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.

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.

Occurrence, removal and risk evaluation of ibuprofen and acetaminophen in municipal wastewater treatment plants: A critical review.

Ibuprofen and acetaminophen as two anti-fever agents have been widely used in human. Due to lack of full understanding, this work firstly summarized their occurrence and fate in municipal wastewater treatment plants (WWTPs) across 30 countries. The respective influent concentrations of ibuprofen and acetaminophen were not detected (ND)-39,830,000 and ND-66440000 ng/L, while their corresponding respective effluent concentrations were ND-58710 and ND-90500 ng/L. The removal efficiencies of ibuprofen and acetaminophen in municipal WWTPs were 6.5-100 % and 14.3-100 % with respective average removal efficiencies of 87.6 % and 94.7 %. There have been many batch studies on ibuprofen biodegradation with kbio values available, while such investigation for acetaminophen was very limited. The theoretically calculated removal efficiency of ibuprofen with kbio agreed well with that of the observed average removal efficiency of on-site investigations on full-scale WWTP, which was quite different from natural estrogens and some other emerging contaminants. One possible reason is that conjugated ibuprofen could be easily cleaved and the cleavage step gives little effect on the biodegradation of ibuprofen. Due to extremely high concentrations of ibuprofen and acetaminophen in influent of municipal WWTP, their concentration levels in effluent likely high enough to pose adverse effects on some aquatic organisms. To protect water environment, advanced treatment is necessary to further remove residue ibuprofen and acetaminophen in the effluent. To the best of our knowledge, this is the systematical summarization on the occurrence and fate of ibuprofen and acetaminophen in municipal WWTP as well as their potential effect on aquatic organisms, which addressed known knowledge and unknowns to be further investigated.

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.