Caiming Tang

Occurrence of steroid estrogens, endocrine-disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China

A scoping study was conducted to investigate the residues of nineteen pharmaceuticals and personal care products (PPCPs), including 4 natural and 3 synthetic steroid estrogens, 7 endocrine-disrupting phenols, and 5 acid pharmaceuticals in three urban streams and the Major Pearl River at Guangzhou, a megapolis in the Pearl River Delta, South China. Estrone was detected in >60% water samples with a maximum concentration of 65 ng L(-1). Endocrine-disrupting phenols (nonylphenol, bisphenol A, triclosan, 2-phenylphenol, methyparaben, and propylparaben) were found to be widely present at rather high concentrations in the urban riverine water of Guangzhou. Salicylic acid, clofibric acid and ibuprofen were detected in most water samples with maximum concentrations of 2098, 248 and 1417 ng L(-1) respectively, whereas naproxen was less frequently detected and also at lower concentration. Both the detection frequencies and median concentrations of the PPCPs appeared higher during the low-flow season than during the high-flow season. The seasonal difference in PPCPs occurrence was probably attributed to the dilution effect caused by the rainfall. PPCPs in the urban riverine water of Guangzhou originated mainly from random discharge and/or leakage of municipal wastewater. PPCPs contamination in the Major Pearl River may be of a potential environmental issue, especially during the low-flow season.

Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China

The concentrations of three currently used non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and tetrabromobisphenol A bis (2,3-dibromopropyl ether) (TBBPA-DBPE), were examined in environmental and biota samples collected from the Pearl River Delta (PRD) and an electronic waste (e-waste) area in southern China. We also examined deca-BDE (decabromodiphenyl ether) and nine tri- through hepta-BDE congeners for comparison. The results indicate that these non-PBDE BFRs occur widely in the environment of the two study areas. We found a noticeable increase in the levels of TBBPA-DBPE and DBDPE in recent sediments, the concentrations of which even exceed those of BDE209 (deca-BDE) in some samples from the PRD. The BFR profiles of the two study areas are distinct. Relatively high proportions of DBDPE and TBBPA-DBPE were found in the PRD environment, whereas the levels of discontinued BFRs (penta-BDEs and BDE183) and BTBPE were higher in the e-waste area. Our results suggest that the industrial activities in the PRD and the recycling of e-waste have introduced distinct types of BFR contamination to the ambient environment and deca-BDE product has been partly replaced by the TBBPA-DBPE and DBDPE in the PRD. Furthermore, BTBPE and DBDPE were detected in bird tissues and BTBPE in the fish tissues collected from the e-waste area. This is the first report of the occurrence of TBBPA-DBPE in environmental samples worldwide. More studies are needed for reaching a better understanding of the behavior, bioaccumulation, and toxicology of these increasingly used BFRs in the environment.

Concentrations, transport, fate, and releases of polybrominated diphenyl ethers in sewage treatment plants in the Pearl River Delta, South China

Wastewater has proved to be a significant source of polybrominated diphenyl ethers (PBDEs) in the environment. Seventeen congeners from tri- to deca-BDEs were determined to characterize the occurrence, fate, and transport of PBDEs in two sewage treatment plants in the Pearl River Delta, South China. The PBDE concentrations varied substantially from 13.3 to 2496.4 ng L(-1) in the raw wastewater, depending on the wastewater types and contents of the suspended particulate matter (SPM). The concentrations declined to 0.9 to 4.4 ng L(-1) in the treated effluent and were closely associated with SPM contents. BDE-209 was the predominant congener in the wastewater and sewage sludge. Most of PBDEs might have ended up in the sewage sludge, with <4.7% being discharged with the treated effluent. The results revealed that PBDEs were not significantly degraded by biological treatment and chlorination in the STPs. An annual release of PBDEs was estimated at 2280 kg/year through wastewater from the Pearl River Delta.

Multiresidue determination of fluoroquinolone, sulfonamide, trimethoprim, and chloramphenicol antibiotics in urban waters in China.

A feasible method has been optimized to simultaneously determine multiclass antibiotic residues, including sulfonamides, fluoroquinolones, trimethoprim, and chloramphenicol in urban riverine water and wastewater by off-line solid phase extraction and high-performance liquid chromatography coupled with a diode-array ultraviolet detector and a fluorescence detector. Internal standard and standard addition methods were used in combination to identify and quantify these antibiotics to compensate for the matrix interference. The method quantification limits (MQLs) were determined to be 0.035 to 0.100 microg/L and 0.100 to 0.300 microg/L for the riverine water and wastewater, respectively. Recoveries of the investigated antibiotics ranged from 63 to 126%. Sulfamethoxazole was the most frequently detected antibiotic residue in Guangzhou section of the Major Pearl River, South China, with a maximum level of 0.510 microg/L. Fluoroquinolone antibiotics were relatively less detected with a maximum level of 0.459 microg/L. The maximum concentration of sulfamethoxazole reached 5.597 microg/L in the raw wastewater from a large-scale sewage treatment plant in Guangzhou city. Around 30% of sulfamethoxazole might survive the primary clarification and biotreatment processes in the sewage treatment plant. None of the investigated antibiotics have been found above MQLs in the final effluent after chlorine disinfection.

Occurrence and behavior of pharmaceuticals, steroid hormones, and endocrine-disrupting personal care products in wastewater and the recipient river water of the Pearl River Delta, South China

The occurrence and behavior of β-blockers, antiepileptic drug carbamazepine and its metabolites, X-ray contrast agent iopromide, natural and synthetic hormones, and several groups of hormone-like personal care products (PCPs), including antiseptics (triclocarban, triclosan, and 2-phenylphenol), parabens and bisphenol A, were investigated in municipal wastewater, sewage sludge, and urban river water of the Pearl River Delta, South China. The pharmaceuticals, natural hormones and PCPs were ubiquitously detected in the raw wastewater from a sewage treatment plant (STP). Only triclocarban and triclosan were detected at significant amounts in the dewatered sludge. Iopromide and the PCPs were greatly removed/transformed from the aqueous phase of the wastewater. The β-blockers were only moderately removed/transformed. Carbamazepine passed through the STP almost unchanged. Biodegradation was the dominant process for elimination/transformation of the pharmaceuticals, hormones, and most PCPs in the STP. However, sorption also played an important role in the fate of triclocarban with nearly 50% of the mass load entering the STP ended up and persisted in the dewatered sludge. The pharmaceuticals, estrone, and PCPs were also widely detected in the Pearl River at Guangzhou. Bisphenol A had the highest concentration. The pharmaceutical concentrations in the Pearl River were higher in March than in May, most likely due to less dilution by lower precipitation. The omnipresence and high levels of the pharmaceuticals and PCPs in the Pearl River may be associated with direct discharge of untreated wastewater and pose potential risks to the ecological system.

Determination of commonly used azole antifungals in various waters and sewage sludge using ultra-high performance liquid chromatography@?tandem mass spectrometry

Sensitive and reliable methods have been developed and validated for determination of commonly consumed azole antifungal pharmaceuticals (clotrimazole, econazole, ketoconazole, and miconazole) and biocides (propiconazole and tebuconazole) in various waters and sewage sludge. Solid phase extraction (SPE) combined with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was used to determine the azole antifungals in waters. Azole antifungals in sewage sludge were extracted with ultrasonic-assisted extraction, followed by SPE cleanup and UHPLC-MS/MS detection. Quantification was performed by internal standard calibration in multiple reaction monitoring mode. Recoveries were mostly in the range of 52-110% with relative standard deviations generally within 20%. Method quantification limits were 0.5-6 ng L(-1) in waters and 3-9 ng g(-1) dry weight (dw) in sewage sludge, respectively. The methods were applied to determine the azole antifungals in wastewater, river water, sediment, and sewage sludge sampled from the Pearl River Delta, China. Clotrimazole, ketoconazole, and miconazole were widely detected at low ng L(-1) in waters, low ng g(-1) dw in river sediment, and low microg g(-1) dw in sewage sludge. The methods can provide valuable tools for investigating occurrence and fate of the azole antifungals in the environment.

Multiresidue Determination of Sulfonamides, Macrolides, Trimethoprim, and Chloramphenicol in Sewage Sludge and Sediment Using Ultrasonic Extraction Coupled with Solid Phase Extraction and Liquid Chromatography-Tandem Mass Spectrometry

A sensitive and feasible method was developed for the simultaneous determination of 10 trace antibiotic residues including sulfonamides, macrolides, trimethoprim, and chloramphenicol in sewage sludge and sediment. The method involved ultrasonic extraction followed by solid phase extraction cleanup and liquid chromatography-tandem mass spectrometry coupled with electrospray ionization in positive mode. The antibiotics were identified and determined by internal standard method in selected multiple reaction monitoring mode. The detection limits were in a range of 2.2–66.9 ng g−1 dry weight for the investigated antibiotic compounds in sewage sludge. The recoveries ranged from 74.7% to 111.8% with relative standard deviations of 1.2%–10.6%. The method was successfully applied to a primary investigation of the occurrence of antibiotic residues in a sewage sludge sample and a river sediment sample collected from Guangzhou. Sulfamethazine, trimethoprim, azithromycin, clarithromycin, dehydrated erythromycin, and roxithromycin were detected in both the sewage sludge and the river sediment, ranging from 6.8–125.6 ng g−1 dry weight.

Occurrence and behavior of non-steroidal anti-inflammatory drugs and lipid regulators in wastewater and urban river water of the Pearl River Delta, South China

Occurrence of five non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, naproxen, indomethacin and diclofenac) and three lipid regulators (bezafibrate, clofibric acid and gemfibrozil) was investigated in wastewater, sewage sludge, and river water of the urban section of the Pearl River at Guangzhou in South China. Behavior and fate of the pharmaceuticals during treatment in two sewage treatment plants (STPs) were also studied in depth by determining concentrations in the influents and effluents at major treatment units and the sewage sludge. Concentrations of the pharmaceuticals in the raw wastewater were mostly at ng L(-1) levels except salicylic acid whose concentrations ranged from 9.6 to 23.3 μg L(-1). No significant amount of the pharmaceuticals was detected in the suspended particulate matter of wastewater and sewage sludge. Salicylic acid, indomethacin, and naproxen were almost completely removed (≥ 99%); gemfibrozil, ibuprofen and bezafibrate were significantly removed (>75%), whereas diclofenac and clofibric acid were removed by 60-70% during treatment in the STPs. Generally, biodegradation was the governing process for elimination of the investigated pharmaceuticals. Anaerobic biodegradation was responsible for most of the removal of diclofenac whereas aerobic biodegradation also played an important role in elimination of the other pharmaceuticals except SA, which was nearly completely removed after the anoxic process. In the Pearl River, the pharmaceuticals were widely detected. Both the concentrations and detection frequency were higher in March 2008 than those in the other seasons, which may be ascribed mainly to less dilution caused by lower precipitation. Besides the STPs, urban canals directly connected with the Pearl River may also be important contributors to the pharmaceutical contamination in the river.

Temporal trends of hydrocarbons in sediment cores from the Pearl River Estuary and the northern South China Sea

Concentrations and fluxes of unresolved complex mixture of hydrocarbons (UCM) and polycyclic aromatic hydrocarbons (PAHs) were analyzed for two (210)Pb dated sediment cores from the Pearl River Estuary (PRE) and the adjacent northern South China Sea (NSCS). Compound-specific stable carbon isotopic compositions of individual n-alkanes were also measured for identification of the hydrocarbon sources. The historical records of PAHs in the NSCS reflected the economic development in the Pearl River Delta during the 20th century. PAHs in the NSCS predominantly derive from combustion of coal and biomass, whereas PAHs in the PRE are a mixture of petrogenic and pyrogenic in origins. The isotopic profiles reveal that the petrogenic hydrocarbons in the PRE originate predominantly from local spillage/leakage of lube oil and crude oils. The accumulation rates of pyrogenic PAHs have significantly increased, whereas UCM accumulation has slightly declined in the NSCS in the recent three decades.

Multi-target determination of organic ultraviolet absorbents in organism tissues by ultrasonic assisted extraction and ultra-high performance liquid chromatography-tandem mass spectrometry.

A sensitive and reliable method was developed for multi-target determination of 13 most widely used organic ultraviolet (UV) absorbents (including UV filters and UV stabilizers) in aquatic organism tissues. The organic UV absorbents were extracted using ultrasonic-assisted extraction, purified via gel permeation chromatography coupled with silica gel column chromatography, and determined by ultra-high performance liquid chromatography-tandem mass spectrometry. Recoveries of the UV absorbents from organism tissues mostly ranged from 70% to 120% from fish filet with satisfactory reproducibility. Method quantification limits were 0.003-1.0ngg(-1) dry weight (dw) except for 2-ethylhexyl 4-methoxycinnamate. This method has been applied to analysis of the UV absorbents in wild and farmed aquatic organisms collected from the Pearl River Estuary, South China. 2-Hydroxy-4-methoxybenzophenone and UV-P were frequently detected in both wild and farmed marine organisms at low ngg(-1)dw. 3-(4-Methylbenzylidene)camphor and most of the benzotriazole UV stabilizers were also frequently detected in maricultured fish. Octocrylene and 2-ethylhexyl 4-methoxycinnamate were not detected in any sample. This work lays basis for in-depth study about bioaccumulation and biomagnification of the UV absorbents in marine environment.