Magnetic surface-imprinted polymer microspheres coupled with HPLC-MS/MS for sensitive detection of amphetamine-type drugs in water.

Magnetic surface imprinted polymer microspheres (Fe3O4@MIPs) were successfully synthesized via Pickering emulsion polymerization, utilizing N-Methylphenethylamine as a surrogate template for amphetamine-type drugs. Fe3O4@MIPs not only possessed excellent dispersibility and enough magnetic properties in aqueous solutions, but also displayed good selectivity towards six amphetamines, with an imprinting factor ranging from 1.8 to 2.6. The adsorption kinetics closely aligned with the pseudo-second-order model, and the adsorption efficiency exceeds 80 % for each amphetamine at equilibrium. Fe3O4@MIPs were then employed as the efficient adsorbents for the extraction of amphetamine drugs. Extraction parameters, including sample pH, the mass of adsorbent, and the type and volume of eluting solvent, were carefully optimized. In combination with the high performance liquid chromatography tandem triple quadrupole mass spectrometry (HPLC-MS/MS), a selective magnetic solid-phase extraction (MISPE) method utilizing Fe3O4@MIPs was developed for the detection of six amphetamines in water samples. The limits of detection and limits of quantitation were determined to be 5.2∼23 ng L-1 and 17∼77 ng L-1, respectively. Recoveries for the six target drugs from lake water and sewage samples fell within the range of 87.2∼110 %. Additionally, the MISPE-HPLC-MS/MS method exhibited excellent repeatability, with a precision below 8.5 % at two spiking levels. The prepared Fe3O4@MIPs possessed the advantages of high selectivity, straightforward preparation, facile separation and good reusability, and was highly suitable for the efficient extraction of amphetamine-type substances in complex environmental water.

[Source Apportionment of Morphine in Wastewater].

It is a new approach to identify legal or illegal use of morphine through information on municipal wastewater. However, the sources of morphine in wastewater are complex, and distinguishing the contribution of different sources has become a key issue. A total of 262 influent samples from 61 representative wastewater treatment plants in a typical city were collected from October 2022 to March 2023. The concentrations of morphine, codeine, thebaine, papaverine, noscapine, and monoacetylmorphine were analyzed in wastewater and poppy straws. Combined with the proportion of alkaloids in poppy straws, the source analysis of alkaloids in wastewater was analyzed using the ratio method and positive matrix factorization model (PMF). Only five alkaloids were detected in wastewater, and monoacetylmorphine, a metabolite of heroin, was not detected. The concentrations of morphine and codeine were significantly higher than those of noscapine, papaverine, and thebaine. By constructing the ratios of codeine/(morphine + codeine) and noscapine/(noscapine + codeine), the source of poppy straw could be qualitatively distinguished. The PMF results showed that three sources of morphine for medical use, poppy straw, and codeine contributed 44.9%, 43.7%, and 9.4%, respectively. The different sources varied in these months due to the COVID-19 and influenza A outbreaks, in which the use of drugs containing poppy straws and codeine was the main source, whereas the use of morphine analgesics remained relatively stable. Inventory analysis further demonstrated the reliability of the source contributions from the PMF model, and morphine was not abused in this city.

Surveillance of COVID-19 and influenza A(H1N1) prevalence in China via medicine-based wastewater biomarkers.

The simultaneous monitoring of individual or multiple diseases can be achieved by selecting therapeutic medicines used to treat the primary symptoms of the condition as biomarkers in wastewater. This study proposes a novel approach to monitor the prevalence of COVID-19 and influenza A (H1N1) by selecting nine medicines to serve as biomarkers, including three antipyretics, three antivirals, and three cough suppressants. To verify our approach, wastewater samples were collected from seventeen urban and five rural wastewater treatment plants (WWTPs) in a Chinese city over a period of one year. The use of antipyretics increased notably during the COVID-19 pandemic, while the consumption of antivirals for influenza A (H1N1) rose in the post-COVID-19 pandemic period, indicating a minor spike in the occurrence of influenza A (H1N1) after the COVID-19 pandemic. Fever is a significant symptom of COVID-19 and can serve as a reliable indicator of disease prevalence. Our research found that the prevalence of COVID-19 in urban areas was significantly higher (at 78.5 %, 95 % CI: 73.4 % - 83.9 %) than in rural areas (with a prevalence of 48.1 %, 95 % CI: 42.4 % - 53.8 %). The prevalence of COVID-19 in urban areas in this study was consistent with the data reported by the Chinese center for Disease Control and Prevention (82.4 %). Continuous monitoring of WWTPs in urban areas with fluctuating populations and complex demographics can provide early disease warning. Our results demonstrate the feasibility of evaluating community disease prevalence by selecting major therapeutic medicines as biomarkers in wastewater.

Dummy molecularly imprinted polymers-agarose gel mixed matrix membrane for extraction of amphetamine-type stimulants in wastewater and urine.

Dummy molecularly imprinted polymers (DMIPs) with high selectivity for amphetamine-type stimulants (ATSs) were synthesized using synephrine molecule as a dummy template. The polymers were irregularly massive with a specific surface area of 330 m2g-1. Adsorption experiments found that the imprinting factors for five ATSs (amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, and 3,4-methylenedioxy-N-ethylamphetamine) were 2.3∼3.7. The DMIPs-agarose gel mixed matrix membranes (MMMs) were further prepared by incorporating DMIPs in the agarose matrix. MMMs were used to extract five ATSs from wastewater and urine samples. Extraction conditions such as membrane matrix, sample pH, dissolved organic matter content, extraction time, and elution reagent were optimized. Under optimal conditions, the developed MMMs-HPLC-MS/MS method exhibited low limits of detection (0.1∼3.0ng L-1), satisfactory recoveries (91.7∼100%), and good repeatability (RSD<7%, n=3). It was then successfully applied to ATSs analysis in wastewater and urine samples. Recoveries of ATSs in spiked wastewater and urine were 82.0∼98.4% and 82.3∼95.7%, respectively. Moreover, compared with other methods, the present method possessed the advantages of high quantitative ability, suitable for typical environmental conditions, and low application cost. The above results suggested that the developed MMMs-HPLC-MS/MS method could be used as a feasible strategy to extract and determine trace ATSs in wastewater and urine samples.

Selective extraction of synthetic cathinones new psychoactive substances from wastewater, urine and cocktail using dummy molecularly imprinted polymers.

Dummy molecularly imprinted polymers (DMIPs) for selective extraction of five common synthetic cathinones (SCs) were prepared by bulk polymerization. DMIPs materials possessed narrow diameter distribution (30-60 µm) and large specific surface area (329.6 m2 g-1). Imprinting factors for cathinone, methcathinone, mephedrone, methylone and ethylone were 1.11-1.82. DMIPs could also quickly adsorb SCs from aqueous solutions within 5 min. Therefore, the materials were used as solid-phase extraction (SPE) sorbents to selectively extract five SCs in complex samples. An accurate and sensitive analytical method based on DMIPs-SPE combined with HPLC-MS/MS was established. Under optimal conditions, the established method showed low limits of detection (0.002-0.1 ng mL-1), satisfactory recoveries (84.1-97.7%) and good repeatability (relative standard deviation (RSD) below 9%). The method was successfully verified using wastewater, urine and cocktail samples. Recoveries of SCs at three spiking levels were in the range of 75.1-98.6%, with RSD values below 7.0%. Compared with commercial sorbents, DMIPs showed better clean-up ability with matrix effect values of -24.1%-8.3% for all SCs in wastewater, urine and cocktail samples. Therefore, the developed DMIPs-SPE-HPLC-MS/MS strategy could be used as a specific and cost-effective method for sensitive determination of SCs in complex samples.

Assessment of correlations between sildenafil use and comorbidities and lifestyle factors using wastewater-based epidemiology.

Sildenafil (SIL) is widely used to treat erectile dysfunction. Information on its consumption and the factors influencing its use is limited in China. In this study, we sampled composite influent wastewater samples from 33 Chinese cities and analyzed SIL using liquid chromatography-tandem mass spectrometry. SIL consumption was estimated using wastewater-based epidemiology (WBE) and ranged from 10.6 mg/d/1000 people to 132 mg/d/1000 people, with a mean of 53 mg/d/1000 people. Prescription sales (3570 kg) accounted for 13.3% of the estimated SIL use (26842 kg) in 2018, thereby implying that SIL illicit use was greater than prescription use in China. Some regional differences were observed in SIL use, which was significantly higher in North China than South China (p < 0.05), thereby reflecting that the prevalence of SIL was affected by differences in lifestyle and socioeconomic factors. We found significant positive correlations between SIL use and consumption of allopurinol, hydrochlorothiazide, nicotine, and alcohol, thereby suggesting that the prevalence of SIL was associated with the prevalence of gout, hypertension, smoking, and drinking. Moreover, age structures, internet use, and marriage rates were positively correlated with SIL use, whereas the unemployment rate was negatively correlated with SIL use. Our study demonstrates that WBE is valuable for medical research to investigate licit and illicit drug use and to assess the underlying associations of different chemical uses.

Dummy molecularly imprinted polymers for class-selective extraction of amphetamine-type stimulants from alcoholic and nonalcoholic beverages.

Molecularly imprinted polymer was constructed for the first time through dummy imprinting strategy with homopiperonylamine as dummy template. The prepared dummy molecularly imprinted polymer (DMIP) showed high class selectivity towards the most popular amphetamine-type stimulants (ATSs) such as methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine, 3,4-methylenedioxy-amphetamine, and 3,4-methylenedioxy-N-ethylamphetamine with the imprinting factors of 2.280∼3.698 and selectivity factors of 1.654∼3.698. Moreover, ATSs could be rapidly adsorbed from water with the equilibrium time within 5 min. Hydrogen-bonding interaction between the amino groups of ATSs and carboxy on DMIP could be dominated adsorption mechanism. DMIP was employed as solid phase extraction (SPE) sorbents. Under the optimum extraction conditions, the method using DMIP-based SPE and high performance liquid chromatography-tandem mass spectrometry showed good linearity in the range of 0.025∼1.00 µmol L-1, good repeatability (RSD 4.8∼8.6%, n = 5) and low limits of quantification (0.007∼0.200 ng mL-1, S/N = 10). Satisfactory recoveries (72.5∼120%) with low RSD values (<10%) were obtained for all targets viz. spiked coke carbonated drinks, beer and cocktail. Compared with other commercial SPE sorbents, DMIP exhibited lower matrix effect (ME) for coke, beer and cocktail with ME values of 101∼124%, 75.8∼80.2% and 103∼128%, respectively. The obtained results suggested that the developed DMIP materials could be a potential candidate for pretreatment of ATSs in alcoholic and nonalcoholic beverages.

The dose effect of dansyl chloride on the derivative products of bisphenols and its application for the determination of bisphenols in human serum by high-performance liquid chromatography-tandem mass spectrometry.

Human exposure to bisphenols has rarely been reported. The most important challenges in this regard are the sensitivity and accuracy of the analytical methods employed. Dansyl chloride derivatization prior to high-performance liquid chromatography-tandem mass spectrometry has been prevalently employed to improve sensitivity. However, the dose effect of the derivatization reagent on the reaction products is not well understood, especially for reactants with two or more active groups. This study investigated the mass ratio of dansyl chloride to bisphenols and found the mass ratio played a vital role in changing the composition of derivatives; further, the optimal ratio for obtaining di-substituted derivatives was confirmed. Under optimal conditions, solid-phase extraction followed by dansyl chloride derivatization coupled with high-performance liquid chromatography-tandem mass spectrometry was used to detect eight bisphenols in human serum samples. The method detection limits of the eight bisphenols were 0.025-0.28 ng/mL, and the recoveries were 72.9-121.7% by spiking bisphenols (2, 5, and 20 ng/mL) into bovine serum. The detection frequencies of bisphenol A and bisphenol F in 73 serum samples obtained from children from Guangzhou were 41.1% and 71.2%, respectively, while the detection frequencies of other bisphenols were below 20%. The concentrations of bisphenol A and bisphenol F were < 0.28-8.0 ng/mL and < 0.028-7.6 ng/mL, respectively.

Assessment of metformin, nicotine, caffeine, and methamphetamine use during Chinese public holidays.

Metformin, nicotine, caffeine, and methamphetamine are widely used in China. However, the consumption pattern of these substances among the general population during Chinese public holidays may be different. Influent wastewater samples were collected from a municipal wastewater treatment plant in Yingkou, China on public holidays (n = 6) and working days (n = 20) to examine the changes in metformin, nicotine, caffeine, and methamphetamine consumption. The consumption of metformin in the city ranged from 1.94 to 14.4 g d-1 1000 people-1, while that of nicotine, caffeine, and methamphetamine ranged from 0.46 to 2.18 g d-1 1000 people-1, 31.8-89.8 g d-1 1000 people-1, and 87.0-657 mg d-1 1000 people-1, respectively. The highest consumption of metformin, caffeine, and methamphetamine was observed during the Spring Festival. The results indicated that the consumption of these substances showed almost the same trend and was higher during the Spring Festival, which may be influenced by personal habits and traditional festival reunions. There is a correlation between the consumption of nicotine and caffeine. Moreover, there are correlations between the consumption of metformin and nicotine, caffeine, as well as methamphetamine. The information based on wastewater epidemiology and consumption behavior, suggests that drug use in the region requires more attention or monitoring during holidays.

Methamphetamine use in typical Chinese cities evaluated by wastewater-based epidemiology.

Methamphetamine has become one of the most widely used illicit drugs in China. To understand the current situation in China, the prevalence and consumption of methamphetamine were estimated through wastewater-based epidemiology (WBE) in the present study. Methamphetamine concentrations ranged from 42.6 ng/L (Harbin) to 700 ng/L (Xi'an) in influent wastewater samples collected from 27 wastewater treatment plants (WWTPs) in 22 Chinese cities. The estimated consumption of methamphetamine was 23.0 (Dingxi) to 376 (Xi'an) mg/day/1000 inhabitants with a mean value of 157 mg/day/1000 inhabitants. The annual consumption in 2018 was estimated to be 84 tons (95% confidence interval, 44-136), which was 26% lower than that in 2014. The prevalence of methamphetamine use was 0.64% (95% confidence interval, 0.18-1.25), indicating that more than five million people used methamphetamine in 2018. Although drug abuse is common in the country, the consumption showed a different spatial pattern, with the highest values in Central China and the lowest use in Northeast China, so drug use is still considered a geographic and culture-dependent behaviour. The results indicated that WBE can not only be used to assess the trends of illicit drug use, but also to analyse the spatial differences in the whole country, which will provide complementary evidence for the prevention and control of methamphetamine use.

Co3O4 nanoparticles supported mesoporous carbon framework interface for glucose biosensing.

The present work reports the preparation of advanced functional nanostructures based on cobalt oxide supported mesoporous carbon framework (Co3O4@MCF) for electrochemical biosensing. Co3O4@MCF was synthesized by simple hythrothermal & pyrolysis method and further characterized by various microscopic and spectroscopic techniques. The transmission electron microscopic (TEM) images show the lattice fringes of crystalline Co3O4 with interlayer spacing of 0.24 nm. The characteristic 311 plane in X-ray diffraction (XRD) studies further confirmed the presence of crystalline Co3O4 on carbon frameworks. Reflection of prominent A1g peak along with D and G band in raman spectra confirmed the successful fabrication of Co3O4@MCF nanocomposite. Prepared Co3O4@MCF manifested great porosity, good biocompatibility and large surface area which allowed effective immobilization of glucose oxidase (GOx) onto its surface using chitosan (Chi) as a binder. Thus, a nanocomposite (Co3O4@MCF-Chi-GOx) modified glassy carbon electrode (GCE) was fabricated for highly selective detection of glucose using amperometry and cyclic voltammetry. The Co3O4@MCF-Chi-GOx/GCE electrode exhibited excellent biosensing performance for glucose monitoring with detection limit of (LOD) of 107.70 µM and reproducibility of 4.7% RSD. Moreover, the biosensor holds great promise for its effective implications in point-of-care diagnostics of small biomolecules.

Assessing the trend of diabetes mellitus by analyzing metformin as a biomarker in wastewater.

According to International Diabetes Federation estimates, China has the highest rate of diabetes in the world. To monitor the prevalence of diabetes mellitus (DM) in near real-time, a first-line medication for the treatment of type 2 diabetes, metformin, was used. Wastewater-based epidemiology (WBE) was applied to estimate the consumption of metformin in Dalian from 2015 to 2018. Quantification of metformin was undertaken using solid-phase extraction (SPE) and N-methyl-bis (trifluoroacetamide) derivatization prior to GC-MS analysis. The concentrations of metformin in eleven wastewater treatment plants (WWTPs) ranged from 1.7 µg/L to 239.0 µg/L, with an average value of 68.3 µg/L. For metformin consumption, there was a gradual increase from 12.1 mg/d/capita in 2015 to 28.4 mg/d/capita in 2018. Meanwhile, the prevalence of metformin in the Dalian population ranged from 1.6% in 2015 to 3.8% in 2018. Similarly, the prevalence of DM showed an increasing trend from 12.2% in 2015 to 21.6% in 2018, which is consistent with the data predicted by traditional surveys (15.2-19.8%). Additionally, the prevalence of DM in 2015 estimated based on WBE was 12.2%, which agreed with the results from the traditional survey (12.3%). These results indicated that the proposed method provided a feasible way to reveal the prevalence of DM through metformin monitoring by the WBE approach.

Wastewater analysis reveals spatial pattern in consumption of anti-diabetes drug metformin in China.

Metformin has been widely used as an oral drug for the treatment of diabetes mellitus. However, its consumption can be influenced by many economic and social factors. In this study, we investigated the spatial consumption pattern of metformin in China through wastewater-based epidemiology (WBE) approach. Influent wastewater samples were collected from 21 wastewater treatment plants (WWTPs) in 19 cities of the northeast China. A method using solid-phase extraction combined with N-Methyl-bis (trifluoroacetamide) derivatization for GC-MS detection was applied for metformin analysis. In 21 days, metformin showed high stability in wastewater at 24 °C and -20 °C. The mean concentrations of metformin in all WWTPs ranged from 2.42 µg L-1 to 53.6 µg L-1. The consumption of metformin was 0.66-15.6 mg d-1 capita-1 with the mean value of 5.54 ±â€¯4.28 mg d-1 capita-1. The prevalence of metformin ranged from 0.09% to 2.10% with an average of 0.74%. Both the consumption and prevalence of metformin displays significant spatial variations in northeast China. A statistical correlation analysis indicated that the consumption of metformin increases with the decrease of per capita disposable income of urban residents. To further predict the use of metformin in China, we developed a regress model and depicted a consumption map. The annual consumption of urban residents in Chinese provinces range from 1085-63,828 kg yr-1 with mean value of 25,347 kg yr-1, which would provide a certain reference value for public health care and diabetes control.

Reduction in methamphetamine consumption trends from 2015 to 2018 detected by wastewater-based epidemiology in Dalian, China.

BACKGROUND: Wastewater-based epidemiology (WBE) has become a useful tool in long-term or short-term continuous monitoring of illicit drugs consumption over the world. METHODS: We investigated the trend of methamphetamine (METH) use between 2015 and 2018 through WBE in Dalian, a typical Chinese city. Samples were collected in 11 municipal wastewater treatment plants (WWTPs). An analytical method, solid-phase extraction combined with trifluoroacetic anhydride derivatization prior to gas chromatography-mass spectrometry (GC-MS) analysis was applied to detect METH concentrations. RESULTS: During the sampling period, the METH concentrations increased slowly from 315 ± 243 ng/L in 2015 to 523 ± 549 ng/L in 2016, followed by a significant decrease with the concentrations 188 ± 187 ng/L in 2017 and 54.6 ± 42.9 ng/L in 2018. Ammonium nitrogen (NH4-N) was applied to estimate population size. The average coefficient of variation for population in 11 WWTPs was 35.3 ± 8.9%, reflecting the dynamic variations of population effectively. For METH consumption, there was a gradual increase from 2015 (231 mg/day/1000 people) to 2016 (414 mg/day/1000 people) and a significant linear decrease to 2017 (206 mg/day/1000 people) and 2018 (53.9 mg/day/1000 people). The prevalence of METH increased from 2015 (0.78%) to 2016 (1.06%), then decreased to 2017 (0.55%) and 2018 (0.17%), showed similar trends with the consumption. CONCLUSIONS: The obvious reduction trends of METH consumption via WBE over the period in Dalian provides objective evidence for declined METH consumption in local population. The reduction is probably due to the severe crack-down of illicit drugs by the government.

Ammonium hydroxide enhancing electrospray response and boosting sensitivity of bisphenol A and its analogs.

As one of the most important analytical techniques for accurate quantification of bisphenol compounds, liquid chromatography coupled to online electrospray ionization (ESI) tandem mass spectrometry exhibits relative weak ESI response in negative mode, which greatly reduces their sensitivity and limits their detection at trace levels, especially in complex samples such as blood. Based on the facilitated deprotonation of bisphenol molecule under alkaline condition, post-column injection of ammonium hydroxide (NH3·H2O) to mass spectrometer was explored to enhance the ionization efficiency of BPA and its eight analogs and improve their analytical sensitivity. Parameters effecting response intensity and stability were investigated, including mass concentration and flow rate of NH3·H2O. Under the optimal conditions with the addition of 2% (w/w) of NH3·H2O at 4 µL min-1, the instrument detection limits for bisphenol compounds were greatly lowered to 0.001-0.04 ng mL-1, which were 2-28.6 times lower than the result obtained without injecting NH3·H2O, except TBBPA (0.03 ng mL-1 in either case). The relative standard deviations (RSDs) for instrument repeatability of BPA and its analogs at three different concentration levels were in a range of 1.2-20%. Furthermore, a decreased matrix effects (90-111%) for bisphenols (except TBBPA) analysis in serum extracts were found compared with the result obtained without NH3·H2O injection (43-111%). The results demonstrated that the improved instrumental method coupled with suitable pretreatment techniques is more feasible to analyze bisphenol compounds in complex bio-samples.

Phenyltrichlorosilane-functionalized magnesium oxide microspheres: Preparation, characterization and application for the selective extraction of dioxin-like polycyclic aromatic hydrocarbons in soils with matrix solid-phase dispersion.

Magnesium oxide microspheres functionalized with phenyltrichlorosilane (PTS-MgO) were synthesized by surface modification through silanization reaction, which was confirmed by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetry analysis (TGA) and N2 adsorption-desorption. The result indicated that PTS-MgO not only possessed the ability of enhancing the retention with PAHs, but also weakening the interference from chlorinated compounds. As a sorbent for the matrix solid-phase dispersion (MSPD) extraction, PTS-MgO was used to selectively extract seven dioxin-like polycyclic aromatic hydrocarbons (DL-PAHs) from soil samples. Various parameters affecting the recoveries of seven DL-PAHs were investigated and optimized, such as sorbent/sample mass ratio, grinding time, rinsing and eluting conditions. Under the optimized conditions, the developed method combining MSPD with HPLC-FLD exhibited good sensitivity (0.02-0.12 ng g-1 detection of limits) and linearity (linear correlation coefficient greater than 0.9997). Satisfactory recoveries with DL-PAHs spiked at two levels (10 and 80 ng g-1) were obtained in the range of 72.2-113.1% with RSD < 9.6%, indicating that PTS-MgO had a potential in MSPD extraction of DL-PAHs in soils. Additionally, the proposed MSPD-HPLC-FLD method was also verified by detecting seven DL-PAHs in the standard reference soil. Based on the developed method, DL-PAHs in soil samples were detected with the concentration ranging from 70.08 to 555.05 ng g-1 dry weight (dw). The total toxic equivalency quotients (TEQ) of seven DL-PAHs varied from 9.93 to 143.94 ng TEQ/g dw.

Hexabromocyclododecane and tetrabromobisphenol A in sediments and paddy soils from Liaohe River Basin, China: Levels, distribution and mass inventory.

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are two kinds of brominated flame retardants and widely present in the environment and biota. The levels, spatial distributions and mass inventories of HBCD and TBBPA were investigated in sediments and paddy soils from the Liaohe River Basin in northeast China. The concentrations of ΣHBCD and TBBPA were in the range of not detected (nd) to 4.02ng/g dry weight (dw) and 0.03 to 4.06ng/g dw, respectively. γ-HBCD was dominated in sediments, while the abundance of α-HBCD was relatively high in paddy soils. The spatial distributions of HBCD and TBBPA in surface sediments and paddy soils indicated that the local point-input was their major source. The significant correlation between total organic carbon (TOC) contents and the HBCD levels suggested that TOC content also exerted an influence on the distribution of HBCD in sediments. Meanwhile, it was found that the irrigation with river water was not the major transportation pathway of HBCD and TBBPA in paddy soils. Based on the study, it was estimated that there were about 1.67tons HBCD and 2.20tons TBBPA deposited into sediments of the Liaohe River system every year. The total mass inventories of HBCD and TBBPA in sediments were far higher than that in paddy soils.

High performance solid-phase extraction cleanup method coupled with gas chromatography-triple quadrupole mass spectrometry for analysis of polychlorinated naphthalenes and dioxin-like polychlorinated biphenyls in complex samples.

A solid-phase extraction (SPE) cleanup method was developed to purify the sample extracts for the analysis of polychlorinated naphthalenes (PCNs) and dioxin-like polychlorinated biphenyls (dl-PCBs). Monodisperse magnesium oxide (MgO) microspheres and basic alumina were used as SPE adsorbents. Important parameters of the SPE procedure were optimized, including the amount of basic alumina and the type and volume of the washing and elution solvents. The optimized SPE cleanup method exhibited excellent purification performance for the removal of organochlorinated compounds, lipid compounds, sulfur, and pigments. Additionally, it was found that the retention activities of congeners differed with the number and position of the chlorine substituents in PCNs. In this study, an analytical method based on a combination of accelerated solvent extraction (ASE) coupled with SPE cleanup and gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) is proposed for the analysis of PCNs and dl-PCBs in complex samples (sediment, pine needle, and scallop samples). The analytical method demonstrates good linearity, acceptable recovery (63-148%) and precision (relative standard deviations less than 26%). The limits of detection (LODs) of PCN and dl-PCB congeners were in the range of 0.6-19.1pgg(-1) and 0.4-8.6pgg(-1), respectively. The PCNs and dl-PCBs levels in these samples ranged from 0.16 to 3.07ngg(-1) dry weight (dw) and from undetectable to 0.07ngg(-1) dw, respectively.

Occurrence, distribution and source apportionment of polychlorinated naphthalenes (PCNs) in sediments and soils from the Liaohe River Basin, China.

The occurrence and spatial distribution of polychlorinated naphthalenes (PCNs) were investigated in sediments, upland and paddy soils from the Liaohe River Basin. Concentrations of ΣPCNs were in the range of 0.33-12.49 ng g(-1) dry weight (dw) in sediments and 0.61-6.60 ng g(-1) dw in soils, respectively. Tri-CNs and tetra-CNs were the dominating homologues. An increasing trend of PCNs contamination was found in sediments with the rivers flowing through industrial areas and cities. Soils collected near cities exhibited higher abundance of PCNs than that of rural areas. The distribution of PCNs was related to the local industrial activities, rather than total organic carbon. Positive matrix factorization (PMF) was used for the source apportionment of PCNs in sediments and paddy soils. The result of PMF indicated that PCNs in sediments and paddy soils were mainly from the industrial processes, with additional contributions from the historical use of Halowax 1014 and atmospheric deposition.