Combined collection systems of sewage and rainfall runoff seriously affect the spatial distributions of natural estrogens and their conjugates in river water: Insights from the Pearl River of China.

So far, little has been known about how the combined collection systems of sewage and rainfall runoff (CCSs) affect emerging contaminants in river water. To fill up the knowledge gap, this study was conducted to investigate the spatial distributions of three natural estrogens (NEs, i.e., estrone (E1), 17ß-estradiol (E2) and estriol (E3)) and their conjugates (C-NEs) in the Pearl River in the wet and dry seasons. Results showed that the respective average concentrations of NEs and C-NEs at different locations alongside the Pearl River in the wet season were 7.3 and 1.8 times those in the dry season. Based on estrogen equivalence (EEQ), the average estimated EEQ level in the Pearl River waters in the wet season was nearly 10 times that in the dry season. These seemed to imply that the CCSs in the wet season not only cause untreated sewage into the receiving water body, but greatly decrease the removal efficiency of NEs and C-NEs in wastewater treatment plant. Furthermore, the estimated annual loads of E1, E2, and E3 to the Pearl River in the wet season accounted for about 88.6 %, 100 %, and 99.3 % of the total annual loads. Consequently, this work for the first time demonstrated that the CCSs in cities with high precipitation are unfavorable for controlling of emerging contaminants.

Analysis and contamination levels of ten phthalic acid esters (PAEs) in Chinese commercial bubble tea: a comparison with commercial milk.

Phthalic acid ester (PAE) contamination in popular drink bubble tea has been hardly studied in the world. In this work, a liquid-liquid extraction following solid phase extraction (LLE-SPE)-UPLC-MS/MS method was first established for trace determination of ten PAEs in bubble tea. The developed method was validated with respect to linearity (R2 > 0.992), low limit of detections (LODs, 0.49-3.16 µg/L), and satisfactory recoveries (61.8-127.6%) with a low relative standard derivations (RSDs, 1.1-16.4%), which was also validated for commercial milk. Six out of ten PAEs, i.e., diethylhexyl phthalate (DEHP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), diethyl phthalate (DEP), dihexyl phthalate (DHP), and diphenyl phthalate (DPP) were detected in Chinese bubble tea with concentrations ranging from not detection (ND) to 53.43 µg/L, while DEHP, DBP, DIBP, DEP, and dimethyl phthalate (DMP) were detected in commercial milk with concentrations ranging from ND to 110.58 µg/L. The respective average concentrations of DEHP in Chinese bubble tea and commercial milk were 19.40 and 23.46 µg/L, which were over two times that in drinking water quality standards of several countries including Israel, Korea, Oman, and Singapore (i.e., 8 µg/L). Calculated with human estimated daily intake (EDI), the average EDIs of five out of seven PAEs in bubble tea were higher than those in commercial milk. For example, the calculated EDI of DIBP in bubble tea was 5 times that in commercial milk, while their respective corresponding EDIs of DBP and DEHP were over 2.4 and 1.6 times. Based on estrogen equivalence (EEQ) with the unit of ng E2/L, the average EEQs of the ten PAEs in Chinese bubble tea and commercial milk were 14.26 and 17.06 ng E2/L, which were 52.8 and 62.3 times the observed effect concentration that could cause egg mortality of zebrafish. It is evident that the potential estrogenic effect of PAEs in bubble tea and commercial milk cannot be negligible. Given the fact that PAE contamination in bubble tea has been hardly investigated, such study is urgently to be performed in a global view.

Twelve natural estrogens and ten bisphenol analogues in eight drinking water treatment plants: Analytical method, their occurrence and risk evaluation.

Bisphenol analogues (BPs) and natural estrogens (NEs) as two important groups of endocrine-disrupting compounds (EDCs) in drinking water treatment plants (DWTPs) have been hardly investigated except bisphenol A (BPA) and three major NEs including estrone (E1), 17ß-estradiol (E2) and estriol (E3). In this study, a GC-MS analytical method was firstly established and validated for trace simultaneous determination of ten BPs and twelve NEs in drinking water, which included BPA, bisphenol B (BPB), bisphenol C (BPC), bisphenol E (BPE), bsiphenol F (BPF), bsiphenol P (BPP), bisphenol S (BPS), bisphenol Z (BPZ), bisphenol AF (BPAF), bisphenol AP (BPAP), E1, E2, E3, 17α-estradiol (17α-E2), 2-hydroestrone (2OHE1), 16hydroxyestrone (16α-OHE1), 4-hydroestrone (4OHE1), 2-hydroxyesstradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 17-epiestriol (17epiE3), 16-epiestriol (16epiE3) and 16keto-estraiol (16ketoE2). This investigation showed that eighteen out of twenty-two targeted compounds were detected in drinking source waters of eight DWTPs with concentrations ranging from not detected to 142.8 ng/L. Although the conventional treatment process of DWTP could efficiently remove both BPs and NEs with respective removal efficiencies of 74.1%-90.9% and 74.5%-100%, BPA, BPS, BPE, BPZ, E1, 2OHE1, and 2OHE2 were found in the finished drinking waters. Chlorination could remove part of BPs and NEs, but the efficiency varied greatly with DWTP and the reason was unknown. In the finished drinking waters of eight DWTPs, the highest chemically calculated estrogen equivalence (EEQ) derived from BPs and NEs was up to 6.11 ngE2/L, which was over 22 times that could do harm to zebrafish, indicating a potential risk to human health. Given the fact that many chlorination products of BPs and NEs likely have higher estrogenic activities, the estrogenic effect of BPs and NEs in finished drinking water should be accurately examined urgently with the inclusion of BPs, NEs as well as their main chlorinated by-products. This study shed new light on the occurrence, removal, and potential estrogenic effects of BPs and NEs in DWTPs.

Ten bisphenol analogues in Chinese fresh dairy milk: high contribution ratios of conjugated form, importance of enzyme hydrolysis and risk evaluation.

This study investigated concentration levels of ten bisphenols (BPs) in 13 Chinese commercial fresh low temperature dairy milk samples (fresh milk) of main local and national brands with or without enzyme hydrolysis. The results showed that at least two BPs were detected in each fresh milk sample without enzyme hydrolysis and the respective mean concentrations of bisphenol AF (BPAF), bisphenol B (BPB), bisphenol C (BPC), bisphenol F (BPF), bisphenol A (BPA), bisphenol S (BPS), bisphenol AP (BPAP), bisphenol PP (BPP), bisphenol Z (BPZ), and bisphenol E (BPE) were 0.73, 0.61, 1.86, 0.87, 0.42, 0.11, 1.06, 1.42, 1.5, and 0.04 ng/mL, while their respective detection frequencies ranged from 23.1-92.3%. These results indicated the frequent detection of BPs in fresh milk samples. With enzyme hydrolysis, the respective mean concentrations of BPAF, BPA, BPB, BPC, BPF, BPS, and BPAP were increased 7.1-107.1%, indicating the long-ignored importance of enzyme hydrolysis. The respective average estimated daily intakes (EDIs) of BPA by adult and children in China via fresh milk were 32.5 and 37.5 ng/kg bw/d, indicating that BPA in fresh milk was a crucial source to human. Six out of nine other BPs had higher average EDIs than that of BPA, among which the EDI of BPAP was almost three times that of BPA, suggesting the widespread contamination of other BPs in Chinese fresh milk.

Simultaneous trace determination of three natural estrogens and their sulfate and glucuronide conjugates in municipal waste and river water samples with UPLC-MS/MS.

Analytical method for three natural estrogens (NEs) and their sulfate and glucuronide conjugates in waste and river waters using solid-phase extraction (SPE) coupled with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) has been available, but problems including poor recovery exist. In order to solve these, some optimizations have been performed in this work. For sample preparation, both rinse and elution solutions were optimized, in which 6 mL of MeOH/water (1:9, v/v), MeOH/Ace/water (10:2:88, v/v/v), and MeOH/NH4OH/water (10:2:88, v/v/v) were determined as the rinse solution, while 6 mL of 2.0% NH4OH/MeOH was determined as the elution solution for conjugated NEs (C-NEs). For mobile phase, addition of NH4F could obviously enhance the signal response of the nine target compounds, and the optimized addition concentration was 0.5 mmol/L. The developed efficient method was validated and showed excellent linearity for each target compound (R2 > 0.998), low limit of quantifications (LOQs, 0.07-1.29 ng/L) in four different water matrices, and excellent recovery efficiencies of 81.0-116.1% in influent, effluent, ultra-pure, and river water samples with low relative standard deviations (RSDs, 0.6-13.6%). The optimized method was successfully applied to influent, effluent, and Pearl River water, among which three NEs were all detected, while five C-NEs were found in the influent, three C-NEs were detected in the effluent, and two C-NEs were found in the Pearl River water, indicating the wide distribution of NEs and C-NEs in different water environments. This work provided a reliable and efficient analytical method for simultaneous trace determination of NEs and C-NEs, which had satisfactory absolute recoveries with low RSDs, low LOQs, and time-saving for both analysis and nitrogen drying.

Twelve natural estrogens in urines of swine and cattle: Concentration profiles and importance of eight less-studied.

Although four major natural estrogens (i.e., estrone (E1), 17ß-estradiol (E2), estriol (E3) and 17α-estradiol (αE2)) have been commonly found in livestock urine, this study reports the occurrence of eight other less-studied natural estrogens in urine of swine and cattle, i.e. 2-hydroxyestone (2OHE1), 4-hydroxyestrone (4OHE1), 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 16-epiestriol (16epiE3), 16α-hydroxyestrone (16αE1), 16-ketoestradiol (16ketoE2), and 17epiestriol (17epiE3). Results showed that each estrogen was found in at least one urine sample, and 6 of 8 the less-studied estrogens were present at frequencies of ≥90% in boars, ≥70% in sows, and ≥50% in dairy cattle. Five of eight the less-studied estrogens were present at frequencies of ≥33.3% in four beef cattle and one bull. On a concentration basis, the 8 less-studied natural estrogens represented 73.2%, 85.2%, 39.9%, 47.7%, 26.9%, 56.0% and 44.1% of total concentrations of the twelve natural estrogens when combining data from all animals. Similar results were observed based on estrogen equivalence, which indicated these newly detected eight less-studied natural estrogens were not negligible. This work is the first to figure out the importance of these less-studied natural estrogens in livestock urine, and their potential environmental risks associated with discharge of livestock wastewater should be urgently assessed in a holistic manner.

Stability properties of natural estrogen conjugates in different aqueous samples at room temperature and tips for sample storage.

It is important to keep natural estrogen conjugates (C-NEs) intact in aqueous environmental sample before sample preparation; otherwise, this may influence the accurate determination of NEs. Therefore, this work thoroughly investigated the stability of C-NEs in three different aqueous environmental samples under four different storage conditions, room temperature, low temperature of 4 °C, low pH of 3, and addition of HgCl2 at 2 g/L. Results showed that C-NEs in aqueous sample were easily deconjugated under low temperature of 4 °C, which has been widely used in sample collection and storage. Both the low pH of 3 and addition of HgCl2 at 2 g/L under room temperature could keep C-NEs intact in domestic wastewaters and river water within 36 h, but the latter could keep C-NEs stable longer. This work is the first to show that low pH of 3 alone could keep C-NEs intact, which suggested that the combined condition at low temperature of 4 °C that has been widely used could be omitted. Meanwhile, compared to pH adjustment, addition of 2 g/L HgCl2 into aqueous sample is more convenient and practical for 24-h composite sampling, which may be widely applied.

17α-ethynylestradiol and its two main conjugates in seven municipal wastewater treatment plants: Analytical method, their occurrence, removal and risk evaluation.

This work shows the existence of both 17-ethinylestradiol-3-sulfate (EE2-3S) and 17-ethinylestradiol-3-glucuronide (EE2-3G) in seven municipal WWTPs with substantial concentrations (n.d-50.10 ng/L). The calculated removal efficiencies of 17-ethinylestradiol (EE2) in the seven municipal WWTPs ranged from 40.8%-100% with an average removal efficiency of 83.3%. However, upon the inclusion of EE2 concentration transformed from EE2-3S and EE2-3G, the corresponding removal efficiencies were increased to 91.4%-100% with an average removal efficiency of 97.3%. This work is the first to clearly illustrate that EE2 conjugates in raw wastewater could greatly underestimate the removal effectiveness of municipal WWTPs on EE2, indicating the importance of the EE2 conjugates in municipal wastewater having been hardly paid with attention. The EE2-derived estrogen equivalence (EEQ) values in the effluents of seven WWTPs ranged from 0 to 0.98 ng E2/L having an average level of 0.45 ng E2/L, which were relatively low. However, upon the inclusion of EE2 transformable from EE2-3S and EE2-3G in effluents, the EE2-derived EEQ values in effluents would be increased to 0.77-4.85 ng E2/L having an average level of 2.71 ng E2/L, which clearly suggested that ignorance of EE2 conjugates in effluent would largely underestimate EE2's environmental risk to receiving water bodies.

Veterinary antibiotics in swine and cattle wastewaters of China and the United States: Features and differences.

Veterinary antibiotics (VAs) have been widely used in livestock for disease prevention, treatment, and growth promotion. This study compared top 20 VAs in Chinese and US swine and cattle wastewater with published literatures. The sulfonamides (SAs) were found to be predominant, accounting for 62% of the top 20 VAs in Chinese swine wastewater, while tetracyclines (TCs) contributed to about 68.7% of the 18 VAs in US swine wastewater. The average concentration of the 20 major VAs in Chinese swine wastewater was estimated to be 1145 µg/L against 253.6 µg/L in the United States. On the other hand, the five major VAs in Chinese cattle wastewater were identified to be oxytetracycline, nafcillin, apramycin, lincomycin, and amikacin, while monensin was found to be dominant in US cattle wastewater. The average concentration of the top 20 VAs in Chinese and US cattle wastewaters were found to be 54.6 and 46.2 µg/L, respectively. These analyses suggested that VAs were probably over-used in Chinese swine industry, eventually causing the development and spreading of antibiotic resistant-bacteria and genes, which should be paid with attention. PRACTITIONER POINTS: Major veterinary antibiotics (VAs) in swine and cattle wastewater were identified. Top 20 VAs in swine and cattle wastewater of China and the United States were compared. VAs concentration in Chinese swine wastewater was 4.52 times that in the United States. VAs concentration in Chinese cattle wastewater was 1.18 times that of the United States.

[Investigation on health workforce in county anti-schistosomiasis institutions of Jiangxi Province, 2010].

OBJECTIVE: To understand and assess changes of health workforce in county anti-schistosomiasis institutions of Jiangxi Province, so as to provide the evidence for improving the health workforce construction. METHODS: The status of health workforce of county anti-schistosomiasis institutions was surveyed with self-designed questionnaire, and the results were compared with the baseline survey results in 2007. RESULTS: The total number of employees was 1 384 in 2010 with the decrease of 71 persons compared with that in 2007. The average number of people per institution was 40.71, with the decrease of 0.86 per institution, compared with that of 2007. Compared with 2007, the employees with bachelor degree increased by 6.17%, those with college degree increased by 6.8%, and the attending rate of training and further study also increased. CONCLUSIONS: The health workforce has improved in county anti-schistosomiasis institutions of Jiangxi Province. The professional workers should be trained continually to improve their diathesis.