dynamic range (0.015-500 µg mL-1), and satisfactory limits of detection and quantification (0.055 and 0.014 µg mL-1, respectively) could be obtained under optimum conditions. The good repeatability and low relative standard deviation (7.2 %), low carry-over (2.7%), good matrix effect (93.6%), high reusability (up to 19 times), and an acceptable percent recovery value (97.2%) proved the selectivity and applicability of the proposed method for the extraction of the trace levels of HA in real urine samples.

Investigation of organophosphorus (OPs) compounds by a needle trap device based on mesoporous organo-layered double hydroxide (organo-LDH).

Organophosphorus (OPs) compounds can endanger human health and the environment by inhibiting the acetylcholinesterase enzyme. But these compounds have been widely used as pesticides due to their effectiveness against all kinds of pests. In this study, a Needle Trap Device (NTD) packed with mesoporous organo-layered double hydroxide (organo-LDH) material and coupled with gas chromatography-mass spectrometry (GC-MS) was employed for the sampling and analysis of OPs compounds (diazinon, ethion, malathion, parathion, and fenitrothion). In this way, the [magnesium-zinc-aluminum] layered double hydroxide ([Mg-Zn-Al] LDH) modified with sodium dodecyl sulfate (SDS) as a surfactant was prepared and characterized by FT-IR, XRD, BET, and FE-SEM, EDS, and elemental mapping techniques. Then, various parameters such as relative humidity, sampling temperature, desorption time, and desorption temperature were evaluated by the mesoporous organo-LDH:NTD method. The optimal values of these parameters were determined using response surface methodology (RMS) and central composite design (CCD). The optimal temperature and relative humidity values were obtained as 20 °C and 25.0%, respectively. On the other hand, the desorption temperature and time values were in the range of 245.0-254.0 °C and 5 min, respectively. The limit of detection (LOD) and limit of quantification (LOQ) were reported in the range of 0.02-0.05 mg m-3 and 0.09-0.18 mg m-3, respectively, which shows the high sensitivity of the proposed method compared to the usual methods. The repeatability and reproducibility of the proposed method (by calculating the relative standard deviation) was estimated in the range of 3.8-10.10 which indicates the acceptable precision of the organo-LDH:NTD method. Also, the desorption rate of the stored needles at 25 °C and 4 °C, was determined to be 86.0% and 96.0%, respectively after 6 days. The results of this study proved that the mesoporous organo-LDH:NTD method can be utilized as a fast, simple, environmentally friendly, and effective method for sampling and determining OPs compounds in the air.

Urinary bio-monitoring of aromatic amine derivatives by new needle trap device packed with the multi-component adsorbent.

Aromatic amines are a large group of chemical compounds that have attracted the attention of researchers due to their toxicity and carcinogenicity. This study aimed to develop an efficient method for sampling and analysis of aromatic amines (Aniline, N, N-dimethylaniline, 2-chloroaniline, and 3-chloroaniline) from the vapour phase (headspace) of urine samples. For the implementation of this plan, a needle trap device packed with the three-component adsorbent consisting of nano-Hydroxy Apatite (nHA), Zeolite (Ze), and Metal-Organic Framework (MOF) equipped with GC-FID was employed for the first phase. Examination of the prepared adsorbents was performed by FT-IR, PXRD, and FE-SEM techniques. The optimal value of considerable parameters such as time and temperature of extraction, salt content, and pH were established using the Response Surface Methodology-Central Composite Design (RMS-CCD) method. In this way, the optimal extraction of targeted analytes was accomplished in 41 min at 41 °C with NaCl content of 33.0% (w/v) and pH: 13.0, respectively. Also, the repeatability and reproducibility of the method were calculated to be in the range of 2.2-7.1% and 3.9-8.1%, respectively, which indicates the acceptable precision of the method. Also, the limit of detection (LOD) and limit of quantification (LOQ) were determined in the range of 0.3-32.0 ng.L-1 and 0.8-350.0 ng.L-1, respectively, which proves the high sensitivity of the proposed method. Furthermore, the recovery percent of the extracted analytes was concluded in the range of 97.0-99.0% after 6 and 30 days of the sampling and storage at 25 °C and 4 °C, respectively. Finally, the designed procedure was employed in the analysis of the above-mentioned aromatic amines in the real urine samples. The achieved results illustrate that the three-component absorbent system (nHA;Ze;MOF@NTD) can be introduced as an efficient, fast-response, sensitive, and versatile procedure for trace analysis of the different aromatic amine compounds in public and occupational health.

Application of MIL-53(Al)-NH2 as a Dispersive Microsolid-Phase Extraction Material for Determination of Cyclophosphamide in Urine by High-Performance Liquid Chromatography.

In this paper, an aluminum-based metal-organic framework (MIL-53(Al)-NH2) was synthesized and employed as a well-known and efficient dispersive microsolid-phase extraction (Dµ-SPE) sorbent for reliable determination of cyclophosphamide in urine samples by the high-performance liquid chromatography (HPLC) technique. The synthesized MIL-53(Al)-NH2 was characterized by FT-IR, PXRD, FE-SEM, and EDS for more details. Then, the effective parameters of the preconcentration and extraction of urinary cyclophosphamide including the amount of the solid sorbent, the pH of the sample, sample volume, extraction and desorption time, and the type and volume of elution solvent were thoroughly investigated and optimized. According to the results, a linear dynamic range of 0.14-120 µg mL-1 with a good correlation coefficient (R 2 = 0.998) and a limit of detection (LOD) of 0.05 µg mL-1 were obtained with intra- and interday relative standard deviations (n = 9) of 3.13 and 3.99% in optimized conditions, respectively. Furthermore, the absolute recovery of urinary cyclophosphamide at three concentrations (0.5, 50.0, and 100.0 µg mL-1) was 94.0%. Finally, the optimal condition of the developed method was successfully applied to the extraction and analysis of cyclophosphamide from the real urine samples with satisfactory recovery (94.0-97.0%) and acceptable precision (<4.1%). The findings proved that MIL-53(Al)-NH2 can be utilized as a suitable adsorbent for highly reliable extraction of cyclophosphamide in biological matrices.

Urinary bio-monitoring of amphetamine derivatives by needle trap device packed with the zirconium-based metal-organic framework.

In this research, zirconium-based metal-organic framework was utilized as a novel and efficient porous adsorbent for headspace extraction of Amphetamine, Methamphetamine, and Fenfluramine from the urine samples by a needle trap device (NTD). The Zr-UiO-66-PDC was electrosynthesized at the green conditions and characterized by various analyses such as FT-IR, XRD, FE-SEM, EDS, and elemental mapping techniques. Then, the effective parameters on the NTD efficiency such as salt content, pH, extraction/desorption temperature and time were evaluated and optimized by response surface methodology. The optimal extraction of amphetamine compounds was accomplished in 50 min at 70 ºC at the situation with NaCl content of 27% and pH: 11.90. The limit of detection, and limit of quantification factors were determined to be 0.06-0.09 and 0.5-0.8 ng mL-1, respectively. Furthermore, the precision and accuracy (intra- and inter-day) of the employed procedure in the term of relative standard deviation (RSD) were calculated in the range of 8.0-9.0% and 6.8-9.8%, respectively. Also, the recovery percent of the extracted analytes were concluded in the range of 95.0-97.0% after 10 days from the sampling and storage at 4 °C. Finally, the proposed procedure was involved in the analysis of amphetamine compounds in the real urine samples. These results were proved the proposed Zr-UiO-66-PDC@HS-NTD technique coupled with GC-FID can be used as an eco-friendly, fast-response, sensitive, and efficient drug test procedure for trace analysis of the amphetamine compounds in urine samples.

Occupational exposure to BTEX and styrene in West Asian countries: a brief review of current state and limits.

The aim of introducing occupational exposure limits (OELs) is to use them as a risk management tool in order to protect workers' health and well-being against harmful agents at the workplace. In this review we identify OELs for benzene, toluene, ethylbenzene, xylene (BTEX), and styrene concentrations in air and assess occupational exposure to these compounds through a systematic literature search of publications published in West Asian countries from 1980 to 2021. OELs for BTEX and styrene have been set in Iran and Turkey to levels similar to those in European countries and the US. The search yielded 49 full-text articles that cover studies of exposure assessment in six countries, but most (n=40) regard Iran. Average occupational exposure to benzene of workers in oil-related industries is higher than recommended OEL, while average occupational exposure to other compounds is lower than local OELs (where they exist). Currently, information about levels of occupational exposure to BTEX and styrene is insufficient in West Asian countries, which should be remedied through OEL regulation and application. Furthermore, coherent research is also needed to determine actual levels of occupational exposure, dose-responses, and the economic and technical capacity of local industries to address current issues.

Sensitive and selective magnetic dispersive microextraction of diazinon from urine samples by molecularly imprinted polymer based on core-shell metal-organic frameworks.

A core-shell magnetic metal-organic framework (Fe3O4 SiO2/ PAEDTC@ MIL- 101 (Fe)) was synthesized as the substrate and then covered with a surface molecularly imprinted polymer (MIP) layer. Next, Fe3O4 SiO2/ PAEDTC@ MIL- 101 (Fe) @ MIP was characterized by XRD, FT-IR, BET, VSM, TEM, and FE-SEM techniques and applied for selective, fast, and sensitive magnetic dispersive solid-phase microextraction (M-DµSPE) of diazinon from urine samples by the GC- FID detection method. The key experimental variables affecting M-DµSPE were studied and optimized by central composite design (CCD). Under optimum conditions (5 mL; sample at pH: 7.0, the mass of solid sorbent; 6 mg, extraction time; 4 min, acetonitrile as an eluent solvent; 1.5 mL, and desorption time; 3 min, and then reconstituted with 100 µL of methanol), the proposed method exhibits high sensitivity with limits of detection and quantification of 0.005 and 0.017 ng mL-1, respectively. Excellent extraction recovery (98.5 %), wide linearity range (0.02-200000 ng mL-1, R2 > 0.992), high enrichment factors (47-53), and satisfactory precision (<6.3 % RSD) were achieved. The MIP- MOF@ M-DµSPE -GC-FID method can be used with high precision and wide linearity to extract and analyze trace levels of diazinon in real urine samples.

Application of a needle trap device packed with a MIP@MOF nano-composite for efficient sampling and determination of airborne diazinon pesticide.

In this research, a novel, selective, and efficient porous adsorbent nano-composite comprising a molecularly imprinted polymer and a metal-organic framework (MIP@MOF) was employed for sampling, extraction and analysis of diazinon from the air by a needle trap device (NTD), for the first time. The synthesized MIP@MOF sorbent was characterized by the FT-IR, XRD, FE-SEM, TEM, and EDS techniques. Then, the effective parameters of the sampling (temperature and humidity) and desorption (time and temperature) process were optimized by response surface methodology (RSM). The optimum values of temperature and humidity of the sampling chamber were estimated to be 20 °C and 25.0%, respectively. Also, the highest response during the analyte desorption was obtained at 262 °C and 4.5 minutes. For more details, the performance of the MIP@MOF:NTD method was evaluated by determination of important parameters such as repeatability, reproducibility, the limit of detection (LOD), and the limit of quantification (LOQ), and then compared with the NIOSH 5600 standard method. The values of LOD and LOQ for the targeted analyte were determined to be 0.02 and 0.1 µg m-3, respectively. Also, the repeatability and reproducibility of the proposed method were obtained in the range of (3.9-5.1)% and (5.1-6.4)%, respectively, which proved the acceptable precision of the method. Furthermore, the results of this study exhibited a high correlation coefficient (R 2 = 0.9781) between the proposed method and the recommended NIOSH method. Finally, the proposed procedure was utilized for sampling and determination of the airborne diazinon in real conditions. These results indicated that the proposed MIP@MOF:NTD method can be employed as a fast, simple, environmentally friendly, selective, and effective procedure for sampling and determining diazinon in air.

Effect of occupational exposure to lead on serum levels of lipid profile and liver enzymes: An occupational cohort study.

The present study was performed to know the effects of chronic lead exposure on serum lipids, lipoproteins, and liver enzymes in a cohort study among of lead mine workers. We followed of 200 Iranian workers for 3- years (2018-2020), 100 of them with known occupational exposure to lead thorough their work in lead mine while the others 100 were with no such exposure. Blood lead level (BLL), serum lipids, lipoproteins, and liver enzymes of the exposure group for 3- years were measured and compared with those attained in the non-exposed workers. The BLL levels of the lead-mine workers were higher than with recommended level and the non-exposed group (24.15 and 6.35 µg/dL, respectively). The findings indicated a positive and significant relationship between BLL and lactate dehydrogenase, aspartate transaminase, alkaline phosphatase, alanine transaminase, and bilirubin levels (P < 0.01). Also while we found a negative and significant correlation between BLL and triglyceride, total protein, albumin, and globulin levels (P < 0.01). This report depicted that chronic lead exposure is a risk factor for hematological, liver, and cardiovascular diseases. Despite the fact that the level of liver function parameters was in the normal range, the results of 3- years follow-up show a significant relationship between BLL and alteration of biochemical parameters levels.

Determination of halogenated hydrocarbons in urine samples using a needle trap device packed with Ni/Zn-BTC bi-MMOF via the dynamic headspace method.

In this study, a nickel/zinc-BTC bi-metallic metal-organic framework (bi-MMOF) was employed as a new and efficient adsorbent in a needle trap device (NTD) for headspace (HS) sampling, extraction and analysis of halogenated hydrocarbons (trichloroethylene, tetrachloroethylene, chloroform, and tetrachloroethylene) from spiked and real urine samples. Characterization of the prepared adsorbent was accomplished by FT-IR, PXRD, EDX, elemental mapping, and FE-SEM techniques. According to experimental results, the optimal temperature and extraction time, salt content, temperature and desorption time of the response surface methodology (RSM) and Box-Behnken design (BBD) were determined to be 56 °C and 30 min, 5.5%, 350 °C and 8 min for the studied halogenated hydrocarbons, respectively. The calculated values of detection limit and quantitation limit parameters were in the range of 1.02-1.10 and 2.01-2.4.0 ng L-1, respectively. Moreover, intermediate precision and repeatability of the method were in the range of 4.90-8.20% and 1.50-4.80%, respectively. The recovery percentages of analytes were obtained to be in the range of 95.0-97.0% 10 days after the sampling and storage at 4 °C. This study showed that the proposed HS-NTD:Ni/Zn-BTC method coupled with a GC-FID can be employed as a simple, fast, and sensitive procedure for non-metabolized halogenated hydrocarbons from urine samples in biological monitoring.

Impact of Filter on the Estimation of Quantitative Mixture Risk Caused by Some Chemical Constituents Generated from Popular Cigarette Brands in Iran.

BACKGROUND: This study was conducted to evaluate the impact of filter on the eventual carcinogenic and non-carcinogenic risks caused by the main toxic constituents of popular cigarette brands in Iran. METHODS: At this laboratory study, the concentration of benzene, formaldehyde, arsenic, and cadmium in the mainstream smoke of 11 popular cigarette brands in Iran, on the without and with-filter modes was determined based on an established method. The hazard quotient (HQ), incremental lifetime cancer risk (ILCR), and mixture quantitative risk assessments (QRAs) were performed based on the QRA method recommended by United States Environmental Protection Agency (USEPA). FINDINGS: The mean of HQ due to benzene, formaldehyde, arsenic, and cadmium in without-filter cigarette smoke was from 3.96 to 3505. The findings indicated that the HQs related to benzene, formaldehyde, arsenic, and cadmium in cigarette smoke were decreased with filter by 48.3%, 25.3%, 37.6%, and 49.1%, respectively. The filter of cigarette decreased ILCR of benzene, formaldehyde, arsenic, and cadmium in cigarette smoke by 53.02%, 25.31%, 37.70%, and 61.01%, respectively. The mixture of non-carcinogenic and carcinogenic estimated risks due to inhalation of studied cigarettes smoke was very high and unacceptable. CONCLUSION: The cigarette filter plays an essential role in reducing inhalation exposure to hazardous compounds in mainstream cigarette smoke; nevertheless, the average of overall mixture HQs and ILCRs estimated caused by studied compounds was higher than the acceptable value. It is recommended that future empirical studies investigate the impact of the type of fiber used in cigarette filter on reducing carcinogenic and non-carcinogenic risks caused by cigarette smoke.

Determination of urinary methylhippuric acids using MIL-53-NH2 (Al) metal-organic framework in microextraction by packed sorbent followed by HPLC-UV analysis.

For the analysis of methylhippuric acids (MHAs) in human urine samples, in this study, a new method based on the metal-organic framework (MOF) of MIL-53-NH2 (Al) in microextraction by packed sorbent (MEPS) was developed. The synthesis of MIL-53-NH2 (Al) was characterized by Fourier transform infrared spectra, field emission-scanning electron microscopy and X-ray diffraction. Response surface methodology was used to investigate the influences of several parameters including type and volume of elution, type of conditional solvent, sample volume and extraction cycle on MEPS efficiency. The results showed good recoveries (>94%) and excellent extraction efficiencies (>96%) at three different concentrations of 50, 500 and 1500 µg ml-1 (as low, mid and high concentrations, respectively) of MHA isomers. Calibration curves of MHAs were linear over the concentration range of 1-1500 µg ml-1 , with high correlation coefficients (r ≥ 0.998). The reproducibility of the proposed MIL-53-MEPS for determination of three isomers of MHA was found to be in the range of 3.5-11.1%. After optimization of the proposed technique, it was used to analyze MHAs in urine samples of workers exposed to xylenes in a petrochemical plant in Asalouyah, Iran. The results indicated that the MOF-MEPS method was selective, sensitive, rapid and efficient for the extraction of urinary MHAs. The technique is also environmentally friendly and inexpensive, and the MOF sorbent is reusable.

Facile and sensitive determination of urinary mandelic acid by combination of metal organic frameworks with microextraction by packed sorbents.

In this study, two hybrid metal organic frameworks including MOF-5@ Fe3O4-NH2 and MOF-5@ SBA-15 for the first time were synthetized and combined with microextraction by packed sorbent (MEPS) to extract of mandelic acid (MA) from urine samples. The synthetized sorbents were characterized using FE-SEM, XRD and FT-IR techniques. The important parameters in MEPS procedure including sample volume, extraction draw_discard cycles, elution solvent volume and desorption draw-eject cycles were optimized using response surface methodology (RSM) with central composite design (CCD). The results indicated that the volume of elution solvent was the most important parameter in the recovery of MA by MOF-MEPS procedure. The optimized MOF-MEPS method offered an acceptable efficiency for the recovery of MA from urine samples (MOF-5@Fe3O4-NH2 and MOF-5@SBA-15: 94.5% and 90.3%, respectively, RSD < 3.54%). The limit of detection (LOD) of MA calculated by MOF-MEPS procedure combined with high performance liquid chromatography for MOF-5@ Fe3O4-NH2 and MOF-5@ SBA-15 were calculated to be 0.10 and 0.13 µg mL-1, respectively. The linearity dynamic ranges (LDRs) determination of urinary MA by MOF-5@ Fe3O4-NH2 and MOF-5@ SBA-15 were 0.2-100 and 0.2-90 µg mL-1, respectively. The results of the present study implied that the proposed technique is a fast and sensitive procedure for extraction and determination of MA from urine samples.