A Single Latent Plant Growth-Promoting Endophyte BH46 Enhances Houttuynia cordata Thunb. Yield and Quality.

Plant growth-promoting endophytes (PGPE) can effectively regulate plant growth and metabolism. The regulation is modulated by metabolic signals, and the resulting metabolites can have considerable effects on the plant yield and quality. Here, tissue culture Houttuynia cordata Thunb., was inoculated with Rhizobium sp. (BH46) to determine the effect of BH46 on H. cordata growth and metabolism, and elucidate associated regulatory mechanisms. The results revealed that BH46 metabolized indole-3-acetic acid and induced 1-aminocyclopropane-1-carboxylate deaminase to decrease ethylene metabolism. Host peroxidase synthesis MPK3/MPK6 genes were significantly downregulated, whereas eight genes associated with auxins, cytokinins, abscisic acid, jasmonic acid, and antioxidant enzymes were significantly upregulated. Eight genes associated with flavonoid biosynthesis were significantly upregulated, with the CPY75B1 gene regulating the production of rutin and quercitrin and the HCT gene directly regulating the production of chlorogenic acid. Therefore, BH46 influences metabolic signals in H. cordata to modulate its growth and metabolism, in turn, enhancing yield and quality of H. cordata.

An assembled bacterial community associated with Artemisia annua L. causes plant protection against a pathogenic fungus.

The microorganisms associated with a plant influence its growth and fitness. These microorganisms accumulate on the aerial and root surfaces of plants, as well as within the plants, as endophytes, although how the interaction between microorganisms protects the plant from pathogens is still little understood. In the current study, the impact of assembled the bacterial communities against the pathogenic fungus to promote Artemisia annua L. growths was investigated. We established a model of bacterium-fungus-plant system. Eight bacterial strains and a fungal pathogen Globisporangium ultimum (Glo) were isolated from wild A. annua roots and leaves, respectively. We assembled the six-bacteria community (C6: Rhizobium pusense, Paracoccus sp., Flavobacterium sp., Brevundimonas sp., Stenotrophomonas sp., and Bacillus sp.) with inhibition, and eight-bacteria community (C8) composing of C6 plus another two bacteria (Brevibacillus nitrificans and Cupriavidus sp.) without inhibition against Glo in individually dual culture assays. Inoculation of seedlings with C8 significantly reduced impact of Glo. The growth and disease suppression of A. annua seedlings inoculated with C8 + Glo were significantly better than those of seedlings inoculated with only Glo. C8 had more inhibitory effects on Glo, and also enhanced the contents of four metabolites in seedling roots compared to Glo treatment only. Additionally, the inhibitory effects of root extracts from A. annua seedlings showed that Glo was most sensitive, the degree of eight bacteria sensitivity were various with different concentrations. Our findings suggested that the non-inhibitory bacteria played a vital role in the bacterial community composition and that some bacterial taxa were associated with disease suppression. The construction of a defined assembled bacterial community could be used as a biological fungicide, promoting biological disease control of plants.

Current Status and Health Risk Assessment of Heavy Metals Contamination in Tea across China.

Tea is a non-alcoholic beverage popular among Chinese people. However, due to the application of chemical and organic fertilizers in the tea planting process, the environment pollutionaround the tea plantation, and the instruments used in the processing, heavy metal elements will accumulate in the tea, which brings health risks for tea consumers. This study summarized heavy metal concentrations from 227 published papers and investigated the current contamination status of tea and tea plantation soils, and, finally, the risk of heavy metal exposure to tea consumers in China is assessed, in terms of both non-carcinogenic and carcinogenic risk. The average contamination of six heavy metals in tea-arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), and lead (Pb)-were 0.21, 0.14, 1.17, 14.6, 0.04, and 1.09 mg/kg, respectively. The areas with high concentrations of heavy metals in tea were concentrated primarily in southwest China, some areas in eastern China, and Shaanxi Province in northwest China. The non-carcinogenic risks of heavy metals in tea are all within safe limits. The national average HI value was 0.04, with the highest HI value of 0.18 in Tibet, which has the largest tea consumption in China. However, the carcinogenic risks of Cd in Shaanxi Province, Anhui Province, and southwest China exceed the acceptable range, and due attention should be given to these areas.

Investigation of water quality and aquatic ecological succession of a newly constructed river replenished by reclaimed water in Beijing.

The potential to create new ecosystems in rivers is possible through the use of reclaimed water as a replenishment source, although the long-term effects of this method are unknown. In this study, the water quality and aquatic ecological evolution of a newly constructed river replenished by reclaimed water in Beijing (the Jing River) were investigated, and the conventional water quality, phytoplankton indicators, and submerged plant growth conditions from October 2018 to December 2020 were analyzed. Spearman's correlation and redundancy analysis between possible influential environmental factors and algal indicators were conducted. The results show that the major water quality indicators could meet the water quality standards for landscape water. There were seven phyla present, including 322 species of phytoplankton. The phytoplankton density increased, followed by a decreasing trend. Phytoplankton densities at each monitoring site reached 10 × 106 to 25 × 106 cells/L in 2019 before decreasing in 2020, then ranging from 8 × 106 to 20 × 106 cells/L. Phytoplankton growth was influenced by changing water quality and ecosystems. Consequently, the submerged plant coverage rate gradually increased from 2018 (0%) to 2020 (26.27%-37.06%), as did biodiversity. Through the implementation of ecological restoration measures in the Jing River, the reclaimed water environment evolved into a more natural water environment, which could provide some reference for similar areas to use reclaimed water as a water replenishment source.

Improved Electric Breakdown Strength and Energy Storage Performances in La(Mg2/3Nb1/3)O3 and MnO2-Modified BiFeO3-SrTiO3 Ceramics.

Dielectric capacitors have become an important component in current pulsed power devices and thus have attracted great research interest in recent years. Among all kinds of dielectric materials, the bismuth ferrite (BiFeO3)-based ceramic capacitors show possible applications in dielectric energy storage because of their large polarization. However, the relatively high conductivity badly limits the improvement of electric breakdown strength, thus leading to low energy density. Herein, the perovskite end-member La(Mg2/3Nb1/3)O3 and sintering aid MnO2 were simultaneously introduced into BiFeO3-SrTiO3 solid solutions to improve the relaxation features and electric breakdown strength. Accordingly, a high recoverable energy density of 6.3 J/cm3 and an acceptable efficiency of 74.3% were realized under 450 kV/cm. In addition, the good frequency/thermal stability and superior charge-discharge performances were also realized. This work provides feasible approaches to modify the capacitive energy storage of BiFeO3-based relaxor ferroelectric ceramics.

Significantly Enhanced Energy Storage Performance of Lead-Free BiFeO3-Based Ceramics via Synergic Optimization Strategy.

Owing to the merits of giant power density and ultrafast charge-discharge time, dielectric capacitors including ceramics and films have inspired increasing interest lately. Nevertheless, the energy storage density of dielectric ceramics should be further optimized to cater to the boosting demand for the compact and portable electronic devices. Herein, an ultrahigh recoverable energy storage density Wrec of 13.44 J/cm3 and a high efficiency η of 90.14% are simultaneously realized in BiFeO3-BaTiO3-NaTaO3 relaxor ferroelectric ceramics with high polarization Pmax, reduced remanent polarization Pr, and optimized electric breakdown strength Eb. High Pmax originates from the genes of BiFeO3-based ceramics, and reduced Pr is induced by enhanced relaxor behavior. Particularly, a large Eb is achieved by the synergic contributions from complicated internal and external factors, such as decreased grain size and improved resistivity and electrical homogeneity. Furthermore, the ceramics also exhibit satisfactory frequency, cycling and thermal reliability, and decent charge-discharge property. This work not only indicates that the BiFeO3-based relaxor ferroelectric materials are promising choices for the next-generation electrostatic capacitors but also paves a potential approach to exploit novel high-performance dielectric ceramics.

Occurrence, Distribution, and Risk Assessment of Antibiotics in the Aquatic Environment of the Karst Plateau Wetland of Yangtze River Basin, Southwestern China.

In this study, the occurrence, distribution, and ecological risk of 40 commonly used antibiotics, including 15 sulfonamides (SAs), 9 fluoroquinolones (FQs), 7 macrolides (MCs), 3 tetracyclines (TCs), 2 chloramphenicols (CAPs), and 4 other categories, in the aquatic environment of the karst plateau wetland Caohai of the Yangtze River basin in southwestern China are reported. In total, 27 antibiotics were detected, with the detection rate ranging from 5% to 100%. The total concentration at each site ranged from 21.8 ng/L to 954 ng/L, with the average concentration being 189 ng/L. FQs and MCs were the most predominant categories, contributing 29.3% and 25.0% of the total antibiotic burden. The five most commonly detected antibiotics were ciprofloxacin (CIP), oxytetracycline (OTC), acetyl sulfamethoxazole (ASMZ), norfloxacin (NOR), and florfenicol (FF). The spatial distribution of the total concentration at each site demonstrated a decreasing trend from the southeastern area upstream adjoining the main counties to the northwestern area downstream, indicating that human activities have a great impact. Meanwhile, the natural attenuation rates of different types of antibiotics in the direction of flow ranged from 17.6% to 100%, which implied the natural purification potential of the wetland for antibiotics. The cluster analysis results indicated that domestic sewage and wastewater from agriculture and animal husbandry were the main sources of contamination in the surrounding wetland. Risk quotients (RQs) assessment showed that most of the individuals were at low to medium risk and that the adverse risks posed by mixtures of antibiotics were higher than those posed by the individual antibiotics.

Latent Pathogenic Fungi in the Medicinal Plant Houttuynia cordata Thunb. Are Modulated by Secondary Metabolites and Colonizing Microbiota Originating from Soil.

Latent pathogenic fungi (LPFs) affect plant growth, but some of them may stably colonize plants. LPFs were isolated from healthy Houttuynia cordata rhizomes to reveal this mechanism and identified as Ilyonectria liriodendri, an unidentified fungal sp., and Penicillium citrinum. Sterile H. cordata seedlings were cultivated in sterile or non-sterile soils and inoculated with the LPFs, followed by the plants' analysis. The in vitro antifungal activity of H. cordata rhizome crude extracts on LPF were determined. The effect of inoculation of sterile seedlings by LPFs on the concentrations of rhizome phenolics was evaluated. The rates of in vitro growth inhibition amongst LPFs were determined. The LPFs had a strong negative effect on H. cordata in sterile soil; microbiota in non-sterile soil eliminated such influence. There was an interactive inhibition among LPFs; the secondary metabolites also regulated their colonization in H. cordata rhizomes. LPFs changed the accumulation of phenolics in H. cordata. The results provide that colonization of LPFs in rhizomes was regulated by the colonizing microbiota of H. cordata, the secondary metabolites in the H. cordata rhizomes, and the mutual inhibition and competition between the different latent pathogens.

Assessment of the risks from dietary lead exposure in China.

The dietary lead (Pb) risk across China was assessed based on the margin of exposure (MOE) approach by comparing the level (1.5 µg/kg/d) based on the Pb concentrations in foodstuffs from1386 published articles. The Pb averages of the 18 foods were lower than their corresponding limits enacted by the Chinese government, ranging from 0.09 to 0.30 mg/kg. Food from plants had a much higher contribution to dietary Pb intake than that from animals (86% vs. 14%), and cereals and vegetables contributed 79% of the Pb intake from plant-based food. Although each category of food contained a relatively low Pb concentration, the accumulated Pb from the total diet posed a high risk to human health. The MOE risk from dietary Pb averaged 1.57 and ranged from 0.13 to 6.18, with high risks in southern, southwestern, eastern, central, and northern China. The MOE risk from Pb could be decreased by adjusting the dietary structure, and the ratio of people categorized as high risk (MOE < 1) would decrease from 56% to 37%, 41%, or 24% if the category of cereal or vegetable or both cereals and vegetables with the lowest Pb concentration in their local areas were selected, respectively.

Endophytic fungi stimulate the concentration of medicinal secondary metabolites in houttuynia cordata thunb.

Endophytic fungi usually establish a symbiotic relationship with the host plant and affect its growth. In order to evaluate the impact of endophytic fungi on the Chinese herbal medicinal plant Houttuynia cordata Thunb., three endophytes isolated from the rhizomes of H. cordata, namely Ilyonectria liriodendra (IL), unidentified fungal sp. (UF), and Penicillium citrinum (PC), were co-cultured individually with H. cordata in sterile soil for 60 days. Analysis of the results showed that the endophytes stimulated the host plant in different ways: IL increased the growth of rhizomes and the accumulation of most of the phenolics and volatiles, UF promoted the accumulation of the medicinal compounds afzelin, decanal, 2-undecanone, and borneol without influencing host plant growth, and PC increased the fresh weight, total leaf area and height of the plants, as well as the growth of the rhizomes, but had only a small effect on the concentration of major secondary metabolites. Our results proved that the endophytic fungi had potential practical value in terms of the production of Chinese herbal medicines, having the ability to improve the yield and accumulation of medicinal metabolites.

[Occurrence Characteristics and Health Risk Assessment of Endocrine Disrupting Chemicals in Groundwater in Wuxi-Changzhou].

The concentrations of 22 endocrine disrupting chemicals, including 4 categories of sex hormones, progesterones, glucocorticoids, and phenolic hormones, in groundwater of Wuxi-Changzhou were analyzed using solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry. The results indicated that 20 EDCs were detected, among which bisphenol A (BPA), estrone (E1), estradiol (E2), and 17α-ethinyl estradiol (EE2) were the main components with detection ratios greater than 90%, followed by estriol (E3) and methyl-prednisolonel (Meprednl), which had detection rates 67.7% and 48.4%, respectively. The average concentration of BPA was the highest (4.95 ng·L-1), followed by that of Meprednl, E2, prednisolone (Prednl), testosterone propionate (TES-pro), and megestrol-acetate (MA; 2.84, 0.71, 0.64, 0.58, and 0.53 ng·L-1, respectively). The total concentration in each site ranged from 0.38 to 147.35 ng·L-1. The sites with higher concentration were mainly distributed in the Xinbei District, Liyang City, and the Zhonglou District of Changzhou City. The potential sources were analyzed by a principal component analysis (PCA) combining the point sources near sample sites. The results showed that domestic sewage, aquaculture, and industrial wastewater were the main sources, following by medical wastewater. A non-carcinogenic risk assessment showed a low risk of EDCs in the groundwater of the study area, and the risk of drinking water was greater than that of skin exposure. EE2 had the highest non-carcinogenic risk and is suggested to be monitored in priority.

Fully automated identification and quantification of five polar pesticides in groundwater by isotope dilution-online solid phase extraction coupled with high-performance liquid chromatography-quadrupole Orbitrap high-resolution mass spectrometry.

A fully automated method for identification and quantification of five polar pesticides in groundwater by isotope dilution-online solid-phase extraction (SPE) coupled with high-performance liquid chromatography-quadrupole Orbitrap high-resolution mass spectrometry was developed. After one step of filtration, an aliquot of a 7.5-ml water sample was automatedly preconcentrated and purified on a turbulent Cyclone SPE column. The analytes were eluted in backflush mode, then separated on an analytical column and acquired by full MS/dd-MS2 scan in negative and positive ions mode. The major parameters for sample loading, cleanup, and elution were optimized in detail. Preconcentration and ionization efficiency were highly improved by using 0.1% acid solution in the mobile phase. The method provided good linearity of calibration coefficients (R2 > 0.995), sensitive method limits of detection (0.5-10.0 ng/L), accurate mass spectra (within 5 ppm error), satisfactory matrix spiking recoveries (98.4% to 109%), and high precision (intraday/interday relative standard deviations 1.57-8.90%). The method was successfully applied to analyze large batch groundwater of National Groundwater Monitoring Project and suspect screening of potential pesticides in groundwater. The study provided a practical alternative for a simple, robust, sensitive, and accurate identification and qualification of five polar pesticides in groundwater.

[Characterization of Microplastic Pollution of Sediments from Urban Lakes].

In recent years, microplastics (MPs) in the environment has become a topic of increasing concern. In this study, typical urban lakes, such as Yushan Lake and Nanhu Lake in Maanshan City, were selected to study the physical morphology and spatial distribution characteristics of MPs in sediments in spring and summer and to explore the sources of MPs in the lakes. On average, MPs in sediments occurred with a content of (0.0284±0.0597) g·kg-1 and abundance of (278.9±529.1) n·kg-1 in spring, and (0.0317±0.0778) g·kg-1 and (277.1±395.6) n·kg-1 in summer, respectively. Using a paired sample T-test, it was found that there was no significant correlation difference between the content (N=22, t=-0.269, P=0.791) and the abundance (N=22, t=0.035, P=0.973) of MPs in the spring and summer sediments. Regarding shape, the MPs in the sediments in the study area were divided into three types:fiber, film, and particle, accounting for 52.9%, 28.9%, and 18.2%, respectively. Size-fraction analysis indicated MPs<1 mm made up the majority, accounting for 83.9% of the total number. It was found that the MPs were mainly polyethylene (PE) and polypropylene (PP) polymers with seriously weathered surfaces. The sediments, which were adjacent either to land with a large stream of people and vehicles or to areas with frequent watersports, had notably high abundance of MPs, revealing the close correlation between the spatial distribution of MPs in lake sediments and human activities. It is thought that atmospheric precipitation (fiber), stormwater, washing of clothes (fiber), degradation of large plastics in the lake, and fishing activities (fishing nets, foam) are the main sources of MPs in lake sediments.

Microplastics in Sediments of River Yongfeng from Maanshan City, Anhui Province, China.

This study was performed to evaluate the microplastics (MPs) pollution of sediments from River Yongfeng. It was observed that the MPs in sediments were present with contents of 0.5-16.75 mg/kg and abundances of 5-72 items/kg, coupled by variation coefficients of 109% and 91%, respectively, indicating that the distribution of MPs had high spatial variation. The land-based source of business zone is thought to be the significant contributor to accumulation of MPs in those sites with high quantity of MPs. Film was the predominant shape of MPs in river sediments followed by the line and fragment ones. Meanwhile, the MPs detected were mainly composed by four types including Polypropylene (24%), Polyethylene (61%), Polyethylene Terephthalate (8%) and Polystyrene (7%) based on number fraction, respectively, which indicates that Polypropylene and Polyethylene were the major types of MPs in the sediments. Size fraction performance suggests that those MPs < 1000 µm were of ubiquitous presence. The weathering of fringes was universally observed regardless of varying surface among MPs. Despite digestion with oxidative acid solution and subsequent washing by distilled water unexpected elements can still be detected, which should be considered as determining the materials associated.

[Distribution of 16 Polycyclic Aromatic Hydrocarbons in Dianchi Lake Surface Sediments After the Integrated Water Environment Control Project].

The external pollution of Dianchi Lake has been effectively controlled with the implementation of the integrated water environment control project. However, further attention should be paid to endogenous pollutants, such as surface sediments. To investigate the distribution of 16 polycyclic aromatic hydrocarbons (PAHs) in surface sediments of Dianchi Lake, PAH concentrations in 19 surface sediment samples (collected in December 2016) were quantitatively measured by gas chromatography-mass spectrometry (GC-MS). The spatial and temporal distribution, sources, and ecological risks were also analyzed. The concentration of total PAHs (TPAHs) in the Dianchi Lake surface sediments varied in the range of 92.31-1546.78 ng·g-1 with an average of 496.30 ng·g-1. The average concentration of TPAHs in the surface sediments from Caohai (932.37 ng·g-1) was much greater than that from Waihai (380.02 ng·g-1). With the implement of the integrated water environment control project, the concentration of TPAHs in the surface sediments from Dianchi Lake was significantly lower than those detected in 2012, and was already relatively low level among other key waterbodies in China. The PAH with the highest concentration was fluoranthene (80.65 ng·g-1) and the substance with the highest toxic equivalent quantity (TEQ) was dibenz[a, h] anthracene (42.97 ng·g-1). The PAHs were mainly composed of 4 ring and 5-6 ring compounds (with the concentration ratio of 40.38% and 40.22%, respectively), which indicated that the proportions of middle-ring and high-ring compounds were generally consistent. The results of the molecular diagnostic ratio analysis showed that the primary source of PAHs in Dianchi Lake surface sediments are biomass and coal combustion. Based on the potential ecological risk marker comparison method, the entire lake was classified as having a low ecological risk, while the ecological risk of Caohai was relatively higher, which should be concerned further. The results provide initial data and act as an important reference for the conservation and improvement of water quality in Dianchi Lake.

Characteristics of particle size distribution and related contaminants of highway-deposited sediment, Maanshan City, China.

Road-deposited sediment (RDS) has been identified as both the source and sink of various pollutants. In this study, the highway-deposited sediment (HDS) in Spring, Summer, Autumn and Winter was characterized. On average, the mass proportions of particles with the size of 830-4750 µm, 500-830 µm, 250-500 µm, 150-250 µm, 63-150 µm and < 63 µm were 23.6 ± 8.6%, 16.9 ± 3.4%, 28.4 ± 3.5%, 10.0 ± 4.3%, 15.7 ± 5.8% and 5.3 ± 2.0%, respectively, wherein the HDS of 63-830 µm accounted for 71% of the total mass load. It was observed that the particle size distribution of HDS could be described using the gamma distribution function based on gravimetric and cumulative basis (R2 (determination coefficient) = 0.9960-0.9995). The bulk pollutant contents of HDS showed seasonal variation with the mean of COD (chemical oxygen demand), nitrogen, phosphorus, Zn (zinc), Pb (lead) and Cd (cadmium) as 57 g/kg, 839 mg/kg, 97 mg/kg, 627 mg/kg, 110 mg/kg and 1.00 mg/kg and the highest COD of 83 g/kg in Autumn, nitrogen 1164 mg/kg Autumn, phosphorus 133 mg/kg Winter, Zn 801 mg/kg Summer, Pb 133 mg/kg Spring and the highest Cd of 1.36 mg/kg in Summer, respectively. The contents of Zn, Pb and Cd in HDS were significantly above their local soil background values. Moreover, the size fractional pollutant contents overall increased as particles' size increased. Averagely, 40-52% pollutant loads were associated with the particles < 250 µm, which can be moved easily by runoff. This study suggests that the behaviors of HDS different from city RDS should be considered as nonpoint source pollution control is performed.

High-performance solution-processed white organic light-emitting diodes based on silica-coated silver nanocubes.

Solution-processed white organic light-emitting diodes (WOLEDs) with silica-coated silver nanocubes (Ag@SiO2 NCs) incorporated at the interface of a hole transporting layer and emission layer are studied. The concentration of Ag@SiO2 NCs is varied to investigate the effect of Ag@SiO2 NCs on the performances of WOLEDs. Owing to the sharp edges and corners, Ag NCs greatly improve the radiative rate and emission intensity of nearby blue excitons. The blue emission at different Ag@SiO2 NC concentrations determines the performance of the WOLEDs. The emission of the orange excitons is strengthened by the high concentration of Ag@SiO2 NCs, which slightly influences the device performance. On the other hand, the SiO2 shell and some SiO2 nanospheres coexisting with Ag NCs reduce the hole transporting, improving the carrier balance in the WOLEDs. The experimental and simulated results also show that excessive Ag@SiO2 NCs may cause a rough film surface, unbalanced carrier injection, and fluorescence quenching, which decreases the device performance. The optimized WOLED with a proper concentration of Ag@SiO2 NCs has a peak current efficiency of 53.9 cd/A, acquiring a significant enhancement factor of 77.3% compared to the control device without Ag@SiO2 NCs.

Dual Detection of Procalcitonin and C-reactive Protein with an Up-converting Nanoparticle Based Lateral Flow Assay.

Procalcitonin (PCT) and C-reactive protein (CRP) are significant complementary inflammatory markers, and their simultaneous detection is of substantial value. In this article, a rapid, simple and cost-effective method for the dual quantitative detection of PCT and CRP in serum is discussed. Two UCNPs of similar size and morphology, but with a different emission spectrum, were prepared for the simultaneous detection of PCT and CRP by lateral flow assay (LFA) technology in a direct method. With the developed dual test strips and signal read system, the assay results present a limit of detection (LOD) of 0.12 ng/mL and 0.24 µg/mL for PCT and CRP, respectively. In addition, both of the coefficients of variation and positive and negative concordance rates for PCT or CRP are well compared with those of the traditional method. The dual detection of PCT and CRP have shown great application potential in medical diagnosis and treatment guidance.

Simultaneous Determination of 32 Polycyclic Aromatic Hydrocarbon Derivatives and Parent PAHs Using Gas Chromatography-Mass Spectrometry: Application in Groundwater Screening.

A simple, practical and precise method for the simultaneous analysis of 32 different polycyclic aromatic hydrocarbon (PAHs) including 16 parent PAHs, 8 oxygenated-PAHs (oxy-PAHs), 4 chloro-PAHs, and 4 nitrogen-containing heterocyclic PACs (N-PACs), in groundwater was established via gas chromatography-mass spectrometry (GC-MS) combined with liquid-liquid extraction (LLE). The obtained detection method possesses instrument detection limits (at a signal to noise of 3:1) in the range of 0.05-10 ng/mL and method detection limits in the range of 1.7-13.2 ng/L. The average recoveries of the 32 analytes were in the range of 54.3%-127.0% with relative standard deviations (RSDs) < 20%, and the recoveries of 16 PAH derivatives ranged from 54.3 to 115.1% with RSDs < 17.9%. The method has been successfully applied to the screening of 64 groundwater samples from eastern China. The results revealed that 30 types of targets including 16 PAHs and 14 PAH derivatives were detected and that the groundwater in most areas is slightly polluted, while the pollution of Jiangsu Province and Shandong Province was more serious.

Headspace Solid-Phase Microextraction Coupled to Comprehensive Two-Dimensional Gas Chromatography Time-of-Flight Mass Spectrometry for the Determination of Short-Chain Chlorinated Paraffins in Water Samples.

Short-chain chlorinated paraffins (SCCPs) are a new type of persistent organic pollutants. In this work, a simple and effective method involving headspace solid-phase microextraction (HS-SPME) and comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS) was developed and optimized for the determination of trace SCCPs in water samples. The key parameters related to extraction and separation efficiency were systematically optimized. The SCCP congener groups were best resolved using an Rxi-5Sil MS (30 m × 0.25 mm × 0.25 µm) column followed by an Rxi-17Sil MS (1.0 m × 0.15 mm × 0.15 µm) column; the optimum extraction conditions were achieved with a 100 µm polydimethylsiloxane SPME fiber, when a 10 mL water sample added with 3.6 g sodium chloride was incubated for 15 min at 90°C and then extracted during 60 min at 90°C and desorption at 260°C for 2 min. The proposed method showed good linearity in the concentration range of 0.2-20.0 µg/L with the determination coefficient greater than 0.995. The detection and quantification limits ranged from 0.06 to 0.13 µg/L and 0.18 to 0.40 µg/L, respectively, which are sufficient to meet the regulatory detection limits as set by most environmental regulations. The accuracy and precision of the method was also good, where the recoveries ranged from 82.5 to 95.4%, and intra- and interday precision was within 7.2% and 14.5%, respectively. The optimized method has been applied to the determination of SCCPs in ten freshwater samples of three different types.