A novel automated online SPE-coupled CE system with high precision has been developed, in which a four-port nano-valve served as an interface. With this system, 10 mL of pretreated water sample was introduced to the online SPE column, and the analytes were preconcentrated. After the cleanup step, the analytes were eluted, and a quantitative volume of the elution plug was injected in the capillary by switching the four-port nano-valve for CE separation. The experimental parameters, including the position of the four-port nano-valve, separation conditions, sample loading flow rate, sample volume, elution flow rate and four-port nano-valve switch time were optimized in detail. The effectiveness of the system was demonstrated by the analysis of six sulfonamide antibiotics in water samples. Good linear ranges were obtained with correlation coefficients from 0.9983 to 0.9997. The intra- and inter-day relative standard deviations were below 4.6 and 5.8%, respectively. The limits of detections were in the range of 2.22 to 3.35 ng mL−1. This proposed method was successfully applied to the analysis of effluent and influent water from a wastewater treatment plant, and the average recoveries of the wastewater samples ranged from 77.3 to 92.0%.

Fullerenols have wide application in the field of life sciences as a result of their extensive biocompatibility and biofunctionality. However, their environmental fate and ecotoxicological risks are largely unknown. In this study, stable isotope (13C) labeling was applied to investigate the bioaccumulation and depuration of fullerenols in Daphnia magna. By incorporation of 13C on the skeleton of fullerenols, the concentrations of fullerenols in the samples could be precisely determined on the basis of carbon isotope ratios (13C/12C). After exposure to 13C-labeled fullerenols in artificial freshwater for 48 h, the steady concentrations of fullerenols in D. magna were nearly 0.39 and 1.37% of the dry body weight in the 0.1 and 1.0 mg/L exposure groups, respectively. After 48 h of depuration, D. magna could excrete 97.34 and 89.56% of the accumulated fullerenols in 0.1 and 1.0 mg/L exposure group, respectively. The depuration of fullerenols from D. magna followed first-order kinetics. Moreover, accumulated fullerenols in gravid D. magna could be transferred to the next generation of neonates. The results in present study demonstrated that stable isotope (13C) labeling is a powerful tool to investigate the environmental fate and the potential impacts of fullerenols in ecological systems.

•A new phosphine modified charged polymer microsphere (PPMs) was synthesized and used as the adsorbent.•Without any foreign reagent, As(III), DMA, MMA and As(V) can be absorbed on the PPMs simultaneously in neutral condition.•SPE was on-line combined with HPLC–ICP-MS for the preconcentration of arsenic species in environmental waters.•The targets were eluted rapidly with a mixed solution of NH4NO3 and NH4H2PO4.•The entire preconcentration procedure could be finished within 5 min, and a relative high enrichment factor has been obtained.A new specific phosphine modified polymer microsphere (PPMs) was designed and used as the core adsorbent to comprehensively enrich both inorganic and organic arsenic species in environmental waters by on line solid-phase extraction (SPE). Avoiding any redox reagent, all the four arsenic species have been quantitatively retained on the home made mini-column with large number of positively charged adsorption groups, and then eluted rapidly (within seconds) with a mixed solution of ammonium nitrate and ammonium dihydrogen phosphate. The trace separation and determination of As(III), DMA, MMA and As(V) species have been simultaneously achieved by high performance liquid chromatography hyphenated to inductively coupled plasma spectrometry (HPLC–ICP-MS) technique. This work has developed a versatile tri-n-butylphosphine functionalized polymer microsphere for an efficient and reliable on-line of simultaneous preconcentration and detection of inorganic and organic arsenic speciation. Under the optimized experimental conditions, the enrichment factors obtained for As(III) and DMA with 25 mL sample solution were 28, while for MMA and As(V) reached 30. The low detection limits of 1.2 ng L−1, 0.96 ng L−1, 0.82 ng L−1 and 0.91 ng L−1, with the relative standard deviations (RSDs) of 3.9%, 5.6%, 3.2% and 4.5% were obtained for As(III), DMA, MMA and As(V), respectively. The developed method was validated by analyzing Certified Reference Materials GSBZ 07-3171-2014, promising for routine monitoring of arsenic species in lake water, river water and seawater samples.

•On-line preconcentration of chromium speices by SPE–HPLC–ICP-MS was developed•Functionalized poly(chloromethyl styrene) was synthesized and used as adsorbent.•The analytes were eluted rapidly with a very low concentration of TBAH.•The preconcentration and detection procedure could be finished within 7 min.•A very high enrichment factor has been obtained.Speciation analysis of inorganic chromium in wastewater is of great significance for the monitoring of environmental pollution. In this work, N,N-bis(2-aminoethyl)ethane-1,2-diamine functionalized poly(chloromethyl styrene-co-styrene) was synthesized, characterized and used as the adsorbent to preconcentrate chromium species in environmental waters by on line solid-phase extraction (SPE). The trace speciation analysis of Cr(III) and Cr(VI) in wastewater has been used by short-column high-performance liquid chromatography hyphenated to inductively coupled plasma spectrometry (HPLC–ICP-MS) after on-line SPE. Cr(III) and Cr(VI) have been adsorbed on the anion exchange column after transforming the cationic Cr(III) to an anionic [Cr(III)–EDTA]− complex devoid of re-dox reagent, and then eluted rapidly (within seconds) with a very low concentration of tetrabutylammonium hydroxide (TBAH) solution. This method provides a reliable on-line preconcentration method and detection coupled technique. Under the optimized conditions, high enrichment factors have been obtained for Cr(VI) and [Cr(III)–EDTA]− with 30 mL sample solution up to 105 and 128, respectively. The low detection limits of 0.0068 ng mL−1 and 0.0041 ng mL−1, with the relative standard deviations (RSDs) of 4.3% and 3.6% were obtained for Cr(VI) and [Cr(III)–EDTA]−, respectively. The developed method was validated by analyzing Certified Reference Materials GSBZ50027-94, and the spike tests were also performed. At the same time, thanks to the merit of simple operation, rapid adsorption/desorption dynamics, high enrichment and low LODs, the established method was applied to analyze three wastewater samples from different discharge port.N,N-bis(2-aminoethyl)ethane-1,2-diamine functionalized poly(chloromethyl styrene-co-styrene) was synthesized, characterized and used as the adsorbent to preconcentrate chromium in environmental waters by on line solid-phase extraction (SPE). Thus, a novel, simple and on-line SPE-HPLC-ICP-MS method has been established.

Fullerenol, an important water-soluble derivative of fullerene carbon nanomaterial, has been increasingly used in medicine and industry. The presence and release of carbon nanoparticles into the environment have raised concerns over potential impacts on human health and the environment. In this study, the bioaccumulation of fullerenol nanoparticles in wheat was investigated using 13C-labelling techniques. The dose and time-dependent bioaccumulation of fullerenol in wheat was observed, and most fullerenol (about 85.68–263.86% ID per g, percentage of dose per gram tissue) was found in roots. With prolonged culture times, the seedlings treated with relatively low concentrations of fullerenol nanoparticles (2.5 μg mL−1) showed significant increases in 13C content in roots, while 10.0 μg mL−1 fullerenol appeared to suppress this accumulation. Only very limited amounts (<4.13% ID per g) of fullerenol nanoparticles were translocated from roots to stems and leaves. The presence of fullerenol nanoparticles was confirmed by scanning electron microscopy, and small particles were found in the vascular cylinder of wheat roots. During the incubations with fullerenol nanoparticles at all test concentrations, the biomass gain of stems and leaves was unaffected, while root elongation was promoted. Fullerenol also improved the synthesis of chlorophyll in wheat during the 7 d observation period.

Analytical technique on oxygen isotope composition of phosphate in soil plays an important role in biogeochemical research. As the composition of the soil is complex with multiple oxygen sources, a liable phosphate enrichment and purification technology is important for phosphate oxygen isotope research. Here we present a protocol on the analysis of the δ18Op of inorganic phosphate in soil, wherein phosphate was purified with multiple mineral precipitations and finally precipitated as Ag3PO4. The efficiency of NH4OH purification method was examined and the purity of the product was verified through XRD and element analysis. The result showed that the treatment of Ag3PO4 sample by recrystallizing with ammonia could remove the impurity efficiently without significantly modify oxygen isotope compositions. The validity of sample processing and the reliability of isotope analyses were confirmed by processing a KH2PO4 stand in parallel with soil samples containing phosphate. The analysis result of three types of soil samples indicated that this method provided good precision of 0.2‰. There were significant differences of δ18Op among three types of soil (from 15.2‰ to 19.5‰), and δ18Op could be used to trace P sources.A protocol on the research of δ18Op in soil was presented and the efficiency of recrystallization purification method with NH4OH was investigated. The analysis result of three types of soils indicated that this method was quite feasible with satisfactory validity, precision and parallel, and different types of soil had significant difference in δ18Op.

Wastewater treatment plants (WWTPs) are regarded as one of the most important sources of antibiotics in the environment. The occurrence, seasonal variation and removal efficiency of 21 antibiotics and 10 metabolites, including five sulfonamides and three of their metabolites, six quinolones, two macrolides, two β-Lactams and five tetracyclines and seven of their metabolites, were investigated in five WWTPs in different seasons in the Jiulongjiang River Region, South China. 16 antibiotics and 6 metabolites in summer and 14 antibiotics and 6 metabolites in winter were found, respectively. The most frequently detected antibiotics were sulfamethazine, sulfamethoxazole, n-acetyl sulfamethazine, n-acetyl sulfamethoxazole, ofloxacin, cephalexin monohydrate and cephradine; of these, the concentration of cephradine was the highest in most of the influent and effluent samples. The highest level of total antibiotics was found in Longyan City WWTPs, where there are more population and swine farms. Seasonal variation of the antibiotics in wastewater samples was also studied. The concentrations of antibiotics in winter were higher than those in summer. The antibiotics could not be removed completely by the WWTPs, and the mean removal efficiency ranged from −71.6 to 56.3%. Of all the antibiotics, the tetracyclines were removed comparatively more efficiently, probably due to their adsorption to sludge. The low removal efficiency of antibiotics in WWTPs could be one of the important reasons for the presence of antibiotics in the environment in Jiulongjiang Region.

A sensitive and reliable method using capillary zone electrophoresis with UV-diode array detection (CZE-DAD) has been developed and validated for trace determination of nineteen pharmaceutical and personal care products (PPCPs) in wastewater. Due to the lack of sensitivity of UV-vis detection, a solid-phase extraction (SPE) method for off-line preconcentration and cleanup of water samples, in combination with an on-line preconcentration methodology named head-column field-amplified sample stacking (FASS), has been applied. Several parameters affecting separation and FASS efficiency were investigated in detail, including the buffer pH and concentration, organic modifier, sample matrix, water plug, and electrokinetic injection voltage and time. Under the optimal FASS-CZE conditions, high efficiency was achieved and nineteen PPCPs were baseline separated within 27 min. The accuracy of this assay was ensured by spiking of real samples with standard known concentrations and the intra-day and inter-day relative standard deviations (RSDs) were below 5.6 and 6.3%, respectively. The average recoveries for water samples with the studied PPCPs were greater than 64.7 ± 1.1%. The limits of detection (LODs) were estimated to range from 1.4 to 46.4 ng L−1 for the studied compounds. This method was successfully applied for the simultaneous determination of PPCPs in wastewater samples from a sewage treatment plant.

In this study, zebrafish (Danio rerio) were exposed to two dietary concentrations of individual HBCD diastereoisomers (α-, β-, and γ-HBCD) for 42 days, followed by clean food for 21 days, to examine bioaccumulation, depuration, and enantiomer fractions (EFs) of HBCD diastereoisomers and to test the bioisomerization of HBCDs in fish. The depuration of α-, β-, and γ-HBCD in zebrafish followed the first-order process. Bioaccumulation parameters of the three diastereoisomers differed between low and high dose, suggesting that the bioaccumulation of them is concentration dependent. Calculated assimilation efficiencies (AEs), biomagnification factors (BMFs), and half-lives (t1/2) of α-HBCD were the highest among the three diastereoisomers. Furthermore, the study showed that zebrafish could biotransform γ-HBCD to α-HBCD. The highest AE, BMF, and t1/2 of α-HBCD and bioisomerization of γ-HBCD to α-HBCD could explain why α-HBCD appears to be dominant in biota samples. The EFs for α- and γ-HBCD in zebrafish estimated at different times of bioaccumulation and depuration were all significantly greater than those in corresponding food (P < 0.05), indicating selective enrichment of (+) α-enantiomer and (+) γ-enantiomer relative to (−) α-enantiomer and (−) γ-enantiomer, respectively.

Estrogenic compounds and antibiotic residues in environment are receiving significant attention because of their potential adverse effects on ecosystems and human health. The objectives of this study were to determine the occurrence and seasonal variability of eight kinds of estrogenic compounds and 14 antibiotics. The study developed an occurrence database of the estrogenic compounds and antibiotics in spatial and temporal scale in Jiulongjiang River, South China, to provide useful information for environmental management of this region.Eight estrogenic compounds and 14 antibiotic compounds were detected in Jiulongjiang River from 19 sampling sites during high-flow and low-flow season in surface water. The samples were preconcentrated by solid-phase extraction for analysis. Eight estrogenic compounds were analyzed by gas chromatography mass spectrometry (Agilent 7890A-5975C), and antibiotics were determined by liquid chromatography-tandem mass spectrometry (LC–MS/MS) system (ABI 3200 Q TRAP).All target compounds could be detected, except 17α-ethynylestradiol, sulfamerazine, and ofloxacin. The median concentrations for seven estrogenic compounds ranged from 6.00 to 610.72 ng/L, with the detection frequency range of 16.00–100%. However, the detection frequencies of 13 antibiotics detected varied from 50% to 100%, with the median concentrations ranged from 0.89 to 117.97 ng/L. Seasonal variations were obvious for most estrogenic compounds in Jiulongjiang River, except for octylphenol and estriol. There were significant (P < 0.001) differences for three tetracyclines, sulfadiazine, and sulfamethoxazole between in low-flow season and in high-flow season. Besides, spatially considerable variations in the concentrations were observed for antibiotics, nonylphenol, octylphenol, and bisphenol A.The Jiulongjiang River water was more seriously contaminated by diethylstilbestrol, estrone, sulfamethazine, and tetracyclines. Higher overall concentration levels of estrogenic compounds and antibiotics were detected in low-flow water than those in high-flow water. The pollution of estrogenic compounds and antibiotics in Jiulongjiang River mainly came from municipal sewage and livestock breeding activities.

The concentrations of six sulfonamides (SAs) and three tetracyclines (TCs) were investigated in Jiulongjiang River during the low water season and the high water season. They were monitored in both surface water and sediment. Total concentrations of all these antibiotics varied from 31 to 25771 ng g−1 in sediment samples. In water they ranged from 60 to 2607 ng L−1 during the low water season and from ND (not detected) to 134 ng L−1 during the high water season. At the sites nearby breeding farms, chlorotetracycline was found to have the highest concentration of 1036 ng L−1 in water and 14666 ng g−1 in sediments. According to the published data, the concentrations of sulfamethazine, sulfameter and TCs at these sites were higher than that in most rivers. The concentrations during the low water season were tens to hundreds of times higher than that in the high water season. The lower concentrations of TCs in the high water season might result from both dilution and photo-degradation, while dilution and bio-degradation might lead to the lower concentrations of SAs. However, further study is needed to clarify the specific reasons. Concerning the relationship between sediment and water samples, the pseudo-partitioning values of TCs were much higher than SAs. It indicates that the TCs are prone to accumulate in the sediment.

Structural dissimilarities of hexabromocyclododecane diastereoisomers could raise substantial differences in physicochemical, biological and toxicological properties. In order to fully assess the environmental safety and health risk of hexabromocyclododecanes (HBCDs), zebrafish embryos were used to evaluate the developmental toxicity of individual HBCD diastereoisomers (α-HBCD, β-HBCD and γ-HBCD). Four-hour post-fertilization (hpf) zebrafish embryos were exposed to different concentrations of HBCD diastereoisomers (0, 0.01, 0.1 and 1.0 mg/l) until 120 hpf. The results showed that exposure to HBCDs can affect the development of zebrafish embryos/larvae in a dose-dependent and diastereoselective manner. The diastereoisomers α-, β- and γ-HBCD at 0.01 mg/l had little effect on the development of zebrafish embryos except that exposure to 0.01 mg/l γ-HBCD significantly delayed hatching (P < 0.05). At 0.1 mg/l, α-HBCD resulted in depressed heart rate of larvae (96 hpf) and delayed hatching, whereas β- and γ-HBCD both caused significant hatching delay and growth inhibition (P < 0.05). In addition, a remarkable and significant increase in mortality and malformation rate was noted at 0.1 mg/l γ-HBCD exposure groups (P < 0.05). At 1.0 mg/l, α-, β- and γ-HBCD significantly affected all of the endpoints monitored (P < 0.05). Additionally, HBCD diastereoisomers could induce the generation of reactive oxygen species (ROS) and the activities of caspase-3 and caspase-9 in a dose-dependent manner. The results indicated that HBCD diastereoisomers could cause developmental toxicity to zebrafish embryos through inducing apoptosis by ROS formation. The overall results showed a good agreement confirming that the order of developmental toxicity of HBCD diastereoisomers in zebrafish is γ-HBCD > β-HBCD > α-HBCD.Highlights► We examined the effects of α-, β- and γ-HBCD on development of zebrafish embryos. ► We examined various endpoints. ► HBCDs could affect development of zebrafish embryos in a dose-dependent manner. ► We showed that α-, β- and γ-HBCD could induce apoptosis in zebrafish embryos. ► The order of developmental toxicity in zebrafish was γ-HBCD > β-HBCD > α-HBCD.

A sensitive and reliable method using capillary zone electrophoresis with UV-diode array detection (CZE-DAD) has been developed and validated for trace determination of nineteen pharmaceutical and personal care products (PPCPs) in wastewater. Due to the lack of sensitivity of UV-vis detection, a solid-phase extraction (SPE) method for off-line preconcentration and cleanup of water samples, in combination with an on-line preconcentration methodology named head-column field-amplified sample stacking (FASS), has been applied. Several parameters affecting separation and FASS efficiency were investigated in detail, including the buffer pH and concentration, organic modifier, sample matrix, water plug, and electrokinetic injection voltage and time. Under the optimal FASS-CZE conditions, high efficiency was achieved and nineteen PPCPs were baseline separated within 27 min. The accuracy of this assay was ensured by spiking of real samples with standard known concentrations and the intra-day and inter-day relative standard deviations (RSDs) were below 5.6 and 6.3%, respectively. The average recoveries for water samples with the studied PPCPs were greater than 64.7 ± 1.1%. The limits of detection (LODs) were estimated to range from 1.4 to 46.4 ng L−1 for the studied compounds. This method was successfully applied for the simultaneous determination of PPCPs in wastewater samples from a sewage treatment plant.

The concentrations of six sulfonamides (SAs) and three tetracyclines (TCs) were investigated in Jiulongjiang River during the low water season and the high water season. They were monitored in both surface water and sediment. Total concentrations of all these antibiotics varied from 31 to 25771 ng g−1 in sediment samples. In water they ranged from 60 to 2607 ng L−1 during the low water season and from ND (not detected) to 134 ng L−1 during the high water season. At the sites nearby breeding farms, chlorotetracycline was found to have the highest concentration of 1036 ng L−1 in water and 14666 ng g−1 in sediments. According to the published data, the concentrations of sulfamethazine, sulfameter and TCs at these sites were higher than that in most rivers. The concentrations during the low water season were tens to hundreds of times higher than that in the high water season. The lower concentrations of TCs in the high water season might result from both dilution and photo-degradation, while dilution and bio-degradation might lead to the lower concentrations of SAs. However, further study is needed to clarify the specific reasons. Concerning the relationship between sediment and water samples, the pseudo-partitioning values of TCs were much higher than SAs. It indicates that the TCs are prone to accumulate in the sediment.

Fullerenol, an important water-soluble derivative of fullerene carbon nanomaterial, has been increasingly used in medicine and industry. The presence and release of carbon nanoparticles into the environment have raised concerns over potential impacts on human health and the environment. In this study, the bioaccumulation of fullerenol nanoparticles in wheat was investigated using 13C-labelling techniques. The dose and time-dependent bioaccumulation of fullerenol in wheat was observed, and most fullerenol (about 85.68–263.86% ID per g, percentage of dose per gram tissue) was found in roots. With prolonged culture times, the seedlings treated with relatively low concentrations of fullerenol nanoparticles (2.5 μg mL−1) showed significant increases in 13C content in roots, while 10.0 μg mL−1 fullerenol appeared to suppress this accumulation. Only very limited amounts (<4.13% ID per g) of fullerenol nanoparticles were translocated from roots to stems and leaves. The presence of fullerenol nanoparticles was confirmed by scanning electron microscopy, and small particles were found in the vascular cylinder of wheat roots. During the incubations with fullerenol nanoparticles at all test concentrations, the biomass gain of stems and leaves was unaffected, while root elongation was promoted. Fullerenol also improved the synthesis of chlorophyll in wheat during the 7 d observation period.

Wastewater treatment plants (WWTPs) are regarded as one of the most important sources of antibiotics in the environment. The occurrence, seasonal variation and removal efficiency of 21 antibiotics and 10 metabolites, including five sulfonamides and three of their metabolites, six quinolones, two macrolides, two β-Lactams and five tetracyclines and seven of their metabolites, were investigated in five WWTPs in different seasons in the Jiulongjiang River Region, South China. 16 antibiotics and 6 metabolites in summer and 14 antibiotics and 6 metabolites in winter were found, respectively. The most frequently detected antibiotics were sulfamethazine, sulfamethoxazole, n-acetyl sulfamethazine, n-acetyl sulfamethoxazole, ofloxacin, cephalexin monohydrate and cephradine; of these, the concentration of cephradine was the highest in most of the influent and effluent samples. The highest level of total antibiotics was found in Longyan City WWTPs, where there are more population and swine farms. Seasonal variation of the antibiotics in wastewater samples was also studied. The concentrations of antibiotics in winter were higher than those in summer. The antibiotics could not be removed completely by the WWTPs, and the mean removal efficiency ranged from −71.6 to 56.3%. Of all the antibiotics, the tetracyclines were removed comparatively more efficiently, probably due to their adsorption to sludge. The low removal efficiency of antibiotics in WWTPs could be one of the important reasons for the presence of antibiotics in the environment in Jiulongjiang Region.