RESUMO
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.
RESUMO
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.
