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.

Degradation of Levofloxacin by a green zero-valent iron-loaded carbon composite activating peroxydisulfate system: Reactivity, products and mechanism.

In this study, a green zero-valent iron-loaded carbon composite (ZVI-SCG) was synthesized using coffee grounds and FeCl3 solution through two-steps method, and the synthesized ZVI-SCG was used in the activation of peroxydisulfate (PDS) to degrade Levofloxacin (LEX). Results revealed that ZVI-SCG exhibited a great potential for LEX removal by adsorption and catalytic degradation in the ZVI-SCG/PDS system, and 99% of LEX was removed in the ZVI-SCG/PDS system within 60 min. ZVI-SCG/PDS system showed a high reactivity toward LEX degradation under realistic environmental conditions. Also, the ZVI-SCG/PDS system could effectively degrade several quinolone antibiotics including gatifloxacin, ciprofloxacin and LEX in single and simultaneous removal modes. A potential reaction mechanism of LEX degradation by ZVI-SCG/PDS system was proposed, SO4•-, HO•, O2•- and 1O2 involved in radical and non-radical pathways took part in catalytic degradation of LEX by ZVI-SCG/PDS system, but HO• might be the main reactive species for LEX degradation. The possible degradation pathway of LEX was also proposed based on the identified ten intermediate products, LEX degradation was successfully achieved through decarboxylation, opening ring and hydroxylation processes. The potential toxicity of LEX and its oxidation products decreased significantly after treatment. This study provides a promising strategy of water treatment for the antibiotics-containing wastewater.

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 adsorption of Cr(VI) and phenol by biochar-based iron oxide composites in water: Performance, kinetics and mechanism.

The pollution of heavy metals and organic compounds has received increased attention in recent years. In the current study, a novel biochar-based iron oxide composite (FeYBC) was successfully synthesized using pomelo peel and ferric chloride solution through one-step process at moderate temperature. Results clearly demonstrate that FeYBC exhibited more efficient removal of Cr(VI) and/or phenol compared with the pristine biochar, and the maximum adsorption amounts of Cr(VI) and phenol by FeYBC could reach 24.37 and 39.32 mg g-1, respectively. A series of characterization data suggests that several iron oxides such as Fe2O3, Fe0, FeOOH and Fe3O4 were formed on the FeYBC surface as well as oxygen-containing groups. Thermodynamics study indicates that Cr(VI) and phenol adsorption by FeYBC were endothermic and exothermic processes, respectively. Langmuir adsorption isotherm and pseudo-second order models could better explain the Cr(VI) and phenol adsorption behaviors over FeYBC. The Cr(VI) adsorption might be primarily achieved through the ion exchange and surface complexation and reduction, whereas the π-π interaction and electron donor-acceptor complex mainly contributed to phenol adsorption. The findings indicate that the biochar-based iron oxide composites material was an efficient adsorbent for the remediation of industrial effluents containing Cr(VI) and phenol.

[Distribution, Sources, and Health Risk Assessment of PAHs in Water Supply Source Regions of Guangzhou].

Trace polycyclic aromatic hydrocarbons (PAHs) in drinking water sources have significant harmful effects on human health. Water and sediment samples from water source regions of three water treatment plants in Guangzhou were collected and the distributions of 16 kinds of PAHs were analyzed. The human risk of PAHs in the water samples was also evaluated using the Risk Assessment Guidance for Superfund (RAGS) of the United States Environmental Protection Agency (USEPA). The results showed that PAHs in the samples from the three water source regions did not exceed the corresponding standard limit for water quality, and the content of ΣPAHs in suspended solids and sediments was below the medium level. The non-carcinogenic risks (HQ and HI) of PAHs in the water samples were less than 1, and the non-carcinogenic risk was negligible. In addition, Riskingest, Riskdermal, and RiskT for the waters were all in range of 5.53×10-7 to 5.34×10-6, indicating that a carcinogen risk was possible but acceptable. The results of the isomer ratio method indicated that the PAHs in the water sources of the three water plants had a mixed input of pollution, including petroleum discharge, petroleum combustion, and incomplete combustion of wood, coal, and biomass. The total organic carbon (TOC) content of the water and sediment samples was positively correlated with the accumulation and enrichment of low-ring PAHs, and there was a significant positive correlation between PAHs and similar molecules in the sediments. The ΣPAHs in the water and sediment samples were also strongly correlated.

[Distribution Characteristics and Ecological Risk Assessment of Organochlorine Pesticides in Surface Sediments of Zhelin Bay in Guangdong Province, China].

The distribution characteristics and pollution degrees of 20 organochlorine pesticides (OCPs) were investigated in surface sediments from Zhelin Bay south of China and the ecological risk of OCPs and integrated ecological risk at the samples stations in sediments were evaluated by risk quotient (RQ) and sediment quality guideline of NOAA. The possible sources of HCHs and DDTs in sediments were preliminarily studied, and the correlation between OCPs and sediment characteristic parameters was discussed. The concentrations of DDTs in surface sediments were found to be higher than those of other OCPs, especially p,p'-DDD, and the concentrations of DDTs were higher than the limited values of Chinese Marine sediment quality criteria. The total concentration of 20 OCPs in surface sediments ranged from 14.14 to 306.88 ng·g-1, with a mean concentration of 78.37 ng·g-1, and the highest total concentration was at site 8(S8). There were inevitable adverse biological effects and high ecological risk of p,p'-DDD and p,p'-DDT, high integrated ecological risk at S8 and S10. The possible sources of HCHs in surface sediments of Zhelin Bay were mainly from the application of Lindane pesticides. At S1,S2,S10,S11 there was input of DDT into mariculture area of Zhelin Bay, and at the other sites the sources of DDT were from the early residue in sediments or the long-term weathering sediments of using pesticides. There was a very significant positive correlation between HCHs, endosulfan, chlordane and dieldrin in sediments, while there was a negative relation between the above OCPs and TOC, which indicated that the presence of TOC could promote their biodegradation. There was a significant positive correlation between p, p'-DDD and Ca, which revealed that DDT used in the early period was deposited with biological carbonate. Increasing size of sediment particles discouraged the accumulation and enrichment of OCPs in sediments.

[Distribution Characteristics of Heavy Metals in Environmental Samples Around Electroplating Factories and the Health Risk Assessment].

This study aimed to investigate the pollution degree and human health risk of heavy metals in soil and air samples around electroplating factories. Soil, air and waste gas samples were collected to measure 8 heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in two electroplating factories, located in Baiyun district of Guangzhou city. Geoaccumulation index and USEPA Risk Assessment Guidance for Superfund (RAGS) were respectively carried out. Results showed that concentrations of Hg and Pb in waste gas and Cr in air samples were higher than limits of the corresponding quality standards, and concentrations of Cd, Hg and Zn in soil samples reached the moderate pollution level. The HQ and HI of exposure by heavy metals in air and soil samples were both lower than 1, indicating that there was no non-carcinogen risk. CRAs and CRCr in soil samples were beyond the maximum acceptable level of carcinogen risk (10(-4)), and the contribution rate of CRCr to TCR was over 81%. CRCr, CRNi and TCR in air samples were in range of 10(-6) - 10(-4), indicating there was possibly carcinogen risk but was acceptable risk. CR values for children were higher than adults in soils, but were higher for adults in air samples. Correlation analysis revealed that concentrations of heavy metals in soils were significantly correlated with these in waste gas samples, and PCA data showed pollution sources of Cd, Hg and Zn in soils were different from other metals.

[Adsorption behavior of exogenous thorium on soil contaminated by rare earth industries].

The adsorption behavior of exogenous thorium on soil was studied to evaluate the contaminated risk on soil. The adsorption capacity, equilibrium time, distribution coefficient and desorption ability were investigated by the experiments of static adsorption. The strong adsorption ability of exogenous thorium on soil samples was observed by high adsorption ratio (> 92%) and low desorption ratio (< 5%) in equilibrium, and the biggest distribution coefficient was over 10(4). The adsorption capacity and equilibrium time were related to soil properties. According to the results of adsorption, Freundlich equation (r > or = 0.9167) and Elovich equation (R2 > or = 0.8980) were primely fit for describing the thermodynamics and kinetics of the adsorption of exogenous thorium on soil samples, respectively, which indicated that the adsorption was belonged to the nonlinear adsorption, and was affected by the diffusion of thorium on soil surface and in mineral interbed. Sequential extraction procedure was employed to evaluate the bound fractions of exogenous thorium adsorbed on soil samples. Based on the extracted results of thorium fractions, exogenous thorium was presented in the labile nonresidual fractions (over 58%) at the low initial concentration (10(-7) - 10(-6) mol x L(-1)), and nonresidual fractions enhanced with the increase of the initial amount, meanwhile more exogenous throium was transferred to the stable residual fractions.