Abstract
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.
Highlights
According to the latest information published by the International Agency for Research on Cancer (IARC), the carcinogenicity of these compounds is classi ed in terms of trichloroethylene in group 1A, tetrachloroethylene in group 2A, and carbon tetrachloride and chloroform in group 2B
The Ni/Zn–BTC bi-metallic metal–organic framework (MOF) was introduced as a water-stable absorbent for the monitoring of non-metabolized halogenated hydrocarbon compounds in the urine matrix, for the rst time
The proposed adsorbent was employed in a dynamic headspace-needle trap device as an impressive and moisture stable absorbent in the laboratory and real-time conditions
Summary
Halogenated hydrocarbons are an important group of volatile compounds that are widely used in industrial applications as solvents, degreasing agents, detergents, and chemical intermediates in the polymerization process.[1,2] According to the latest information published by the International Agency for Research on Cancer (IARC), the carcinogenicity of these compounds is classi ed in terms of trichloroethylene in group 1A (carcinogenic to humans), tetrachloroethylene in group 2A (probably carcinogenic to humans), and carbon tetrachloride and chloroform in group 2B (possibly carcinogenic to humans).due to the toxicity of halogenated hydrocarbons, trying to nd an accurate, fast, and highly sensitive analysis method for biomonitoring these compounds in the human body is still important. One of the acceptable techniques for the bio-monitoring of halogenated hydrocarbon compounds is the use of speci c biomarkers in urine.[3] The non-metabolized form of chemical compounds usually has more speci c biomarkers than their metabolite forms(s), because the metabolized compounds may be derived from other exogenous or endogenous compounds.[4,5] The non-metabolized forms of chloroform, trichloroethylene, tetrachloroethylene and carbon tetrachloride in the urine sample as reliable and sensitive biomarkers have been measured using conventional techniques such as thin layer headspace, solid-phase extraction, and HS-SPME.[6,7,8,9,10,11] Despite the eye-catching advantages of the SPME method, limited adsorption capacity and ber fragility are some of the disadvantages
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