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.

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.

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.

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.

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.

Efficient extraction of aromatic amines in the air by the needle trap device packed with the zirconium based metal-organic framework sorbent.

In this study, development of a needle trap device (NTD) packed with UiO-66 adsorbent was used for the sampling of the aromatic amine compounds (including aniline, N,N-dimethylaniline and o-toluidine) followed by gas chromatography (GC) with flame-ionization detector (FID) analysis. The UiO-66 sorbent was synthesized and then packed inside a spinal needle (Gauge 22). The synthesized sorbent was characterized with the XRD, FE-SEM, EDS and FT-IR techniques. This study was conducted both in the laboratory and in the real samples. In the laboratory, the sampling parameters (such as temperature and humidity) and desorption parameters (including desorption temperature and desorption time) were optimized using Response Surface Methodology (RSM) by Central Composite Design (CCD). The results indicated that the performance of the sampling device decreased with increasing the sampling humidity and temperature. Moreover, the highest peak area responses of the studied analytes were observed at a desorption time of 3 minutes and desorption temperature of 270 °C. The values of the limit of detection (LOD) and limit of quantitation (LOQ) were in the range 0.01-0.02 and 0.03-0.05 ng mL-1, respectively. Our findings demonstrated that NTD packed with synthesized UiO-66 has good repeatability (RSD = 1.3-6.8%) and acceptable reproducibility (with three NTDs) (RSD = 1.3-9.7%). Comparison of the results between NTD-UiO-66 and NIOSH2002 showed a sufficient correlation (0.98-0.99) between two methods. Therefore, the results indicated that the NTD packed with the UiO-66 adsorbent can be used as a powerful technique for occupational and environmental monitoring.

Nano-hydroxyapatite/polyaniline composite as an efficient sorbent for sensitive determination of the polycyclic aromatic hydrocarbons in air by a needle trap device.

Hydroxyapatite is a readily available, inexpensive, environmentally friendly adsorbent with high adsorption capacity. In this study, a polyaniline-doped nano-hydroxyapatite (PANI@HA) adsorbent was synthesized and employed in a needle trap device for the extraction of polycyclic aromatic hydrocarbons such as naphthalene, fluoranthene, benzo[a]anthracene, phenanthrene, and benzo[a]pyrene for the first time. The synthesized adsorbent was characterized by X-ray diffraction, field emission scanning electron microscopy, and Fourier-transform infrared spectroscopy analysis. Initially, effective variables such as the carryover effect, storage time, accuracy, and precision of the method were examined in the laboratory. The desorption conditions were optimized using the response surface methodology and central composite design methods. From the standpoint of quantitative parameters, the limit of detection and limit of quantitation were determined to be between 0.001 and 0.003 and 0.021 and 0.051 ng mL-1, respectively, which indicates the high sensitivity of the proposed method. Additionally, no significant changes were detected after storage of analytes inside the needle at 4 °C after 60 days. The results of this study also provide a high correlation between the results of sampling with needles containing PANI@HA and with XAD-2 adsorbent tubes (standard NIOSH 5115 method) (R 2 = 0.98). Finally, the proposed method was successfully employed in the extraction and determination of polycyclic aromatic hydrocarbons in field (real) samples. In general, it can be concluded that a needle packed with PANI@HA is a reliable and high-performance method for sampling polycyclic aromatic hydrocarbons compared to the NIOSH method.

Development of a needle trap device packed with titanium-based metal-organic framework sorbent for extraction of phenolic derivatives in air.

We developed a novel method of needle trap device packed with titanium-based metal-organic framework for the extraction of phenolic derivatives in air followed by gas chromatography-flame ionization detector analysis. The synthetized adsorbent was packed inside a 22-gauge spinal needle. This method was first tested at laboratory scale, and then was used for field sampling of phenolic derivatives in air. A glass chamber placed on a heater at 60°C was used to provide different concentrations of phenolic derivatives. The desorption conditions and breakthrough volume were optimized using response surface methodology. The limit of detection and limit of quantitation of the proposed method were estimated to be in the range of 0.001-0.12 and 0.003-0.62 ng/mL, respectively, indicating a high sensitivity for the suggested sampler. Storing the packed needle trap device in a refrigerator at 4˚C for 60 days did not dramatically affect the storage stability. Our findings indicated that there was a high correlation coefficient (R2  = 0.99) between the measurement results of this method and the NIOSH recommended method (XAD-7 sorbent tube). Therefore, it can be concluded that the needle trap device packed with titanium-based metal-organic framework can be used as a efficient method for extraction of phenolic derivatives in air.

Exhaled breath malondialdehyde, spirometric results and dust exposure assessment in ceramics production workers.

INTRODUCTION: The study aimed at measuring exhaled breath malondialdehyde (EBC-MDA) in workers exposed to dust containing silica and at its comparison with the non-exposed control group. MATERIAL AND METHODS: The cross sectional, case-control study (N = 50) was performed in a tile and ceramics production factory in Yazd, Iran. EBC-MDA was quantified in exhaled breath of the participants by a lab made breath sampler. Exposure intensity was measured according to the NIOSH 0600 method in selected homogeneous exposure groups. Additionally, spirometry test was conducted to investigate a correlation between EBC-MDA and spirometric findings in the exposed workers. RESULTS: There was no difference in the observed exposure intensities of silica containing dust in different units. However, "coating preparation" was the unit with the highest concentration of dust. Although, the level of EBC-MDA in the cases was slightly higher than in the controls, the difference was not statistically significant (U = 252, p = 0.464). A significant and positive correlation was found between dust exposure intensity in working units and the measured EBC-MDA of workers (r = 0.467, N = 25, p = 0.027). There were also no statistically significant differences among job categories in the exposed group for the values of FEV1% (F(3, 44) = 0.656, p = 0.584), FVC% (F(3, 44) = 1.417, p = 0.172), and FEV1/FVC% (F(3, 44) = 1.929, p = 0.139). CONCLUSIONS: The results showed a significant correlation between respirable dust exposure intensity and the level of EBC-MDA of the exposed subjects. However, our results did not show a significant correlation between lung function decreases and EBC-MDA.

Occupational cancer risk perception in Iranian workers.

This cross-sectional study examined the occupational cancer risk perception among 269 Iranian industrial workers according to their knowledge, job titles hazard, and demographical properties. The structured questionnaire was used to measure participants' knowledge and perception toward occupational cancers (reliability of the perception questions = .72). There was significant difference in both knowledge and perception about occupational cancers in different age and educational groups. It was significant relation between knowledge and perception (p = .001). True answer to some questions was less than 20%. An optimistic bias was found in participants' perception. These findings prove that cancer risk perception in industrial workforces is affected by several factors. Further efforts should be placed in the training of workers to enhance their knowledge and subsequently their perception toward occupational cancers.

Cancer Risk Assessment in Welder's Under Different Exposure Scenarios.

BACKGROUND: Welders exposure to nickel and hexavalent chromium in welding fumes is associated with increase of cancer risk in welders. In this study we calculated cancer risk due to exposure to these compounds in welders. METHODS: The role of exposure parameters in welders on derived incremental lifetime cancer risk were determined by stochastic modeling of cancer risk. Input parameters were determined by field investigation in Iranian welders in 2013 and literature review. RESULTS: The 90% upper band cancer risk due to hexavalent chromium and nickel exposure was in the range of 6.03E-03 to 2.12E-02 and 7.18E-03 to 2.61E-02 respectively. Scenario analysis showed that asthmatic and project welders are significantly at higher cancer risk in comparison with other welders (P<0.05). Shift duration was responsible for 37% and 33% of variances for hexavalent chromium and nickel respectively. CONCLUSIONS: Welders are at high and unacceptable risk of cancer. Control measures according to scenario analysis findings are advisable.