High Performance Liquid Chromatography-negative Electrospray Research Articles

Contamination profile and risk assessment of per- and polyfluoroalkyl substances in Guanting Reservoir, a former drinking water source with degraded water quality

The water quality of Guanting Reservoir couldn't meet the requirement of the standard for drinking water sources in China from 1997 since its pollution. The present work studied the pollution characteristics of per- and polyfluoroalkyl substances (PFASs) in water and sediments in Guanting Reservoir, 4 tributaries and WWTPs by high-performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). The sources and risks of the identified PFASs were analyzed. There were 11 PFASs detected in the Guanting Reservoir, the average PFASs concentration was 267.89 ng/L in water and 2.17 ng/g in sediment, respectively, which are higher than those in other water sources within and outside China. Perfluorooctanoic acid (PFOA) was the main pollutant in both water and sediments, and it has potential ecological risk (0.1 < RQ < 1) in both water and sediment samples as well as potential health risk with HR value ranges in 0.25–0.64 in water in Guanting Reservoir. Sanggan River and Yongding River are the main input sources of PFASs pollution, and the direct emission from industrial production and the degradation of precursors have been shown to make a great contribution to the PFASs in Guanting Reservoir. The results suggest that continuous monitoring and integrated risk assessment in Guanting Reservoir catchment and more attention should be paid on the pollution control from Sangan River and Yongding River.

Perfluorinated Compounds (PFCs) in Soil of the Pearl River Delta, China: Spatial Distribution, Sources, and Ecological Risk Assessment.

This study investigated the levels, spatial distribution, sources, and ecological risks of 16 perfluorinated compounds (PFCs) in 68 surface soil samples (0-20cm) from 7 cities in the Pearl River Delta (PRD), China. Sixteen target PFCs, including perfluoroalkyl carboxylic acids (PFCAs, C5-C14, C16, and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8, and C10), were analyzed by high-performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Concentrations of total PFCs (∑PFCs) ranged from 2.19 to 98.5μgkg-1 (dry weight, dw), with an average of 5.97μgkg-1dw. Perfluorooctane sulfonate (PFOS) was the dominant PFC, accounting for 23.9% of ∑PFCs. The highest ∑PFCs was found in the soil sample collected from Dongguan with a large number of manufacturing industries. There were no significant differences of ∑PFCs among unban, industrial, and agricultural soils, indicating similar pollution sources in soil of the PRD. More than 70% of ∑PFCs in soil of the PRD could be attributed to the four principal components, represented by PFOS and perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA) and perfluorohexanoic acid (PFHxA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUdA). Ecological risk assessment indicated that PFOA had low risk to soil plants and animals. However, the risk of PFOS to soil plants was relatively high in some studied regions.

Perfluorinated compounds (PFCs) in the atmosphere of Shenzhen, China: Spatial distribution, sources and health risk assessment

This study investigated the occurrence of perfluorinated compounds (PFCs) in the atmosphere of Shenzhen, China. 11 PFCs, including two perfluoroalkyl sulfonic acids (PFSAs, C6 and C8) and perfluoroalkyl carboxylic acids (PFCAs, C4–12) were determined by high performance liquid chromatography–negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Total PFC concentrations (∑ PFCs) in the atmospheric samples ranged from 3.4 to 34pgm−3 with an average of 15pgm−3. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were the two most abundant PFCs and on average accounted for 35% and 22% of ∑ PFCs, respectively. ∑ PFCs and total PFCA concentrations (∑ PFCAs) showed a tendency of low-lying East West, while the distribution of total PFSA concentrations (∑ PFSAs) was uniform. Higher concentrations of ∑ PFCs were found in Bao’an District which had very well-developed manufacturing industries. PCA model was employed to quantitatively calculate the contributions of sources. The results showed that PFOA-factor, long chain PFCs-factor and PFOS-factor were the three main source categories for PFCs in the atmosphere. Meanwhile, long-distance transport of pollutants from southeastern coastal areas might be another source of PFCs in Shenzhen atmosphere. PFCs in the atmosphere were more positively correlated with the levels PM10 than PM2.5, which indicated PFCs were more likely to adhere to particles with relatively large sizes. The hazard ratios of noncancer risk through breathing based on PFOS and PFOA concentrations were calculated and were less than unity, suggesting that PFCs concentrations may pose no or immediate threat to the residents in Shenzhen.

Spatial distribution and partition of perfluoroalkyl acids (PFAAs) in rivers of the Pearl River Delta, southern China.

This study investigated the occurrence of perfluoroalkyl acids (PFAAs) in surface water from 67 sampling sites along rivers of the Pearl River Delta in southern China. Sixteen PFAAs, including perfluoroalkyl carboxylic acids (PFCAs, C5-14, C16 and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8 and C10) were determined by high performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Total PFAA concentrations (∑ PFAAs) in the surface water ranged from 1.53 to 33.5 ng·L(-1) with an average of 7.58 ng·L(-1). Perfluorobutane sulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonic acid (PFOS) were the three most abundant PFAAs and on average accounted for 28%, 16% and 10% of ∑ PFAAs, respectively. Higher concentrations of ∑ PFAAs were found in the samples collected from Jiangmen section of Xijiang River, Dongguan section of Dongjiang River and the Pearl River flowing the cities which had very well-developed manufacturing industries. PCA model was employed to quantitatively calculate the contributions of extracted sources. Factor 1 (72.48% of the total variance) had high loading for perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), PFBS and PFOS. For factor 2 (10.93% of the total variance), perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUdA) got high loading. The sorption of PFCAs on suspended particulate matter (SPM) increased by approximately 0.1 log units for each additional CF2 moiety and that on sediment was approximately 0.8 log units lower than the SPM logKd values. In addition, the differences in the partition coefficients were influenced by the structure discrepancy of absorbents and influx of fresh river water. These data are essential for modeling the transport and environmental fate of PFAAs.

Rapid simultaneous determination of dexamethasone and betamethasone in milk by liquid chromatography tandem mass spectrometry with isotope dilution

A simple, sensitive and reliable analytical method for the rapid simultaneous determination of dexamethasone and betamethasone in milk by high performance liquid chromatography–negative electrospray ionization tandem mass spectrometry (HPLC–NESI-MS/MS) with isotope dilution was developed. Samples were directly purified through C 18 cartridge. Then the eluate was dried under nitrogen and residues were dissolved in mobile phase. Samples were analyzed by HPLC–MS/MS on a Hypercarb graphite column with a mixture of acetonitrile–water–formic acid as mobile phase. The samples were quantified using dexamethasone-D 4 as an internal standard. The procedure was validated according to the European Union regulation 2002/657/EC determining specificity, decision limit (CCα), detection capability (CCβ), trueness, precision, linearity and stability. The method is demonstrated to be suitable for the determination of dexamethasone and betamethasone in milk. The total time required for the analysis of one sample was about 35 min.

A comparative study on oxidative damage and distributions of perfluorooctane sulfonate (PFOS) in mice at different postnatal developmental stages

Effects of perfluorooctane sulfonate (PFOS) on maleic dialdehyde (MDA) content, superoxide dismutase (SOD) activity and total antioxidation capability (T-AOC) were compared in mice at different postnatal developmental stages, and concentrations and distributions of PFOS in different tissues were measured simultaneously. The male and female mice at postnatal day (PD) 7, PD 14, PD 21, PD 28 and PD 35 were distributed randomly to dosage group (50 mg/kg body weight) and control group (0 mg/kg body weight). Mice were administered with PFOS by once subcutaneous injection. Subsequently, after 24 hr, MDA content, SOD activity and T-AOC in brain and liver were analyzed. The PFOS concentrations in blood, brain and liver were determined by high-performance liquid chromatography negative electrospray tandem mass spectrometry (LC-MS). PFOS induced degression of the body weights of mice evidently and increase of relative weights of liver. Meanwhile, it depressed the SOD activity and T-AOC in brain and liver. The concentrations and distribution percentages of PFOS in blood, brain and liver of mice were significantly different at various postnatal developmental stages. Achieved results in this study indicate that younger mice pups were more sensitive to PFOS exposure. In addition, significant distinctions in concentrations and distribution percentages of PFOS in various tissues were demonstrated in this study. The gender difference observed was greater in the older mice. Thus it is worth giving attention especially to adverse effects of PFOS on foetus and children.