•The OPEs were widely detected in the urban soil.•TBOEP was the most abundant OPEs.•The spatial distribution of OPEs was site-specific.•Human activities influence the distribution of OPEs in the urban soils.67 soil samples from the road greenbelts, the paddy/vegetable fields, the parks, the commercial and residential areas in the subtropical city, Guangzhou, China, were collected and analyzed for 11 organophosphate esters (OPEs) and triphenylphosphine oxide (TPPO). OPEs were detected in all soil samples analyzed, which indicate that OPEs are ubiquitous environmental contaminants. The ∑11OPEs concentrations ranged from 0.041 mg kg−1-dry weight (dw) to 1.37 mg kg−1-dw, with the mean and median concentrations of 0.25 mg kg−1-dw and 0.24 mg kg−1-dw, respectively. High concentrations of OPEs were observed in the roadside soils collected from the commercial areas with heavy traffic and extensive anthropogenic activities. Of 11 OPEs, tris(2-butoxyethyl) phosphate (TBOEP), tri-cresyl-phosphate (TMPP), tributyl phosphate (TNBP) and tris(2-chloroethyl) phosphate (TCEP) were the most abundant OPEs, contributing 42.8 ± 15.4%, 17.2 ± 11.9%, 10.9 ± 6.85% and 9.70 ± 9.56% of ∑11OPEs, respectively. Principal component analysis (PCA) suggested that OPEs accumulation in the urban soils derived from different sources. As compared to the results for other studies, the urban soils of Guangzhou were moderately polluted by OPEs.Download high-res image (130KB)Download full-size image

In the present study, the performances of the commonly used solid phase extraction (SPE) materials, i.e. alumina, Florisil and silica gel, for separating organophosphate esters (OPEs) from potential co-extracted interferents such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs), were evaluated. Silica gel/alumina (Si/Al) multilayer SPE for OPE sample preparation could effectively reduce matrix effects. A novel and selective method, based on sample preparation by microwave-assisted extraction (MAE) and Si/Al multilayer SPE cartridge cleanup, for the determination of OPEs in soil samples by gas chromatography-mass spectrometry (GC/MS), was developed. The method quantification limits for OPEs ranged from 0.09 to 2.39 ng g−1. A good linearity (r2 > 0.991) between MQLs and 1000 × MQLs was achieved. The developed method was successfully applied to determine OPEs in soil samples collected from the campus of Sun Yat-sen University, China. Of the 11 OPEs analyzed, triethyl phosphate (TEP), tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tributoxyethyl phosphate (TBEP) and triphenylphosphate (TPhP) were present in all of the soil samples, and dominated by TBEP, TCEP, TnBP and TCPP. As compared to the results of other studies, the campus soils of Sun Yat-sen University, China, were moderately polluted by OPEs.

•A new method for the simultaneous determination of multiple phytohormones in plant samples by LC–ESI-MS/MS was developed.•Widely used extraction and purification procedures have been optimized and compared.•Oasis MCX SPE coupled with ethyl acetate LLE purification technique could effectively eliminate interfering substances.•The method was successfully applied for the determination of multiple phytohormones in leaf tissues of Brassica napus L.Sample preparation is often the bottleneck in the analysis of phytohormones in plant samples. In the present study, sample pretreatment involving extraction by acidified and non-acidified organic solvents and extract purification using solid-phase extraction (SPE) and/or liquid–liquid extraction (LLE) has been optimized and compared for the determination of multiple phytohormones, including auxins, cytokinins (CKs), abscisic acid (ABA), gibberellins (GAs), jasmonic acid (JA) and salicylic acid (SA) in biological samples by liquid chromatography–electrospray ionization-tandem mass spectrometry (LC–ESI-MS/MS) under multiple-reaction monitoring (MRM). A novel and efficient sample pretreatment method for multiple phytohormones in acidified acetonitrile extracts of plant samples using polymer-based mixed-mode cation-exchange solid phase extraction (SPE) with Oasis MCX cartridges combined with ethyl acetate LLE has been developed. The method detection limits (MDLs) for the target phytohormones ranged from 0.0013 to 0.021 ng·mL− 1, and the recoveries were obtained by spiking the target phytohormones in the two-month-old leaves of oilseed rape (Brassica napus L.) at concentrations of 0.20, 2.0 and 10 ng·g− 1, which ranged from 75.1 to 111%, 79.6 to 113% and 89.2 to 111%, respectively. The intra-day precisions were in the range of 1.15 to 10.2%, and the inter-day precisions ranged from 2.92 to 12.4%. Additionally, matrix effects were substantially decreased. The proposed sample pretreatment method has been successfully applied to the analysis of multiple phytohormones in the leaf samples of oilseed rape (B. napus L.).

•MAE-GPC silica gel SPE GC/MS method was developed for determining OPEs in biota samples.•The method can remove the lipid compounds and co-extract interferences efficiently.•The method reduces amounts of elution solvents and losses of volatile OPEs by use of self-made narrow GPC and SPE column.•The method was successfully applied for the analysis of fish and bird samples.An analytical method for the determination of 14 organophosphorus flame retardants (OPFRs), including halogenated OPFRs, non-halogenated OPFRs and triphenyl phosphine oxide (TPPO) in biological samples was developed using gas chromatography–mass spectrometry (GC/MS). Biological samples were extracted using microwave-assisted extraction (MAE) with hexane/acetone (1:1, v/v) as the solvent; then, a two-step clean-up technique, gel permeation chromatography (GPC) combined with solid phase extraction (SPE), was carried out before GC/MS analysis. Experimental results showed that the developed method efficiently removed the lipid compounds and co-extract interferences. Moreover, using the relatively “narrow” column (with an i.d. of 10 mm) significantly decreased the elution volume and, therefore, prevented the loss of the most volatile OPFRs, especially trimethyl phosphate (TMP) and triethyl phosphate (TEP). The method detection limits (MDLs) for OPFRs in the biological samples ranged from 0.006 to 0.021 ng g−1 lw, and the recoveries were in the range of 70.3–111%, except for TMP (38.9–55.6%), with relative standard deviations (RSDs) of less than 14.1%. The developed method was applied to determine the amount of the target OPFRs in biological samples (i.e., fish and domestic birds) that were collected from the Pearl River Delta (PRD) region in southern China. Of the 14 OPFRs, tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(chloropropyl) phosphate (TCPP) and tributoxyethyl phosphate (TBEP) were present in all of the biological samples that were analyzed, and dominated by TnBP, TCEP and TBEP. The concentrations of OPFRs in the biological samples that were collected from the PRD region were higher than those reported in other locations.

Herein we report the electrochemical synthesis of porous Pr(OH)3 nanobelt arrays (NBAs), nanowire arrays (NWAs), nanowire bundles (NWBs), and nanowires (NWs) and their applications as dye absorbents in water treatment. These Pr(OH)3 nanostructures exhibit high efficient and selective adsorption of the dyes with amine (−NH2) functional groups such as Congo red, reactive yellow, and reactive blue. The high efficiency and selectivity is attributed to the large effective surface area of the porous structure, plentiful hydroxyl groups, and basic sites on the Pr(OH)3 surface. Furthermore, the toxicity studies of these porous Pr(OH)3 nanostructure show a negligible effect on seed germination, indicating that they hold great potential as environmentally friendly absorbents in water treatment.

•We investigated the correlation between the PAHs in blood samples and semen qualities.•Concentrations of PAHs in blood were significantly correlated to semen motility.•Smoking and drinking habits were proved to relate to PAHs concentrations in blood.This study is the first one investigating the correlation between the concentration of polycyclic aromatic hydrocarbon (PAHs) in blood and semen qualities for residents in the Pearl River Delta (PRD) region in China. Blood samples from 53 infertile volunteers were studied for measures of semen quality and 16 PAHs. Information on the study subjects' living habits (such as smoking, drinking and preference of consumption for food) and general information (age, body-mass-index (BMI) and educational background) were also collected. Statistical results showed that age and BMI were significantly and negatively related to semen motilities. The total concentrations of PAHs (∑16 PAHs) in the  blood were 12,010, 7493, 9105 and 8647ng/g for factory workers, office workers, technicians and salespersons, respectively. In addition, ∑16 PAHs in the blood of smokers, drinkers and heavy-taste food consumers were 11,950, 11,266 and 12,141 ng/g, which were higher than those observed in nonsmokers (10,457 ng/g), nondrinkers (10,920 ng/g) and light-taste food consumers (9202 ng/g), individually. Furthermore, the Pearson correlation analysis results showed significant positive correlations between BMI and ∑16 PAHs in the blood. Statistically significant correlations were observed between semen motilities and ∑16 PAHs in the blood as well. Logistic regression results showed that for each 1 ng/g increase in ∑16 PAHs in blood samples, the log odds of experiencing a pregnancy decrease by 0.039 on average. However, more evidences are needed to clarify the impact of PAHs in the blood to male infertility.