Hierarchical health risk assessment and influence factors of an ecological post-restoration oil shale mining area based on metal bioavailability.

The environmental problems caused by mining are continuous and multifaceted, in order to help manage and plan restored mining areas, the bioavailability of metals is an effective tool for measuring the potential risks to human health. This study analyzes the geochemical fractions of eight metals (As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn) to compare their bioavailability and establishes a Hierarchical health risk (HHR) model to assess the human health risks of the mine area after restoration. The results indicated that children have the highest non-carcinogenic risks exposed through ingestion (HI-ingestion) due to their special behaviors; HI-dermal may be enriched in the body; and HI-inhalation is lowest, as it is related to soil particle size. Affected by local economic development, environmental climate, soil type, and mining, the carcinogenic risk of exposure through the skin (CR-dermal) for adults significantly exceeds the acceptable safety level (ASL). The spatial distribution shows that the harm of mining to human health is a continuous process. There was still a significant CR for adults after remediation, and the HI of tailings exposure was more serious. The Classification and Regression Tree (CART) model of metal bioavailability was developed by integrating the extrinsic and intrinsic factors of metals to explore the effects of different factors on metal bioavailability and predict. The results showed that the bioavailability of metals was a dynamic process that combined land use, the distance to traffic roads, physicochemical properties of soil, and geochemical fractions of metal, and that it affects human health both directly and indirectly. Due to the fragility and sensitivity of the ecosystem after the mining area is restored, it may face greater environmental health risks.

Integrated ecological risk assessment of heavy metals in an oil shale mining area after restoration.

Although the mining area has been restored, the environmental problems caused by years of large-scale oil shale mining are still continuing, coupled with the intensive distribution of the surrounding petrochemical industry, posing a serious threat to the local ecological environment. In this study, we investigated eight heavy metals (Cu, Ni, Pb, Cd, As, Cr, Mn and Zn) contamination and distribution around mining area, evaluated the potential risks of environment, identified the main sources of metal pollution and performed source apportionment. The results showed that the original north and south dumps were seriously polluted, and the CF values were significantly higher than other sampling sites. Ni, Zn and Mn have high coefficients of variation, which may be greatly affected by human factors and especially the waste slag piled up. The concentration of heavy metals in the water was lower than in the soil; soil particles, pH, Eh and acid mine drainage influence the variation of heavy metal concentrations. As and Cd have very high RAC values, and accordingly they were mainly present in the exchangeable and reduced fractions. Mn was exposed to higher ecological risks, followed by Pb, although there were high loads on carbonate bound and oxidizable fractions. APCS-MLL receptor model was used to identify and apportionment three main sources of contamination. The mean contribution rates of industrial activity, atmospheric deposition and mixed sources accounted for 39.77%, 22.24% and 37.99%, respectively. Cluster analysis further classified the metal pollution sources according to the spatial distance of sampling points.

Effect of nitrate on the phototreatment of Triton X-100 simulated washing waste containing 4,4'-dibromodiphenyl ether: Kinetics, products and toxicity assessment.

This study aimed to investigate the effects of nitrate on the ultraviolet (UV) treatment of simulated washing wastes containing Trion X-100 (TX-100) surfactant and 4,4'-dibromodiphenyl ether (BDE-15) pollutant. The presence of nitrate accelerated the photodegradation of BDE-15 and TX-100, because they reacted with reactive oxygen species (ROS) produced from conversion between nitrate and nitrite. Due to nitrite having a stronger radical quenching property than nitrate, nitrite hindered TX-100 decay while the photodegradation rate of BDE-15 was similar to that in the presence of nitrate. This indicated that nitrate/nitrite affected BDE-15 photodegradation by photosensitization and TX-100 loss by ROS attack. An increased TX-100 concentration increased the loss of total inorganic nitrogen possibly owing to an increase in organic nitrogen formation through TX-100 nitration reactions. At pH < 7 HOONO rapidly isomerized to NO3-, and at pH = 7-9 it homolyzed to ONOO-, which increased OH production to decay the BDE-15 and TX-100 and also increased NO2- formation. BDE-15 mainly underwent debromination, and some rearrangement, ring formation, nitration and hydroxylation products were detected, indicating that the produced OH and NO2 attacked the BDE-15 and products. Furthermore, broken-chain, carboxylation, hydroxylation and nitro products were detected by Liquid chromatography high resolution mass spectrometry (LC-HRMS). Escherichia coli was used to assess the toxicity of washing waste containing nitrate: the presence of nitrate will increase the wastes' toxicity during UV treatment. Therefore, the presence of nitrate is deleterious to the UV treatment of washing wastes, and it is important to remove nitrates and nitrites from washing waste before UV irradiation.

Ecological risk assessment of trace metals and comprehensive contamination indicators in the coastal waters of Macao, South China Sea.

Few systematic and scientific assessments have been conducted on marine environmental quality in the coastal waters of Macao, a major city in the Pearl River Delta, China. In this study, we investigated the spatial distribution of trace metals (TMs) and comprehensive contamination indicators of marine water in Macao and evaluated their ecological risks. The total amount of typical TMs (∑TMs) in surface water ranged from 2.71 µg/L to 201 µg/L. ∑TMs (Hg, As, and Cd) in sediments ranged from 0.34 mg/kg to 54.8 mg/kg. TM contamination in surface water was influenced by spatial position and tidal current direction. The spatial distribution and correlation analysis of TMs and comprehensive contamination indicators were assessed, and ecological risk assessment indicated that the surface water and sediments in coastal waters of Macao are of relatively good quality, although high sulfide levels could be detected in surface water.

Degradation mechanism, intermediates and toxicology assessment of tris-(2-chloroisopropyl) phosphate using ultraviolet activated hydrogen peroxide.

Organophosphate flame retardants (OPFRs), one kind of emerging flame retardants, have received prevalent attention owing to their ubiquity in aquatic matrices and their characteristics of being refractory to biodegradation. In current research, the degradation mechanism of tris-(2-chloroisopropyl) phosphate (TCPP), one of OPFRs, and its toxicological evaluation using UV-driven hydroxyl radical oxidation were investigated. A pseudo-first order reaction was fitted with an apparent rate constant (Kobs) of 0.1328 min-1 on transformation of TCPP in the case of CH2O2 0.1 mM, pH 6.6-7.1 and 4.7 mW cm-2 UV irradiation. High resolution mass spectroscopy analyses identified nine degradation products (eg., C6H13Cl2O4P (m/z 251.0002), C9H17Cl2O5P (m/z 307.0266), C9H17Cl2O6P (m/z 323.0217), C9H18Cl3O5P (m/z 343.0033)) during transformation of TCPP. The removal efficiency dropped by inhibitory effect of natural organic matters and anions, implying that the complete mineralization of TCPP may be difficult in actual water treatment process. The toxicity assessment has shown an decrease in reactive oxygen species (ROS) and apoptosis, membrane potential (MP) elevation of Escherichia coli, and biological molecular function revision (eg., metabolism and DNA biosynthesis), indicating that toxicity of degradation products were conspicuously decreased in comparison with intact TCPP. To sum up, effective detoxification of TCPP can be realized by a UV driving radical-based oxidation, which will provide an alternative safe treatment method to control TCPP in water matrix.

Oxidation degradation of tris-(2-chloroisopropyl) phosphate by ultraviolet driven sulfate radical: Mechanisms and toxicology assessment of degradation intermediates using flow cytometry analyses.

Organophosphate flame retardants (OPFRs) were frequently detected in biotic and abiotic matrix owing to their persistence and recalcitrant degradation. Some specific OPFRs, such as tris-(2-chloroisopropyl) phosphate (TCPP), pose a significant potential risk to human health due to their high water solubility. Therefore, an environmentally sound and high efficient technique is in urgent need of controlling TCPP. This research is focused on degrading TCPP using ultraviolet-persulfate (UV/PS) technique. The degradation reaction of TCPP followed a pseudo-first order kinetics with an apparent rate constant (kobs) at 0.1653 min-1. As the photocatalytic reaction proceeded, TCPP was transformed to twelve degradation intermediates via the selective electron-transfer reactions induced by activated sulfate radical. Anions existence and pH value significantly inhibited the degradation efficiency, implying that it was hard for TCPP to reach up to complete mineralization in actual water treatment process. Additionally, toxicological assessment of degradation intermediate mixture was conducted using Flow cytometry (FCM) analyses, and the result showed that the intracellular reactive oxygen species (ROS) and cell apoptotic rates significantly declined, and membrane potential (MP) increased in comparison with original TCPP. On the other hand, the negative impacts of these degradation products on DNA biosynthesis in Escherichia coli were weakened based on cell cycle analysis, all of which indicated that toxicity of these degradation intermediates was obviously reduced via UV/PS treatment. To summarize, an appropriate mineralization is effective for TCPP detoxification, suggesting the feasibility of TCPP control using UV/PS treatment in water matrix.

Biodegradation of decabromodiphenyl ether (BDE-209) using a novel microbial consortium GY1: Cells viability, pathway, toxicity assessment, and microbial function prediction.

GY1, a novel microbial consortium with efficient ability to degrade decabromodiphenyl ether (BDE-209) has been isolated and the sequencing analysis has been conducted. The results revealed that Hyphomicrobium, Pseudomonas, Aminobacter, Sphingopyxis, Chryseobacterium, Bacillus, Pseudaminobacter, Stenotrophomonas, Sphingobacterium and Microbacterium were the dominant genera, and the function genes involved in BDE-209 conversion were predicted by PICRUSt. When BDE-209 concentration increased from 0.5 to 10mg/L, its degradation efficiency declined from 57.2% to 22.3%. Various kinds of debrominated metabolites were detected during the biodegradation process, including BDE-208, BDE-207, BDE-206, BDE-205, BDE-190, BDE-181, BDE-155, BDE-154, BDE-99, BDE-47, BDE-17 and BDE-7. Also, the proportion of necrotic cells was observed during GY1 mediated degradation of BDE-209 to reveal the changes of cells viability under BDE-209 stress. Subsequent analysis showed that the reaction of BDE-209 with GY1 was a detoxification process and bioaugmentation with GY1 effectively enhanced BDE-209 degradation in actual water and water-sediment system.

Estimated human excretion rates of natural estrogens calculated from their concentrations in raw municipal wastewater and its application.

Natural estrogens are important endocrine disrupting compounds (EDCs), which may pose adverse effects on our environment. To avoid time-consuming sample preparation and chemical analysis, estimation of their concentrations in municipal wastewater based on their human urine/feces excretion rates has been generally adopted. However, the data of excretion rates available are very limited and show significant difference among countries. In the context of increasing reporting on the concentrations of natural estrogens in municipal wastewater around the world, this study presented a simple method to estimate their human excretion rates based on the concentrations of natural estrogens in raw sewage. The estimated human excretion rates of natural estrogens among ten countries were obtained, which totally covered over 33 million population. Among these, Brazilians had the largest excretion rates with estrone (E1) and 17ß-estradiol (E2) as 236.9 and 60 µg/day/P, respectively, while Iran had the lowest value of 2 µg/day/P for E1 and 0.5 µg/day/P for E2. The average estimated human excretion rates of E1, E2, and estriol (E3) are 17.3, 6.4, and 39.7 µg/day/P, respectively. When the estimated human excretion rates obtained were applied for prediction, the predicted results showed better accuracies than those based on human urinary/feces excretion rates. The method in this study is simple, cost-effective and time-saving, which may be widely applied.

Do we underestimate the concentration of estriol in raw municipal wastewater?

The main source of natural estrogens to municipal wastewater is human excretions via urine or feces, thus their concentrations in raw wastewater should show positive linear relationship with their human excretions. This study mainly focused on their concentration relationship in raw wastewater. Based on comparison between chemical analyses and predictions through human excretion rates, the observed concentrations of estriol (E 3) in municipal wastewater were found to be noticeably lower than the predicted values. The main cause for the disparity is that substantial conjugated E 3 also exists in raw wastewater. This work suggested that monitoring both E 3 and its conjugates is necessary to get more accurate E 3 removal performance of wastewater treatment plants (WWTPs).