[Show abstract][Hide abstract] ABSTRACT: Per- and polyfluoroalkyl substances (PFASs) are used in various industries, which results in their ubiquitous occurrence in the environment. This study determined the concentrations of eighteen PFASs in muscle and liver of nine wild freshwater fish species collected from rivers in the Pearl River Delta (PRD) region, South China, and assessed their bioaccumulation and potential health risks to local people. The results showed that eight and twelve PFASs were detected in the fish muscle and liver samples, respectively. Perfluorooctane sulfonate (PFOS) was found to be the predominant PFAS both in muscle and liver with its highest concentrations of 79ng/g wet weight (ww) in muscle and 1500ng/g ww in liver, followed by Perfluoroundecanoic acid (PFUnDA) and Perfluorotridecanoic acid (PFTrDA) with trace concentrations. The mean PFOS concentrations in fish muscle and liver tissues of the nine collected species ranged from 0.40ng/g in mud carp to 25ng/g in snakehead, and from 5.6ng/g in mud carp to 1100ng/g in snakehead, respectively. Significant positive correlations were found among PFASs both in water and fish, indicating a similar pollution source for these PFASs. In tilapia samples, PFOS concentrations showed an increasing trend with increasing length and weight, but no significant difference between genders. Bioaccumulation factors (logBAF) in fish for the PFASs were in the range from 2.1 to 5.0. The calculated hazard ratios (HR) of PFOS for all fishes were in the range of 0.05-2.8, with four out of nine species (tilapia, chub, leather catfish and snakehead) having their HR values more than 1.0. The results suggest that frequent consumption of these four fish species may pose health risks to local population.
Ecotoxicology and Environmental Safety 07/2014; 107C:192-199. · 2.20 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Biocides are widely formulated in household and personal care products. We investigated the distribution and ecological risks of 16 household biocides in aquatic environments of a highly urbanized region in South China, evaluated triclosan as a chemical indicator for this group of household chemicals, and proposed a novel approach to predict the environmental occurrence and fate of these household biocides by using triclosan usage data and a level-III fugacity model. Eleven biocides were quantitatively detected at concentrations up to 264 ± 15.3 ng/L for climbazole in surface water, and up to 5649 ± 748 ng/g for triclocarban in sediment of four rivers in the region. The distribution of biocides in the aquatic environments was significantly correlated with environmental variables such as total nitrogen, total phosphorus and population. Domestic sewage in the region was the dominant pollution source for most biocides such as azole fungicides (fluconazole, climbazole, clotrimazole, ketoconazole, miconazole, and carbendazim) and disinfectants (triclosan and triclocarban). Preliminary risk assessment showed high ecological risks posed by two biocides carbendazim and triclosan in river waters. Mostly important, triclosan was found to be a reliable chemical indicator to surrogate household biocides both in water and sediment based on the correlation analysis. In addition, the fugacity modeling could provide simulated concentrations comparable to the monitoring results. Therefore, with the usage data of the chemical indicator triclosan and correlation formula with other biocides, this model can be applied for predicting the occurrence and fate of various household biocides in a catchment.
Water Research 04/2014; 58C:269-279. · 4.66 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Benzotriazoles (BTs) and benzotriazole ultraviolet (UV) stabilizers (BUVSs) are commonly used industrial and household chemicals, but little is known about their dissipation behavior in the soil environment associated with biosolid application. The authors investigated the occurrence and dissipation of 4 BTs (BT, 5-methyl-1H-benzotriazole [5-TT], 5-chloro-1H-benzotriazole [CBT], and 5,6-dimethyl-1H-benzotriazole [XT]) and 5 BUVSs (UV-326, UV-327, UV-328, UV-329, and UV-P) in biosolid-amended soil of 3 trial sites (Zhejiang, Hunan, and Shandong) in China following 2 treatments (treatment 1: a single application of biosolid; treatment 2: repeated application of biosolid). The results showed that except for CBT and XT, the other 7 compounds could be detected in most of the biosolid and biosolid-amended soils at levels of a few to tens of nanograms per gram and that the concentrations of the 7 compounds for treatment 2 were obviously higher than those for treatment 1. In the 1-yr monitoring of the Shandong site, 2 BTs (BT and 5-TT) and 5 BUVSs (UV-326, UV-327, UV-328, UV-329, and UV-P) were significantly dissipated in the biosolid-amended soils. The field half-lives of BT and 5-TT ranged from 217 d to 345 d, while those for the BUVSs ranged between 75 d and 218 d. The field half-lives of target compounds in soil were found to be comparable to the modeling results. The results suggest the persistence of BTs and BUVSs in soil environments with quite slow dissipation rates.
Environmental Toxicology and Chemistry 04/2014; 33(4):761-7. · 2.62 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Benzotriazole ultraviolet stabilizers (BUVSs) have been commonly used in industrial and household product formulations, and have been detected in biosolids from wastewater treatment plants. However, little is known about their occurrence and dissipation behavior in the soil environment associated with biosolid application. This study investigated the occurrence and dissipation of five typical BUVSs (UV-326, UV-327, UV-328, UV-329 and UV-P) in biosolid-amended soils, and the uptake of these biocides by plants. The field trial includes two treatment groups: old groups with biosolid application at rates of 5, 10, 20 and 40 t ha(-1) every year within 5 years, and new groups with only one biosolid application. The results showed that the five BUVSs could be detected in most biosolid-amended soils at a few to tens of ng g(-1) levels, but not detected in the control soils. These chemicals were not found in the crop plants collected from the trial plots. Moreover, high biosolid application rates and repeated biosolid applications resulted in high accumulation of these BUVSs in soil. During one year monitoring, the five BUVSs were significantly dissipated in the biosolid-amended soils with their half-lives ranging from 79 to 223 days, which were comparable with the modeling results. The results from this study demonstrated the persistence of BUVSs in soil environments with quite slow dissipation rates.
[Show abstract][Hide abstract] ABSTRACT: The azole fungicide fluconazole has been reported to be persistent in conventional wastewater treatment plants. This study investigated the photodegradation of fluconazole under UV-254 in aqueous solutions. The results revealed that the photodegradation of fluconazole was pH-dependent (2.0-12.0) following the pseudo-first-order kinetics with quantum yield values ranging from 0.023 to 0.090 mol einstein(-1), and it underwent a direct and self-sensitized mechanism involving (1)O2. The main photodegradation by-products were identified and semi-quantitated. The proposed photodegradation pathway included hydroxylative defluorination reaction. The 72 h-NOEC and 72 h-LOEC values for fluconazole using a freshwater unicellular green alga Pseudokirchneriella subcapitata were 10 μM and 15 μM. Overall, the photodegradation of fluconazole produced a significant decrease in algal toxicity. It also proved that the photodegradation by-products will not present extra toxicity to this alga than fluconazole itself.
Water Research 01/2014; 52C:83-91. · 4.66 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The antimicrobial agents triclocarban (TCC) and triclosan (TCS) and synthetic musks AHTN (Tonalide) and HHCB (Galaxolide) are widely used in many personal care products. These compounds may release into the soil environment through biosolid application to agricultural land and potentially affect soil organisms. This paper aimed to investigate accumulation, dissipation and potential risks of TCC, TCS, AHTN and HHCB in biosolid-amended soils of the three field trial sites (Zhejiang, Hunan and Shandong) with three treatments (CK: control without biosolid application, T1: single biosolid application, T2: repeated biosolid application every year). The one-year monitoring results showed that biosolids application could lead to accumulation of these four chemicals in the biosolid-amended soils, with the residual concentrations in the following order: TCC>TCS>AHTN>HHCB. Dissipation of TCC, TCS, AHTN and HHCB in the biosolid-amended soils followed the first-order kinetics model. Half-lives for TCC, TCS, AHTN and HHCB under the field conditions of Shandong site were 191, 258, 336 and 900days for T1, and 51, 106, 159 and 83days for T2, respectively. Repeated applications of biosolid led to accumulation of these personal care products and result in higher ecological risks. Based on the residual levels in the trial sites and limited toxicity data, high risks to soil organisms are expected for TCC and TCS, while low-medium risks for AHTN and HHCB.
Science of The Total Environment 11/2013; 470-471C:1078-1086. · 3.26 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Natural and synthetic steroid hormones such as progesterone and norgestrel in the aquatic environment may cause adverse effects on aquatic organisms. This study investigated the biotransformation of progesterone and norgestrel in aqueous solutions by two freshwater microalgae Scenedesmus obliquus and Chlorella pyrenoidosa and elucidated their transformation mechanisms. More than 95% of progesterone was transformed by the two microalgae within 5d. For norgestrel, almost complete transformation by S. obliquus was observed after 5d, but nearly 40% was remained when incubated with C. pyrenoidosa. The results also showed that these two compounds were not accumulated in the algal cells. Biotransformation was found to be the main mechanism for their loss in the aqueous solutions, and it followed the first-order kinetic model. For progesterone, three main transformation products, i.e. 3β-hydroxy-5α-pregnan-20-one, 3,20-allopregnanedione and 1,4-pregnadiene-3,20-dione, and six minor androgens were identified. For norgestrel, only two transformation products, 4,5-dihydronorgestrel and 6,7-dehydronorgestrel, were identified for the first time. Hydroxylation, reduction and oxidation are proposed to be the main transformation pathways. Among the two microalgae species, S. obliquus was found more efficient in the transformation of the two target compounds than C. pyrenoidosa. The results clearly demonstrated the capability of the two microalgae to transform the two progestogens. The biotransformation and products could have significant environmental implications in the fate and effects of the two steroids.
[Show abstract][Hide abstract] ABSTRACT: Biosolid application in the agricultural land may contaminate soils with various household chemicals and personal care products. This study investigated the occurrence and dissipation of typical azole biocides climbazole, clotrimazole and miconazole in biosolid-amended soils, and the uptake of these biocides by plants. The field trial includes two treatment groups: old groups with biosolid application at a rate of 5, 10, 20 and 40 t/ha every year within 5 years, and new groups with only one biosolid application. The results showed that climbazole, clotrimazole and miconazole were detected in the biosolid-amended soils, but not detected in the control soils. These biocides were not found in the crop plants collected from the trial plots. The dissipation half-lives for climbazole, clotrimazole and miconazole under the field conditions were 175-179, 244 and 130-248 days, respectively. High biosolid application rates and repeated biosolid applications could lead to higher persistence of the biocides in the agricultural soils. An exposure model could effectively predict the residual concentrations of climbazole and miconazole in the biosolid-amended soils of the old treatments with different biosolid application rates. Thus the field trial demonstrated high persistence of these three biocides in the soil environments.
Journal of Agricultural and Food Chemistry 06/2013; · 2.91 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This study investigated the occurrence and dissipation of three azole biocides climbazole, clotrimazole and miconazole in biosolid-amended soils of the three sites (Zhejiang, Hunan and Shandong) in China following three treatments (CK: control without biosolid application; T1: one biosolid application; T2: biosolid application every year). The results showed that climbazole, clotrimazole and miconazole were present in the biosolid and biosolid-amended soils, but absent in the control soils. In the soils treated with biosolids, the concentrations of climbazole, clotrimazole and miconazole were mostly lower in the Zhejiang soils than in the Shandong or Hunan soils, suggesting that these three biocides are more readily dissipated under the flooding condition. During the one year monitoring, the concentrations of climbazole, clotrimazole and miconazole in the biosolid-applied soils showed only slight variations. The dissipation half-lives for miconazole calculated under the field conditions of Shandong site were 440days for T1 and the half-lives for clotrimazole were 365days for T2. The results suggested the persistence of these three biocides in the soil environments.
Science of The Total Environment 03/2013; 452-453C:377-383. · 3.26 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Wastewater treatment plants (WWTPs) are regarded as one of the most important sources of antibiotics in the environment. Two sampling campaigns over a period of one year in two wastewater treatment plants (plant A: activated sludge with chlorination, and plant B: oxidation ditch with UV) of Guangdong Province, China were carried out to assess the occurrence and fate of 11 classes of 50 antibiotics. The wastewater samples were extracted by Oasis HLB cartridges (6mL, 500mg), while the solid samples (sludge and suspended solid matter) were extracted by ultrasonic-assisted extraction with solvents (acetonitrile and citric acid buffer), followed by an enrichment and clean-up step with solid-phase extraction using SAX-HLB cartridges in tandem. The results showed the presence of 20 and 17 target compounds in the influents and effluents, respectively, at the concentrations ranging from low ng/L to a few μg/L. Sulfamethoxazole, norfloxacin, ofloxacin, anhydro erythromycin and trimethoprim were most frequently detected in the WWTPs wastewaters. Twenty-one antibiotics were found in the sewage sludge from the two WWTPs at the concentrations up to 5800ng/g, with tetracycline, oxytetracycline, norfloxacin and ofloxacin being the predominant antibiotics. The total mass loads of antibiotics per capita in the two plants ranged from 494 to 901μg/d/inhabitant (672±182μg/d/inhabitant) in the influents, from 130 to 238μg/d/inhabitant (175±45μg/d/inhabitant) in the effluents and from 107 to 307μg/d/inhabitant (191±87.9μg/d/inhabitant) in the dewatered sludge, respectively. The aqueous removals for sulfonamides, macrolides, trimethoprim, lincomycin and chloramphenicol in the WWTPs were mainly attributed to the degradation processes, while those for tetracyclines and fluoroquinolones were mainly due to the adsorption onto sludge.
Science of The Total Environment 03/2013; 452-453C:365-376. · 3.26 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The objective of this study was to screen the occurrence of 50 antibiotics in a typical swine farm in southern China, which includes animal feeds, waste collection and treatment systems (lagoons and anaerobic digesters), and receiving environments (vegetable fields, streams, and private wells). Nine antibiotics were found in the feeds for different stages of the development of pigs in the swine farm, at concentrations ranging from 2.37 ± 0.16 ng g(-1) (sulfamethazine) to 61 500 ± 11 900 ng g(-1) (bacitracin). 11, 17 and 15 target compounds were detected in feces, flush water, and suspended particles in the swine farm, respectively. Based on the survey of feeds and animal waste from the farm, chlortetracycline, tetracycline, bacitracin and florfenicol in the feces, flush water and suspended particles mainly originated from the feeds, while most sulfonamides, including doxycycline, oxytetracycline, fluoroquinolones, macrolides and trimethoprim, were mainly from injection and other oral routes. The daily excretion masses of antibiotics per pig calculated based on animal waste had the following order: sows (48.3 mg per day per pig), piglets (18.9 mg per day per pig), growing pigs (7.01 mg per day per pig) and finishing pigs (1.47 mg per day per pig), indicating that the usage of antibiotics (type and dosage) and excretion masses are related to the growth stage of pigs. Chlortetracycline and bacitracin are the main contributors to the total excretion mass of antibiotics from pigs at different stages of development in the farm. The waste treatment system (lagoons and anaerobic digesters) was found to be ineffective in the elimination of antibiotics. The detection of some antibiotics in the surrounding environments of the farm (the well water, stream water and vegetable field soil) was a reflection of pollution from the swine farm.
[Show abstract][Hide abstract] ABSTRACT: This paper evaluated the excretion masses and environmental occurrence of 11 classes of 50 antibiotics in six typical swine and dairy cattle farms in southern China. Animal feeds, wastewater and solid manure samples as well as environmental samples (soil, stream and well water) were collected in December 2010 from these farms. Twenty eight antibiotics, including tetracyclines, bacitracin, lincomycin, sulfonamides, fluoroquinolones, ceftiofur, trimethoprim, macrolides, and florfenicol, were detected in the feeds, animal wastes and receiving environments. The normalized daily excretion masses per swine and cattle were estimated to be 18.2mg/day/swine and 4.24mg/day/cattle. Chlortetracycline (11.6mg/day/swine), bacitracin (3.81mg/day/swine), lincomycin (1.19mg/day/swine) and tetracycline (1.04mg/day/swine) were the main contributors to the normalized daily excretion masses of antibiotics per swine, while chlortetracycline (3.66mg/day/cattle) contributed 86% of the normalized daily excretion masses of antibiotics per cattle. Based on the survey of feeds and animal wastes from the swine farms and interview with the farmers, antibiotics excreted by swine were mainly originated from the feeds, while antibiotics excreted by dairy cattle were mainly from the injection route. If we assume that the swine and cattle in China excrete the same masses of antibiotics as the selected livestock farms, the total excretion mass by swine and cattle per annum in China could reach 3,080,000kg/year and 164,000kg/year. Various antibiotics such as sulfonamides, tetracyclines, fluroquinolones, macrolides, trimethoprim, lincomycin and florfenicol were detected in well water, stream and field soil, suggesting that livestock farms could be an important pollution source of various antibiotics to the receiving environments.
Science of The Total Environment 12/2012; 444C:183-195. · 3.26 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A sensitive and robust method using solid-phase extraction and ultrasonic extraction for preconcentration followed by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS-MS) has been developed for determination of 19 biocides: eight azole fungicides (climbazole, clotrimazole, ketoconazole, miconazole, fluconazole, itraconazole, thiabendazole, and carbendazim), two insect repellents (N,N-diethyl-3-methylbenzamide (DEET), and icaridin (also known as picaridin)), three isothiazolinone antifouling agents (1,2-benzisothiazolinone (BIT), 2-n-octyl-4-isothiazolinone (OIT), and 4,5-dichloro-2-n-octyl-isothiazolinone (DCOIT)), four paraben preservatives (methylparaben, ethylparaben, propylparaben, and butylparaben), and two disinfectants (triclosan and triclocarban) in surface water, wastewater, sediment, sludge, and soil. Recovery of the target compounds from surface water, influent, effluent, sediment, sludge, and soil was mostly in the range 70-120 %, with corresponding method quantification limits ranging from 0.01 to 0.31 ng L(-1), 0.07 to 7.48 ng L(-1), 0.01 to 3.90 ng L(-1), 0.01 to 0.45 ng g(-1), 0.01 to 6.37 ng g(-1), and 0.01 to 0.73 ng g(-1), respectively. Carbendazim, climbazole, clotrimazole, methylparaben, miconazole, triclocarban, and triclosan were detected at low ng L(-1) (or ng g(-1)) levels in surface water, sediment, and sludge-amended soil. Fifteen target compounds were found in influent samples, at concentrations ranging between 0.4 (thiabendazole) and 372 ng L(-1) (methylparaben). Fifteen target compounds were found in effluent samples, at concentrations ranging between 0.4 (thiabendazole) and 114 ng L(-1) (carbendazim). Ten target compounds were found in dewatered sludge samples, at concentrations ranging between 1.1 (DEET) and 887 ng g(-1) (triclocarban).
Analytical and Bioanalytical Chemistry 10/2012; · 3.66 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Fate and occurrence of fourteen androgens, four estrogens, five glucocorticoids and five progestagens were investigated in three swine farms and three dairy cattle farms with different farming scales and wastes disposal systems in China. Twenty-one, 22, and 12 of total 28 steroids were detected in feces samples with concentrations ranging from below method limit of quantitation (<LOQ for estrone) to 8100 ± 444 ng/g (progesterone), in wastewater samples with concentrations ranging from <LOQ (estrone) to 20,700 ± 1490 ng/L (androsterone), in suspended particles with concentrations ranging from <LOQ (17β-trenbolone) to 778 ± 82.1 ng/g (5α-dihydrotestosterone) in the six farms, respectively. The steroids via swine farms and human sources were mainly originated from wastewater into the receiving environments while those steroids via cattle farms were mainly from cattle feces. The total contributions of steroids to the environment in China are estimated to be 139, 65.8 and 60.7 t/year from swine, dairy cattle and human sources, respectively.
[Show abstract][Hide abstract] ABSTRACT: The occurrence and fate of fourteen androgens, four estrogens, five glucocorticoids and five progestagens were investigated by rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS) in a typical swine farm with lagoon waste disposal systems, in south China. Nineteen, 22 and 8 of 28 steroids were detected at concentrations ranging from 2.2 ± 0.1 ng/g (androsta-1,4-diene-3,17-dione) to 14,400 ± 394 ng/g (progesterone) in the feces samples, from 6.1 ± 2.3 ng/L (17β-boldenone) to 10,800 ± 3190 ng/L (norgestrel) in the flush water samples, and from 5.0 ± 0.2 ng/g (progesterone) to 225 ± 79.4 ng/g (5α-dihydrotestosterone) in the suspended particles, respectively. By comparing the types and concentrations of steroids in different treatment stages of the lagoon systems, it demonstrated that the lagoon systems used in the farm were not effective method to reduce various steroids in wastewater. Among the thirteen synthetic steroids detected in the swine feces and flush water, only seven (methyl testosterone, 17α-trenbolone, 17β-trenbolone, 17α-ethynyl estradiol, dexamethasone, medroxyprogesterone, and norgestrel) were regarded as the parent/metabolite compounds of animal exogenous usage. According to the estimated masses of steroids from feces and flush water, the excretion of steroids for sows were mainly from feces, but for piglets or barrows, most excreted steroids were through flush water rather than feces. The total daily excreted masses of androgens, estrogens, glucocortcoids and progestagens in the sow feces were in the range of 90.7-6310 μg/d, which were up to a thousand fold of those in the feces of other growth stages indicating that the proportion of sow number in the swine farm directly influenced the total excretion mass of steroids. In addition, two natural steroids 4-androstene-3,17-dione and progesterone were worth notice due to their relatively high concentrations per sow excretion, 277 μg/d and 6380 μg/d, respectively, which are approximately equivalent to the daily excretion of 100 persons. Some steroids were also detected in the well water, vegetable field and receiving stream, and may pose potential high risks to some sensitive organisms in the receiving environment.
Water Research 04/2012; 46(12):3754-68. · 4.66 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The occurrence and fate of fourteen androgens, four estrogens, five glucocorticoids and five progestagens were investigated in two different types of wastewater treatment plants (Plant A: activated sludge with chlorination, and Plant B: oxidation ditch with UV) of Guangdong province, China. 14, 14, and 10 of 28 target compounds were detected in the influent, effluent and dewatered sludge samples with the concentrations ranging from below 1.2 ± 0.0 ng L(-1) (stanozolol) to 1368 ± 283 ng L(-1) (epi-androsterone), below 1.0 ± 0.0 ng L(-1) (progesterone) to 23.1 ± 1.0 ng L(-1) (5α-dihydrotestosterone), 1.0 ± 0.1 ng g(-1) (estrone) to 460 ± 4.4 ng g(-1) (5α-dihydrotestosterone), respectively. The concentrations of total androgens (1554-1778 ng L(-1) in influent, 13.3-47.8 ng L(-1) in effluent, 377-923 ng g(-1) in dewatered sludge) were much higher than those of total estrogens (41.5-60.2 ng L(-1) in influent, 5.6-13.5 ng L(-1) in effluent, 13.9-57.8 ng g(-1) in dewatered sludge), glucocorticoids (171-192 ng L(-1) in influent, 2.2-6.3 ng L(-1) in effluent, N.D.-4.4 ng g(-1) in dewatered sludge), and progestagens (39.6-40.5 ng L(-1) in influent, 6.9-12.1 ng L(-1) in effluent, N.D. in dewatered sludge) in these two WWTPs. According to mass balance analysis, the removal rates of most target steroids in Plant A had exceeded 90%, while those in Plant B for nearly half of detected target steroids were lower than 80%. It is obvious that the treatment capacity of the activated sludge system (Plant A) is superior to the oxidation ditch (Plant B) in the degradation of steroids in sewage treatment systems. Androgens, estrogens and progestagens were mainly removed by sorption and degradation, while the reduction of glucocorticoids was primarily due to degradation.
Journal of Environmental Monitoring 11/2011; 14(2):482-91. · 2.09 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: We investigated occurrence of selected compounds (4-t-octylphenol: 4-t-OP; 4-nonylphenols: 4-NP; bisphenol-A: BPA; estrone: E1; 17β-estradiol: E2; triclosan: TCS) and estrogenicity in surface water and sediment of the Yellow River in China by using combined chemical analysis and in vitro yeast screen bioassay. Estrogenic compounds 4-t-OP, 4-NP, BPA, E1, E2 and TCS were measured in the water samples, with their average concentrations of 4.7, 577.9, 46.7, 1.3, ND and 6.8 ng/L, respectively. In sediment, the average concentrations of 4-t-OP, 4-NP, BPA and TCS were 35.7, 0.5, 1.7 and 0.7 ng/g while E1 and E2 were not detected in the sediments of all selected sites. In general, the estrogenic compounds in surface water and sediment of the Yellow River were at relatively low levels, thus having medium to minimal estrogenic risks in most sites except for the site of east Lanzhou with high estrogenic risks.
[Show abstract][Hide abstract] ABSTRACT: 4-Nonylphenol (4-NP), bisphenol-A (BPA) and triclosan (TCS) are three industrial chemicals used widely in daily products. This study investigated 4-NP, BPA and TCS levels in urine samples of 287 children and students aged from 3 to 24years old in Guangzhou, China. Total (free and conjugated) amounts of 4-NP, BPA and TCS in the urine samples were detected using gas chromatography-mass spectrometry with negative chemical ionization. The detection rates of 4-NP, BPA and TCS were 100%, 100% and 93% respectively, given the detection limits of 3.8, 0.5 and 0.9ng/L respectively. Data for 4-NP, BPA and TCS were presented in both creatinine-adjusted (microgram per gram creatinine) and unadjusted (microgram per liter) urinary concentrations. The geometric mean (GM) concentrations of urinary 4-NP, BPA and TCS were 15.92μg/g creatinine (17.40μg/L), 2.75μg/g creatinine (3.00μg/L) and 3.55μg/g creatinine (3.77μg/L) respectively. Multiple regression models considering age, gender, preferred drinking bottle and log-transformed creatinine were used to calculate the adjusted least square geometric mean (LSGM). Among these subjects, the females had higher LSGM concentrations of 4-NP, BPA and TCS than the males; and the only statistically significant difference was found for the LSGM concentrations of triclosan (p=0.031). Participants who reported to use ceramic cups more frequently had significantly lower LSGM concentrations of BPA than those who used plastic cups (p=0.037). Meanwhile, a three-week test of using polycarbonate bottles and ceramic cups to drink bottled water and boiled tap-water was carried out among 12 graduate students of 25years old. The GM concentrations of urinary BPA at the end of the first week after using ceramic cups to drink bottled water were 7.16μg/g creatinine, then decreased significantly to 3.49μg/g creatinine after the second week of using ceramic cups to drink boiled tap-water (p<0.05), and finally increased to 4.15μg/g creatinine after the third week of using polycarbonate bottles in drinking boiled tap-water. The results indicate that in daily life the use of polycarbonate bottles or drinking of bottled water is likely to increase the ingestion of BPA, resulting in an increase in urinary BPA levels.
Environment international 07/2011; · 6.25 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This paper reports screening of multiple hormonal activities (estrogenic and androgenic activities, antiestrogenic and antiandrogenic activities) for surface water and sediment from the Pearl River system (Liuxi, Zhujiang, and Shijing rivers) in South China, using in vitro recombinant yeast bioassays. The detection frequencies for estrogenic and antiandrogenic activities were both 100% in surface water and 81 and 93% in sediment, respectively. The levels of estrogenic activity were 0.23 to 324 ng 17β-estradiol equivalent concentration (EEQ)/L in surface water and 0 to 101 ng EEQ/g in sediment. Antiandrogenic activities were in the range of 20.4 to 935 × 10(3) ng flutamide equivalent concentration (FEQ)/L in surface water and 0 to 154 × 10(3) ng FEQ/g in sediment. Moreover, estrogenic activity and antiandrogenic activity in sediment showed good correlation (R(2) = 0.7187), suggesting that the agonists of estrogen receptor and the antagonists of androgen receptor co-occurred in sediment. The detection frequencies for androgenic and antiestrogenic activities were 41 and 29% in surface water and 61 and 4% in sediment, respectively. The levels of androgenic activities were 0 to 45.4 ng dihydrotestosterone equivalent concentration (DEQ)/L in surface water, and the potency was very weak in the only detected sediment site. The levels of antiestrogenic activity were 0 to 1,296 × 10(3) ng tamoxifen equivalent concentration (TEQ)/L in surface water and 0 to 89.5 × 10(3) ng TEQ/g in sediment. The Shijing River displayed higher levels of hormonal activities than the Zhujiang and Liuxi rivers, indicating that the Shijing River had been suffering from heavy contamination with endocrine-disrupting chemicals. The equivalent concentrations of hormonal activities in some sites were greater than the lowest-observed-effect concentrations reported in the literature, suggesting potential adverse effects on aquatic organisms.
Environmental Toxicology and Chemistry 07/2011; 30(10):2208-15. · 2.62 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A sensitive rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS) method, combined with solid-phase extraction, ultrasonic extraction and silica gel cartridge cleanup, was developed for 28 steroids including 4 estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethynyl estradiol (EE2), diethylstilbestrol (DES)), 14 androgens (androsta-1,4-diene-3,17-dione (ADD), 17α-trenbolone, 17β-trenbolone, 4-androstene-3,17-dione, 19-nortestoserone, 17β-boldenone, 17α-boldenone, testosterone (T), epi-androsterone (EADR), methyltestosterone (MT), 4-hydroxy-androst-4-ene-17-dione (4-OHA), 5α-dihydrotestosterone (5α-DHT), androsterone (ADR), stanozolol (S)), 5 progestagens (progesterone (P), ethynyl testosterone (ET), 19-norethindrone, norgestrel, medroxyprogesterone (MP)), and 5 glucocorticoids (cortisol, cortisone, prednisone, prednisolone, dexamethasone) in surface water, wastewater and sludge samples. The recoveries of surface water, influents, effluents and sludge samples were 90.6-119.0% (except 5α-DHT was 143%), 44.0-200%, 60.7-123% and 62.6-138%, respectively. The method detection limits for the 28 analytes in surface water, influents, effluents and freeze-dried sludge samples were 0.01-0.24 ng/L, 0.02-1.44 ng/L, 0.01-0.49 ng/L and 0.08-2.06 ng/g, respectively. This method was applied in the determination of the residual steroidal hormones in two surface water of Danshui River, 12 wastewater and 8 sludge samples from two wastewater treatment plants (Meihu and Huiyang WWTPs) in Guangdong (China). Ten analytes were detected in surface water samples with concentrations ranging between 0.4 ng/L (17β-boldenone) and 55.3 ng/L (5α-DHT); twenty analytes in the wastewater samples with concentrations ranging between 0.3 ng/L (P) and 621 ng/L (5α-DHT); and 12 analytes in the sludge samples with concentrations ranging between 1.6 ng/g (E1) and 372 ng/g (EADR).
Journal of Chromatography A 03/2011; 1218(10):1367-78. · 4.61 Impact Factor