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.

Deconjugation potentials of natural estrogen conjugates in sewage and wastewater treatment plant: New insights from model prediction and on-site investigations.

Natural estrogen conjugates play important roles in municipal wastewater treatment plant (WWTP), but their deconjugation potentials are poorly understood. This work is the first to investigate the relationships between the enzyme activities of arylsulfatase/ß-glucuronidase and deconjugation potentials of natural estrogen conjugates. This work led to three important findings. First, the enzyme activity of ß-glucuronidase in sewage is far higher than that of arylsulfatase, while their corresponding activities in activated sludge were similar. Second, a model based on ß-glucuronidase could successfully predict the deconjugation potentials of natural estrogen glucuronide conjugates in sewage. Third, the enzyme activity of arylsulfatase in sewage was too low to lead to evident deconjugation of sulfate conjugates, which means that the deconjugation rate of estrogen sulfates can be regarded as zero. By comparing their theoretical removal based on enzyme activity and on-site investigation, it is reasonable to conclude that reverse deconjugation of estrogen conjugates (i.e., conjugation of natural estrogens to form conjugated estrogens) likely exist in WWTP, which explains well why natural estrogen conjugates cannot be effectively removed in WWTP. Meanwhile, this work provides new insights how to improve the removal performance of WWTP on natural estrogen conjugates. SYNOPSIS: This work is the first to show how arylsulfatase/ß-glucuronidase could affect deconjugation of natural estrogen conjugates and possible way to enhance their removal in wastewater treatment plant.

Simultaneous determination of twelve natural estrogens in dairy milk using liquid-liquid extraction and solid-phase extraction coupled with gas chromatography-mass spectrometry.

There have been many analytical methods for natural estrogens in commercial dairy milk samples, but in most of which, only four major estrogens (estrone (E1), 17ß-estradiol (E2), estriol (E3), and 17α-estradiol (αE2)) were included. This work developed an effective GC-MS analytical method for simultaneous analysis of twelve natural estrogens in commercial dairy milk sample, in which eight far-less well-known natural estrogens (2-hydroxyestone (2OHE1), 4-hydroxyestrone (4OHE1), 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 16-epiestriol (16epiE3), 16α-hydroxyestrone (16αOHE1), 16-ketoestradiol (16ketoE2) and 17epiestriol (17epiE3)) were included besides the four major natural estrogens. With liquid-liquid extraction and solid phase extraction, twelve natural estrogens in commercial dairy milk could be effectively extracted. The established method showed good linearity (R2 > 0.9991), low limits of detections (LODs, 0.02-0.11 ng/g), as well as excellent recoveries (64-117%) with satisfactory low relative standard deviations (RSDs, 0.8-14.7%). This established method was applied to seven commercial dairy milk samples, and all the twelve natural estrogens were frequently detected except for 4OHE2 without detection in any sample. Our results showed that the concentration contribution ratios of the eight far-less well-known natural estrogens in commercial dairy milk samples contributed to 32-83%, while the corresponding contribution ratios based on estrogen equivalence (EEQ) were 21-62%. This work highlighted the high abundance of the eight far-less well-known natural estrogens in commercial dairy milk based on both concentration and EEQ, which has been neglected for a long time.

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.

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.

Trace determination of fifteen free amino acids in drinking source water via solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

Amino acids (AAs) are important nitrogen-containing organics in water, and a large number of reports have proven that they were the precursors of many nitrogen-containing disinfection by-products, some of which have cytotoxicity and carcinogenicity. However, little has been done on their occurrence in drinking source water. Therefore, a trace determination method via solid-phase extraction coupled with ultra-high pressure liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for 15 free AAs (FAAs) was developed, which was successfully applied for drinking source water samples. For sample preparation, strong cation-exchange stationary solid-phase extraction (SPE) cartridge showed better extraction performance to that of reverse phase stationary oasis HLB SPE cartridge. The optimal water pH was determined to be 2.8 before extraction. Strong matrix effects for most FAAs were observed in this work; thus, sample extraction with SPE was recommended to eliminate the matrix effects. The developed method showed excellent linearity (R2 > 0.991), low limits of detection (LODs, 0.01-0.27 nmol/L), and good recoveries of 69.8-117.9% in drinking source water with low relative standard deviations (RSDs, 0.3-13.2%). The developed method was finally applied to eight drinking source water samples, and the top five FAAs were found to be serine, glycine, leucine, alanine, and isoleucine.

Property of arylsulfatase and ß-glucuronidase extracted from digestive tracts of Cipangopaludina chinensis and their cleavage performance on conjugated natural estrogens.

Arylsulfatase and ß-glucuronidase are the two substantial enzymes having a significant role in the cleavage of conjugated natural estrogens (C-NEs). The present study reports that arylsulfatase and ß-glucuronidase have been abundantly found in the digestive tracts of Cipangopaludina chinensis; in which, their corresponding activities were 60 and 5 U/g wet waste, respectively. The arylsulfatase from Cipangopaludina chinensis could show high activity at low temperatures. Hence, its activity still remained at 53.2% of maximal activity even at an extremely low temperature of 4 ℃; while the corresponding activities of arylsulfatase from Helix pomatia or activated sludge were less than 20% and 10%, respectively. The arylsulfatase and ß-glucuronidase from Cipangopaludina chinensis could efficiently cleave C-NEs suggesting that they could be alternative enzymes derived from Helix pomatia that are used for cleavage of conjugated compounds in environmental or biological sample analysis. Meanwhile, they might also be used to enhance the cleavage of C-NEs in municipal wastewater.

Twelve natural estrogens in urines of six threatened or endangered mammalian species in Zoo Park: implications and their potential risk.

This work was the first to report twelve natural estrogens (NEs) in the urines of six threatened or endangered mammalians in a Zoo Park of Guangzhou (i.e., panda, gorilla, elephant, African lion, jaguar, and leopard). Ten out of twelve NEs were detected at least in one urine sample of the six mammalians studied, including the four major NEs (i.e., estrone (E1), 17ß-estradiol (E2), 17α-estradiol (αE2), estriol (E3)), and six other NEs (i.e., 4-hydroxyestrone (4OHE1), 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 16α-hydroxyestrone (16α-OHE1), 16ketoestradiol (16ketoE2), and 17epiestriol (17epiE3)). The six studied mammalians, ranked in the order of high to low urinary concentration of total NEs, were jaguar, African lion, gorilla, elephant, panda, and leopard, with respective urinary concentrations of 110.4, 86.4, 71.4, 66.0, 55.9, and 52.8 ng/mL. According to the average urinary concentration of NE in the six mammalians ranked from high to low, the top five NEs detected were 16α-OHE1, 4OHE1, E1, E3, and 17epiE3, respectively. These clearly indicated the occurrence of NEs other than the four major types in urines of animals in a Zoo Park. Moreover, the daily excretion rates of the five detected NEs by one elephant ranged from 1162-2254 µg/d with a total daily excretion rate of 8260 µg/d, suggesting that the total urinary excretion of NEs by one adult elephant was equivalent to that by 170 premenopausal women or 506 adult men. Consequently, it appears from this study that NEs in the urines of zoo animals should be considered an emerging source of NEs.

17α-Estradiol, an ignored endogenous natural estrogen in human: Updated estrogen metabolism pathways and its environmental risk analysis.

E1 and E2 are considered as the parent natural estrogens (NEs) in human metabolism pathways of NEs, while the enantiomer of E2, αE2 was not included and ignored. In this study, αE2 along with the other eleven NEs with estrogenic activities were found in six healthy human urines with the total concentration levels of 62.9-99.3 µg/L. The concentration contributed ratios (CCRs) of αE2 to the total twelve NEs ranged from 4.7% to 11.0% with an average CCR of 7.0%. On the basis of the average CCR, αE2 was 1.5 times that of E2, which suggested that αE2 was one important NE in humans. As the main source of NEs in municipal wastewater was derived from human urine, αE2 should also be an important NE in municipal wastewater that can be proven by previous limited studies, in which the municipal effluent concentrations of αE2 ranged from not detection to 144.2 ng/L with an average concentration of 11.9 ng/L, indicating αE2 in municipal effluent was an important source to the natural environment. Although αE2 is a NE with weak estrogenic potency, the estrogenic effect of αE2 via municipal effluent to its receiving water body cannot be ignored because it can be bio-transformed into E2 under aerobic environment. This work is the first to indicate that αE2 is an ignored NE in human and its environmental risk via municipal effluent discharging cannot be ignored, which should be paid with attention.

Sulfite may disrupt estrogen homeostasis in human via inhibition of steroid arylsulfatase.

Steroid arylsulfatase is an important enzyme in human, which plays an important role in dynamic equilibrium of natural estrogens. On the other hand, sulfite can be endogenously produced as a consequence of human body's metabolism of sulfur-containing amino acids, while its main sources to human are mainly derived from food as it is a widely used additive. Sulfite-sensitivity is a well-known phenomenon to a small proportion of populations. However, its potential adverse effects on healthy individuals have been hardly reported. It was for the first time reported in this study that sulfite could effectively inhibit arylsulfatase, and its IC50 values for the snail- and human urine-derived arylsulfatase were determined to be 71.9 and 142.8 µM, which were lower than the concentration of sulfite in some healthy population. Consequently, it appears that sulfite might disrupt estrogen homeostasis in human, and this deserves further investigation.

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.

Chlorogenic acid and ß-glucan from highland barley grain ameliorate ß-cell dysfunction via inhibiting apoptosis and improving cell proliferation.

Recent studies have reported that highland barley as a whole grain diet has anti-hyperglycemic effects, however little information is available about the active compounds that ameliorate pancreatic ß-cell dysfunction and the related mechanisms. In this study, chlorogenic acid (CA) and ß-glucan (BG) were identified as the active compounds that ameliorated ß-cell dysfunction. CA ameliorated ß-cell dysfunction by inhibiting cell apoptosis and improving glucose-stimulated insulin secretion via targeting G protein-coupled receptor 40 (GPR40) and regulating the phospholipase C ß (PLCß) pathway. BG ameliorated ß-cell dysfunction by improving cell proliferation via targeting mammalian target of rapamycin (mTOR) and regulating the protein kinase B (Akt)/glycogen synthase kinase-3ß (GSK-3ß) pathway. Furthermore, CA and BG improved ß-cell sensitivity and pancreatic insulin secretion, and inhibited ß-cell apoptosis in impaired glucose tolerance (IGT) mice. Notably, CA restored homeostasis model assessment (HOMA)-ß values and Ca2+-ATP and K+-ATP levels back to normal levels, and BG at 300 mg per kg BW restored ß-cell insulin contents back to normal levels in IGT mice. Additionally, the combination of CA and BG had an additive effect on ameliorating ß-cell dysfunction. These results help develop whole highland barley grain as a functional food for preventing type 2 diabetes by ameliorating pancreatic ß-cell damage.

Procyanidin B1 and p-Coumaric Acid from Highland Barley Grain Showed Synergistic Effect on Modulating Glucose Metabolism via IRS-1/PI3K/Akt Pathway.

INTRODUCTION: Phenolic extract in highland barley grain has showed hypoglycemic effect, while little information is available about the active compounds and whether there exist additive or synergistic effect on modulating glucose metabolism. METHODS AND RESULTS: Procyanidin B1 (PB) and p-coumaric acid (CA) are the active compounds in highland barley grain and show synergistic effect on improving glucose uptake and glycogen synthesis by upregulating glucose transporter (GLUT4) and downregulating glycogen synthase kinase-3ß (GSK-3ß) protein expression, respectively. The mechanism may be attributed to target insulin receptor (IRß) and regulate insulin receptor substrate-1 (IRS-1)/phosphatidylinositol 3-kinase (PI3K)/ protein kinase B (Akt) pathway. Furthermore, PB + CA exhibits synergistic effect on restoring glucose intolerance and insulin resistance, and improving hepatic glycogen synthesis in impaired glucose tolerance (IGT) mice. The postprandial blood glucose (PBG), homeostasis model assessment (HOMA)-IR values and serum insulin contents in PB + CA-treated IGT mice with dosage of 300 mg kg-1 BW are reversed to normal levels. Additionally, PC + CA shows additive effect on inhibiting gluconeogenesis in vitro and in vivo. CONCLUSION: PB + CA in highland barley grain synergistically modulate glucose metabolism. These results may provide evidence of whole highland barley grain diet achieve superior effect on restoring IGT than isolated components.

A review of 17α-ethynylestradiol (EE2) in surface water across 32 countries: Sources, concentrations, and potential estrogenic effects.

17α-ethynylestradiol (EE2) is a synthetic estrogen with very strong estrogenic potency. Due to its wide usage in human and livestock as well as its high recalcitration to biodegradation, it was ubiquitous in different environment. This review summarized EE2 concentration levels in surface waters among 32 countries across seven continents. EE2 concentrations varied greatly in different surface waters, which ranged from not detected to 17,112 ng/L. The top 10 countries ranked in the order of high to low average EE2 concentration in surface water, were Vietnam, Cambodia, China, Laos, Brazil, Argentina, Kuwait, Thailand, Indonesia and Portugal, with the respective mean concentrations of 27.7, 22.1, 21.5, 21.1, 13.6, 9.6, 9.5, 8.8, 7.6 and 6.6 ng/L. Generally speaking, the EE2 concentration levels in surface waters in developing countries were much higher than those in developed countries. EE2 in effluent of municipal wastewater treatment plant (WWTP) was the dominant source to most countries, which suggested that improving the EE2 removal performance of municipal WWTP is the key to mitigate EE2 contamination to surface water body. Livestock, hospital, pharmacy factory and aquaculture wastewaters were also the important sources, but further work should be performed to elucidate their contribution. Evaluation based on estrogenic effects, the EE2-derived estrogen equivalence in surface waters ranged from 0 to 33 ng E2/L, among which about 65% of surface waters among 32 countries were at risk or high risk, indicating global serious EE2 contamination. MAIN FINDING: EE2 concentration in surface waters across 32 countries were summarized, along which its potential estrogenic effects were evaluated.

Trace determination of eleven natural estrogens and insights from their occurrence in a municipal wastewater treatment plant and river water.

As endocrine disruptors, natural estrogens including estrone (E1), 17ß-estradiol (E2), and estriol (E3) in wastewaters of municipal wastewater treatment plant (WWTP) as well as other environmental matrix have been widely studied. However, the far-less studied natural estrogens such as 2-hydroxyestrone (2OHE1), 16α-hydroxyestrone (16α-OHE1), 4-hydroxyestrone (4OHE1), etc., found in human urine have been almost ignored. Therefore, it is important to investigate the occurrence of these far-less studied natural estrogens in municipal WWTP and other environment. In this study, a GC-MS analytical method was firstly established and validated for trace determination of eleven natural estrogens in waste and surface waters, including E1, E2, E3, 2OHE1, 16α-OHE1, 4OHE1, 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 17-epiestriol (17epiE3), 16-epiestriol (16epiE3), and 16keto-estradiol (16ketoE2). All the eleven natural estrogens were detected in the influent of one municipal WWTP, which ranged from 7.9 to 62.9 ng/L. The top five natural estrogens in the influent were E1, E3, 16α-OHE1, 16ketoE2, and 2OHE1 with respective concentrations of 62.9, 62.6, 46.9, 32.7, and 28.8 ng/L. Most of them were detected in both the effluent and river water, in which their detected concentrations were n.d-14.7 and n.d-51.7 ng/L, respectively. This work is the first to indicate that the so far less commonly studied natural estrogens in the environment likely pose adverse health effect on humans and wildlife due to their relative strong estrogenic potencies and high levels in wastewater and river water. More work should be done to understand their removals in municipal WWTPs and their occurrence in surface waters.

Bisphenol analogues in Chinese bottled water: Quantification and potential risk analysis.

Polycarbonate (PC) and polyethylene terephthalate (PET) as the package materials have been widely used for Chinese bottled water, from which estrogenic bisphenol analogues might migrate into bottled water. Therefore, there is a strong need to investigate the occurrence and potential risk of such estrogenic bisphenol analogues in Chinese bottled waters. In this study, a GC-MS method was first established and validated for determination of trace-level ten kinds of bisphenol analogues, including bisphenol A (BPA), bisphenol B (BPB), bisphenol C (BPC), bisphenol E (BPE), bisphenol F (BPF), bisphenol P (BPP), bisphenol S (BPS), bisphenol Z (BPZ), bisphenol AP (BPAP), and bisphenol AF (BPAF). BPA was detected in all eleven brands of PET bottled waters with concentrations of 12.4-44.9 ng/L. Some bisphenol analogues were detected in PET bottled waters, and the average concentrations of BPA, BPE, and BPAF in PET bottled waters were found to be 20.8, 1.8, and 2.2 ng/L, respectively. The other eight bisphenol analogues were not detected in PET bottled waters. On the other hand, BPA was detected with high concentrations of 111.8 to 6452.8 ng/L in ten brands of PC bottled water. The average concentrations of BPA, BPS, BPAP, and BPAF were determined to be 1394.3, 1.9, 1.4 and 1.0 ng/L, respectively, while the other seven bisphenol analogues were not detected. High BPA concentration detected in PC bottled waters would remarkably increase human BPA daily intake through daily consumption of such bottled waters. Meanwhile, high estrogen equivalence (EEQ) in PC bottled waters of China is mainly due to the presence of BPA, which may imply adverse effect on human. Therefore, further investigation should be dedicated to assess PC bottled water-associated BPA risks in a more holistic manner.

Global review of phthalates in edible oil: An emerging and nonnegligible exposure source to human.

This work investigated the presence of seven major phthalates in nine different kinds of edible oils (i.e. olive, rapeseed, peanut, sesame, tea seed, corn, soybean, sunflower, and blended oil) and their potential impacts on human. The respective total average phthalates concentrations in the oils studied were found to be 6.01, 2.79, 2.63, 2.03, 1.73, 1.66, 1.57, 1.26, and 0.72 mg/kg. On the other hand, the seven main phthalates in the edible oils with the average concentration ranked from high to low were in order of DiNP, DEHP, DiDP, DBP, DiBP, DEP, and BBP, with 0.90, 0.81, 0.79, 0.71, 0.22, 0.17, and 0.10 mg/kg, respectively. The estimated maximum human daily intakes (EDI) of DEHP, DBP, DiBP, DiNP, BBP, DEP, and DiDP via edible oils were determined to be 552, 2996, 121, 356, 268, 66, and 563 µg/p/d, respectively. It was further revealed that the maximum human EDI of DEHP, DBP, BBP, and DiBP through consumption of edible oils were 2.92, 6.79, 1.24, and 1.06 times higher than those via bottled water. The calculated average estrogenic equivalence (EEQ) values of the seven major phthalates in edible oils fell into the range of 2.7-958.1 ng E2/L, which were 45-396 times of those in bottled water. With published works, the complete distributions of 15 phthalates in nine kinds of edible oils were established and assessed for the health risks based on EDI and EEQ. This work provided the first evidence that edible oil is a potential source of phthalates, thus the potential adverse estrogenic effects on human health should need to be assessed in a holistic manner.

Synergistic effects and related bioactive mechanisms of Potentilla fruticosa Linn. leaves combined with green tea polyphenols studied with microbial test system (MTS).

Previous research found Potentilla fruticosa leaf extracts (PFE) combined with green tea polyphenols (GTP) showed obvious synergistic effects based on chemical mechanisms. This study further confirmed the synergy of PFE + GTP viewed from bioactivities using the microbial test system (MTS). The MTS antioxidant activity results showed the combination of PFE + GTP exhibited synergistic effect and the ratio 3:1 showed the strongest synergy, which were in accordance with the results in H2O2 production rate. The combination of PFE + GTP promoted CAT and SOD enzyme activity and their gene expression especially at the ratio 3:1. Therefore, the synergism of PFE + GTP may be due to the promotion of CAT and SOD genes expression which enhanced the CAT and SOD enzyme activities. These results confirmed the synergy of PFE + GTP and could provide theoretical basis to produce a compounded tea made of a mixture of leaves from Potentilla species.