Optimization of Odorous Compounds Analysis in Water Using Headspace-SPME and GC-MSD, and Detection Characteristics in the Nakdong River Basin

Objectives : This study developed a simple and automated analytical method using headspace-SPME (solid phase microextraction) and GC (gas chromatography)-MSD (mass selective detector) to simultaneously analyze ten odorous compounds (dimethyl trisulfide (DMTS), 3-hexenylacetate (HA), 2-isopropyl-3-methoxypyrazine (IPMP), 2-methylbenzofuran (MBF), 2-isobutyl-3-methoxypyrazine (IBMP), β-cyclocitral (CC), trans-2-decenal (DCNL), 2-trans-4-trans-decadienal (DENL) 2,4,6-trichloroanisole (TCA) 및 β-ionone (ION)), evaluating their distribution characteristics throughout the Nakdong River basin.Methods : To optimize the extraction efficiency of the headspace-SPME method for ten odorous compounds, we evaluated various SPME fiber materials, extraction temperatures, extraction times, desorption temperatures, desorption times and salt (NaCl) dosages. Additionally, using the optimized headspace-SPME, we investigated the detection concentrations at ten main stream sites and six tributary sites in the Nakdong River basin.Results and Discussion : The most suitable SPME fiber material for the pretreatment of ten odorous compounds was CAR/PDMS/DVB. The optimal SPME extraction temperature and time were 75°C and 60 minutes, respectively, and the optimal desorption temperature and time at the GC injection port were 250°C and 3 minutes. Additionally, the optimal salt (NaCl) dosage for a 10 mL water sample was 2 g. Using the optimized headspace-SPME pretreatment method for GC-MSD analysis, the detection limits and quantification limits for the ten odorous compounds ranged from 2 to 10 ng/L and 5 to 25 ng/L, respectively, with HA exhibiting the highest detection and quantification limits. The evaluation of the distribution characteristics of odorous compounds throughout the Nakdong River basin revealed that only three compounds—DMTS, CC and ION—were detected. Among these, DMTS was found at the highest concentration of 115.5 ng/L in the tributary Jincheon-cheon, while CC was detected at the highest concentration of 30.6 ng/L in the main river at Goryeong. In the case of the Nakdong River basin, there was no contamination by odorous compounds in the upstream area. In the middle reach, influenced by effluent of wastewater treatment plants, the detection concentrations of three odorous compounds increased, but they showed a decreasing trend as they moved downstream.Conclusion : Since odorous compounds can lead to distrust in water quality even at extremely low concentrations in the ng/L range in tap water, regular monitoring of water sources is necessary during algal bloom season, including the dry season. Furthermore, continuous research is needed on various odorous compounds beyond the 10 odorous compounds in this study, including the optimization of analytical methods and the detection characteristics in water sources.