Adsorption of dissolved organic matter (DOM) on polystyrene microplastics in aquatic environments: Kinetic, isotherm and site energy distribution analysis.

Microplastics and dissolved organic matter (DOM) are ubiquitous in aquatic environments. The adsorption behavior of DOM on microplastics in aquatic environments is a prominent concern. In this study, the adsorption of two types of DOM, Suwannee River Humic Acid (HA) and Suwannee River Fulvic Acid (FA), on polystyrene microplastics (PSMPs, 10 µm) in aquatic environments was investigated. The adsorption of both HA and FA on PSMPs could be well described by using pseudo second-order and Freundlich models. The adsorption of HA and FA on PSMPs was low pH-dependent, particularly for FA adsorption. However, the elevated ionic strength slightly increased the adsorption of HA and FA on PSMPs. Based on Freundlich model, the site energy distribution of HA and FA adsorption on PSMPs under the experimental conditions were estimated. HA and FA first occupied the high-energy adsorption sites and then diffused to the low-energy adsorption sites on PSMPs. With higher site energies, HA demonstrated a much stronger adsorption affinity to PSMPs than FA. The adsorption site heterogeneity (σe*) on PSMPs under the experimental conditions were close. Hydrophobic interaction and π-π electron donor acceptor interaction acted simultaneously in the HA and FA adsorption on PSMPs. The results of this study suggested that the environmental behaviors of microplastics would be influenced by the amount and the type of DOM as well as solution chemistry.

Occurrence and distribution of organophosphate esters in urban soils of the subtropical city, Guangzhou, China.

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.

A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120 ng g(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples.

Occurrence and distribution of phthalate esters in riverine sediments from the Pearl River Delta region, South China.

Sixty-eight sediment samples collected from Dongjiang River, Xijiang River, Beijiang River and Zhujiang River in the Pearl River Delta (PRD) region, Southern China, were analyzed for 16 phthalate esters (PAEs). PAEs were detected in all riverine sediments analyzed, which indicate that PAEs are ubiquitous environmental contaminants. The Σ16PAEs concentrations in riverine sediments in the PRD region ranged from 0.567 to 47.3 µg g(-1) dry weight (dw), with the mean and median concentrations of 5.34 µg g(-1) dw and 2.15 µg g(-1) dw, respectively. Elevated PAEs concentrations in riverine sediments in the PRD region were found in the highly urbanized and industrialized areas. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs, with the mean and median concentrations of 1.12 µg g(-1)dw, 0.420 µg g(-1) dw and 3.72 µg g(-1) dw, and 0.429 µg g(-1) dw, 0.152 µg g(-1) dw and 1.55 µg g(-1) dw, respectively, and accounted for 94.2-99.7% of the Σ16PAEs concentrations. Influenced by local sources and the properties of PAEs, a gradient trend of concentrations and a fractionation of composition from more to less industrialized and urbanized areas were discovered. As compared to the results from other studies, the riverine sediments in the PRD region were severely contaminated with PAEs. Information about PAEs contamination status and its effect on the aquatic organisms in the PRD region may deserve further attention.

Microwave-assisted extraction combined with gel permeation chromatography and silica gel cleanup followed by gas chromatography-mass spectrometry for the determination of organophosphorus flame retardants and plasticizers in biological 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.

Characteristics and assessment of phthalate esters in urban dusts in Guangzhou city, China.

Phthalate esters (PAEs) were examined in indoor and outdoor dust samples from the subtropical city of Guangzhou, China. The ∑(16)PAEs concentrations ranged from 121 to 3,223 µg g(-1) dust, with the median concentration of 840 µg g(-1) dust. Significantly higher concentrations of PAEs in dust samples were found in offices where electrical and electronic devices, carpet pads, and office furniture were widely used. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in indoor and outdoor dust samples, and accounted for >96.8% and >93.1% of the ∑(16)PAEs concentrations, respectively. The median daily inhalation exposure of ∑(16)PAEs were 3.53 and 0.247 µg kg(-1) body weight day(-1), and at the 95(th) percentile were 7.62 and 0.530 µg kg(-1) body weight day(-1), up on the measured concentrations and estimated dust ingestion rates, respectively, for toddles and adults. The ubiquitous distribution of PAEs as noted in this study suggests the need for detailed assessment of PAEs concentrations using more sites and to further investigate the factors influencing PAEs exposure in China.

Seasonal distribution of phthalate esters in surface water of the urban lakes in the subtropical city, Guangzhou, China.

Urban lakes are vulnerable to the accumulation of toxic and/or potentially toxic contaminants, such as phthalate esters (PAEs) from urban stormwater runoff, atmospheric deposition, as well as untreated discharge of industrial wastewater and municipal sewage. The concentrations of 16 PAEs in surface water from 15 urban lakes in the subtropical city, Guangzhou, were measured, respectively in spring, summer and winter 2006, to elucidate the effect of the seasonal variation in climate conditions on the distribution of PAEs. Seasonal variations of the Sigma(16)PAEs concentrations, ranging, respectively from 0.47 to 6.19 microg L(-1) and from 24.9 to 221 microg g(-1), were measured in the dissolved and suspended particulate matter (SPM) phases. The highest concentrations of PAEs were present in summer. The spatial distribution of PAEs was site-specific. Of the 16 PAEs, dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), di(4-methyl-2-pentyl) phthalate (DMPP), di(2-ethylhexyl) phthalate (DEHP) were present in all the samples analyzed, and dominated by DnBP, DiBP and DEHP. Composition profile of PAEs indicated that the application of DnBP/DiBP is relatively high in the Pearl River Delta (PRD). Longer/branching alkyl PAEs likely adsorb to SPM in aquatic environments. Normalized partition coefficient (K(OC)) between the dissolved water and SPM was correlated with n-octanol/water partition coefficient (K(OW)) to understand the environmental behavior of PAEs.

Distribution of phthalate esters in urban soils of subtropical city, Guangzhou, China.

Surface soils from 37 sampling sites including roadsides (RS), parks (PA) and residential areas (RE) of the Subtropical City, Guangzhou, were collected in December of 2005 and analyzed for 16 phthalate esters (PAEs). PAEs were detected in all surface soils analyzed, which indicate that PAEs are ubiquitous environmental contaminants. The summation operator(16)PAEs concentrations ranged from 1.67 to 322 microg g(-1)-dry weight (dw), with the median concentration of 17.7 microg g(-1)-dw, mainly originating from municipal solid waste leachate, discarded plastic effusion, municipal sewage and atmospheric depositions. Concentrations of PAEs were poorly correlated with soil organic carbon content, suggesting mixing process between local and on-going sources. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs, with the median concentrations of 1.63 microg g(-1)-dw, 1.80 microg g(-1)-dw and 14.8 microg g(-1)-dw, respectively, and accounted for 74.2-99.8% of the summation operator(16)PAEs concentrations. Principal Component Analysis (PCA) was applied to the distribution patterns of PAEs in the urban soils. Significant correlations existed among DiBP, DnBP, and DEHP, and between dimethyl phthalate (DMP) and diethyl phthalate (DEP). No significant differences of PAE congeneric profiles were observed between this and studies conducted elsewhere, which is consistent with the application of similar commercial PAEs around the world. As compared to the results from other studies, the urban soils of Guangzhou city were severely contaminated with PAEs. The environmental and human health risks posed by PAEs in the urban soils of Guangzhou city may deserve further attention.

Phthalate esters (PAEs): emerging organic contaminants in agricultural soils in peri-urban areas around Guangzhou, China.

This study reports the first data on the concentrations and distribution of phthalate esters (PAEs) in the agricultural soils from the peri-urban areas of Guangzhou city. Sigma(16)PAEs concentrations ranged from 0.195 to 33.6 microg g(-1)-dry weight (dw). Elevated levels of PAEs were recorded in the vegetable fields located next to the urban districts, and a decreasing trend exists following the distance away from the urban center. Diisobutyl phthalate (DiBP), Di-n-butyl phthalate (DnBP), and Di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in the agricultural soils. Significant relationship (correlation coefficient R(2)=0.85, p<0.01, n=40) was present between the accumulation of PAEs and total organic carbons in agricultural soils. In addition, both pH and texture of soils are found to be important factors affecting the level of PAEs. This study shows that the agricultural soils in the peri-urban area of Guangzhou city were moderately polluted by PAEs.

Occurrence of phthalate esters in water and sediment of urban lakes in a subtropical city, Guangzhou, South China.

Extensive use of phthalate esters (PAEs) in both industrial processes and consumer products has resulted in the ubiquitous presence of these chemicals in the environment. This study reports the first data on the concentrations of 16 phthalate esters (PAEs) in water and sediments of the urban lakes in Guangzhou City. PAEs were detected in all samples analyzed, mainly originating from urban stormwater runoff, atmospheric deposition, as well as untreated discharge of industrial wastewater and municipal sewage. The Sigma(16)PAEs concentrations in water and sediments ranged from 1.69 to 4.72 microg L(-1) and 2.27 to 74.94 microg g(-1)-dry weight (dw), with the mean concentrations of 2.91 microg L(-1) and 20.85 microg g(-1)-dw, respectively, which indicates that sediment is a significant sink for PAEs. Variability of the Sigma 16PAEs concentrations in water and sediment in the urban lakes was almost consistent. The spatial distribution of PAEs was site-specific. Of the 16 PAEs, DMP, DEP, DnBP, DiBP, DMPP, and DEHP were present in all water and sediment samples. DnBP was abundant in water (53.0-81.2%), while no single dominant congener was found in sediments. The abundances of DiBP were similar to those of DEHP, and DiBP and DEHP collectively accounted for 77.2-97.6% of the Sigma 16PAEs concentrations. Congener specific analysis confirmed that DnBP was a predictive indicator for the dissolved summation operator16 PAEs concentration (correlation coefficient r=0.968, p<0.01), and that DiBP was a predictive indicator for the sediment summation operator16 PAEs concentration (r=0.975, p<0.01). As compared to the results for other studies, the urban lakes of Guangzhou were moderately polluted by PAEs.

[Mercury concentration and its distribution in Nycticorax nycticorax and Chinese Ardeola bacchus fledglings at Huangpu District of Guangzhou City, China].

In this study, live fledglings of Nycticorax nycticorax and Ardeola bacchus at the Huangpu District of Guangzhou City were collected, and their primary feather, breast feather, tail feather, liver, chest muscle and egg shell were sampled for mercury determination. The results showed that these two heron species had a very similar distribution pattern of mercury concentration in their tissues and organs, i. e., tail feather > breast and primary feather > liver > chest muscle > egg shell. Ardeola bacchus had higher levels of mercury in all its tissues than Nycticorax nycticorax. There were significant interspecific differences in mercury level for breast feather and primary feather. Because the collection of breast feather is easier and not harmful to birds, it is better to use it rather than primary or tail feather to monitor environmental pollution. The mercury level in breast feather was ten times higher than that in liver, lower than that in tail feather, but not significantly different to that in primary feather. The mercury concentrations in the tissues of Nycticorax nycticorax and Ardeola bacchus from Huangpu District of Guangzhou were similar to those from the suburbs of Chengdu, Sichuan Province, but lower than those from Taihu Lake, Jiangsu Province and higher than those from Hong Kong.