Hybrid wavelength selection strategy combined with ATR-FTIR spectroscopy for preliminary exploration of vintage labeling traceability of sauce-flavor baijiu.

The allure of substantial profits has perpetuated the illicit trade of counterfeit vintage labels for baijiu. While various approaches have been employed to intelligently ascertain the vintage of baijiu, many of them are both cost-intensive and time-consuming. This work pioneered the use of Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, coupled with chemometric analysis, offering a non-destructive and economically viable method for discriminating sauce-flavor baijiu across different aging periods (1-, 2-, and 3-year). In this research, principal component analysis (PCA) was first conducted to explore clustering trends among distinct vintage groups. Subsequently, the effect of spectral pre-processing on modeling performance was explored. For wavelength selection, four wavelength selection methods (ReliefF, random forest variable importance (RFVI), variable importance in projection (VIP), and Venn) were first used to identify the subset of candidate features that potentially best mapped the vintage labels. Immediately following this, to explore the possibility of further improving the identification capabilities of the model as well as to reduce the redundant data that may still be present, sequential backward selection (SBS) was utilized for secondary feature reduction within the subset of candidates. The amalgamation of these two techniques is termed a "hybrid wavelength selection strategy." Additionally, the dimensionality reduction effects of PCA and kernel principal component analysis (KPCA) were compared to demonstrate the robustness of the proposed method. Finally, classification models such as partial least squares discriminant analysis (PLS-DA), random forest (RF), and grasshopper optimization algorithm-based support vector machine (GOA-SVM) were developed. The results show that the spectral data need not be pre-processed, and the proposed hybrid wavelength selection strategy can further improve the identification ability of the model. Among the many models developed, ReliefF-SBS-GOA-SVM emerged as the most proficient classification model, yielding accuracy, sensitivity, and specificity rates of 94.44%, 95.23%, and 94.44%, respectively. This method not only holds promise for the discrimination of baijiu class attributes such as brand, origin, flavor, and vintage but also exhibits potential applicability in other non-targeted identification studies involving spectroscopy methodologies.

Toxic effects of environmentally persistent free radicals (EPFRs) on the surface of tire wear particles on freshwater biofilms: The alleviating role after sewage-incubation-aging.

The aquatic ecological risks posed by the surface-active components of tire wear particles (TWPs) are not fully understood. This study aimed to determine the acute (24 h exposure) aquatic toxicity effects of TWPs on freshwater biofilms in terms of total organic carbon (TOC), chlorophyll-a (Chl-a) abundance, quantum yield (ФM), and adenosine triphosphate (ATP). Three types of TWP were tested: TWPs produced via the typical wear of tires and roads (i.e., rolling friction (R-TWPs) and sliding friction (S-TWPs)) and cryogenically milled tire treads (C-TWPs). The results showed that the surface structural properties of the three TWPs differed significantly in morphology, bare composition, functional groups, and surface-active components (environmental persistent free radicals). The exposure of biofilms to the TWPs increased TOC and ATP at low concentrations (1 mg L-1) but inhibited them at high concentrations (50 mg L-1). All TWP types inhibited biofilm photosynthesis (reduced Chl-a and ФM) and altered the community structure of algae to varying degrees; in addition, the toxicity mechanisms of the TWPs contributed to the accumulation of reactive oxygen species and cell membrane (or cell-wall) fragmentation, leading to lactate dehydrogenase release. S-TWPs were the most toxic because their surface carried the highest environmental persistent free radicals. R-TWPs were the second most toxic, which was attributed to their smaller particle size. The toxicity of all TWPs was tested after sewage incubation aging. The results showed that the toxicity of all TWPs reduced as the sewage covered their surface components and active sites. This process also reduced the differences in toxicity among the TWPs. This study filled a research gap in our understanding of aquatic toxicity caused by the surface structural properties of tire microplastics and has implications for the study of microplastic biotoxicity mechanisms.

ATR-FTIR spectroscopy combined with chemometrics to assess the spectral markers of irradiated baijius and their potential application in irradiation dose control.

Although some methods have been proposed for the identification of irradiated baijius, they are often costly, time-consuming, and destructive. It is also unclear what instrumentation can be used to fully characterize the quality changes in irradiated baijius. To address this issue, this study pioneers the use of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy in combination with chemometrics to open up new avenues for characterizing irradiated baijius and their quality control. Principal component analysis, five spectral pre-processing methods (Savitzky-Golay smoothing (S-G), second-order derivative (SD), multiple scattering correction (MSC), S-G + SD and S-G + MSC), five wavelength selection methods (random forest variable importance (RFVI), two-dimensional correlation spectroscopy (2D-COS), variable importance in projection (VIP), ReliefF, and Venn), and three classification models (partial least squares-discriminant analysis (PLS-DA), random forest (RF), and grasshopper optimization algorithm-based support vector machine (GOA-SVM)) were integrated into the analytical framework of ATR-FTIR spectroscopy, aiming to accurately identify baijiu samples according to different irradiation doses and to search for irradiation-induced spectral difference characteristics (spectral markers). The results showed that SD was the best spectral pre-processing method, and RF models constructed using the 20 most competitive and discriminative spectral markers (selected by Venn) could achieve accurate identification of baijiu samples based on irradiation dose (0, 4, 6, and 8 kGy). After Pearson correlation analysis, the five significantly (P＜0.05) changed spectral markers (1596, 2025, 2309, 2329, and 2380 cm-1) were attributed to changes in the content of total acids, alcohols, and aromatic compounds. These findings demonstrate for the first time the potential of ATR-FTIR spectroscopy as a fast, low-cost, and non-destructive tool for the characterization and identification of irradiated baijiu samples. This approach may also offer a promising solution for labeling management of irradiated foods, vintage identification of baijius, and brand protection.

Synthesis of NaA zeolite from foundry dust and its adsorption capacity of ammonia.

Eutrophication of water bodies due to excess ammonia nitrogen (NH4+-N) is harmful to aquatic organisms and human health. In this study, foundry dust (FD) from foundry industry was used to synthesize NaA zeolite to use as an adsorbent to remove NH4+-N from wastewater. Results demonstrate that FD could be successfully synthesized to form a foundry dust-based NaA zeolite (FZA) through adjustment of the silica-alumina ratio of n (SiO2)/n (Al2O3) at 2 at 95 °C. Specific surface area, total pore volume, and cation exchange capacity (CEC), and maximum adsorption NH4+-N of FZA was respectively 43.185 cm2/g, 0.0364 cm3/g, 212.35 mmol/100 g and 37.81 mg/g, which was 4.74, 1.54, 1.52 and 1.62 times as much as the NaA zeolite (SZA). FZA with higher adsorption NH4+-N capacity was related to higher specific surface area and CEC. The NH4+-N adsorption amount of 28.57 mg/g by FZA was obtained after the fourth regeneration, which was notably higher than that of SZA (23.27 mg/g). The desorption rate of NH4+-N from FZA was 87% by the fourth regeneration. FZA effectively removed NH4+-N from swine wastewater containing 153.32 mg/L NH4+-N. Results suggest that FZA could be used as absorbent to removal NH4+-N from wastewater.

Nutrient released characteristics of struvite-biochar fertilizer produced from concentrated sludge supernatant by fluidized bed reactor.

With the exacerbating water eutrophication globally, it is important to recover nitrogen (N) and phosphorus (P) from sewage for recycle. In this study, coconut shell biochar and ethylene diamine tetraacetic acid (EDTA) were added into the designed fluidized bed reactor (FBR) to create struvite-biochar. N and P released from struvite-biochar and the recovery efficiency of N and P from concentrated sludge supernatant were analyzed. Results showed that the optimal operation condition for hydraulic retention time (HRT), pH, Mg/P molar ration, and addition amount EDTA were 90 min, 9.5, 1.2, and 0.2 g/L, respectively. The recovery efficiency of NH4+-N and PO43--P, and purity struvite for FBR were 34.41%-38.05%, 64.95-68.40%, and 84.15%, respectively. The recovery efficiency of NH4+-N and PO43--P were respectively increased by 7.23% and 5.36% when FBR with addition of 0.33 g/L coconut shell biochar, but purity struvite from struvite-biochar decreased by 45.70%. Contents of As, Cd, Pb, and Cr in struvite and struvite-biochar were all lower than Chinese Standard Limits of Fertilizer. Compared to commercial chemical fertilizer, such as superphosphate and urea, struvite-biochar and struvite have slowly released N and P. The amounts of released P, NO3--N and NH4+-N from struvite-biochar were higher than struvite during the five leaching times. Compared with struvite, the total amounts of released P, NO3--N and NH4+-N from struvite-biochar increased by 4.9%, 3.5% and 8.3%, respectively. Therefore, it is valuable to add biochar into FBR to recovery N and P from concentrated sludge supernatant and make struvite-biochar as a slow-release fertilizer.

A review on the generation, discharge, distribution, environmental behavior, and toxicity (especially to microbial aggregates) of nano-TiO2 in sewage and surface-water and related research prospects.

This article reviews the nano-effects and applications of different crystalline nano­titanium dioxide (nano-TiO2), identifies their discharge, distribution, behavior, and toxicity to aquatic organisms (focusing on microbial aggregates) in sewage and surface-water, summarizes related toxicity mechanisms, and critically proposes future perspectives. The results show that: 1) based on crystal type, application boundaries of nano-TiO2 have become clear, extending from traditional manufacturing to high-tech fields; 2) concentration of nano-TiO2 in water is as high as hundreds of thousands of µg/L (sewage) or several to dozens of µg/L (surface-water) due to direct application or indirect release; 3) water environmental behaviors of nano-TiO2 are mainly controlled by hydration conditions and particle characteristics; 4) aquatic toxicities of nano-TiO2 are closely related to their water environmental behavior, in which crystal type and tested species (such as single species and microbial aggregates) also play the key role. Going forward, the exploration of the toxicity mechanism will surely become a hot topic in the aquatic-toxicology of nano-TiO2, because most of the research so far has focused on the responses of biological indicators (such as metabolism and damage), while little is known about the stress imprint caused by the crystal structures of nano-TiO2 in water environments. Additionally, the aging of nano-TiO2 in a water environment should be heeded to because the continuously changing surface structure is bound to have a significant impact on its behavior and toxicity. Moreover, for microbial aggregates, comprehensive response analysis should be conducted in terms of the functional activity, surface features, composition structure, internal microenvironment, cellular and molecular level changes, etc., to find the key point of the interaction between nano-TiO2 and microbial aggregates, and to take mitigation or beneficial measures to deal with the aquatic-toxicity of nano-TiO2. In short, this article contributes by 1) reviewing the research status of nano-TiO2 in all aspects: application and discharge, distribution and behavior, and its aquatic toxicity; 2) suggesting the response mechanism of microbial aggregates and putting forward the toxigenic mechanism of nanomaterial structure; 3) pointing out the future research direction of nano-TiO2 in water environment.

Simultaneous adsorption of ammonia and phosphate using ferric sulfate modified carbon/zeolite composite from coal gasification slag.

Removal of nutrients in water is crucial to control eutrophication. Fly ash has been increasingly used to synthesize zeolite to remove nutrients, but it is still poorly understood about the removal capacity of zeolite synthesized from coal gasification slag (CGS), which has not been well recycled in many countries. In this study, the CGS was acid leached, alkali dissolved, and synthesized to carbon/zeolite composite (C/ZC) under induction by medical stone. After being modified by ferric sulfate, the composite was analyzed for the adsorption of NH4+ and PO43-. Results showed that the maximum adsorption capacity by C/ZC is 5.17 mg/g, but C/ZC has no adsorption capacity of PO43-. The ferric sulfate was used to modify C/ZC to obtain carbon/zeolite composite modified by iron (M-C/ZC). M-C/ZC has a higher specific surface area (348.3 m2/g), and the negatively charge of M-C/ZC can adsorb NH4+ and form Fe-O-P between PO43- and Fe-OH bonds. The maximum adsorption capacity of NH4+ and PO43- by M-C/ZC are 7.44 mg/g and 6.94 mg/g, respectively. The removal efficiency of NH4+ and PO43- are up to 88% and 99% under initial NH4+ (5 mg/L) and PO43- (10 mg/L) concentration. The regeneration capacity of M-C/ZC of NH4+ was stronger than that of PO43-. After three cycles, the regeneration rate of M-C/ZC of NH4+ was still up to 76.96%. Our findings suggest the good application potential of M-C/ZC for removing NH4+ and PO43- from wastewater.

Nutrient loss by runoff from rice-wheat rotation during the wheat season is dictated by rainfall duration.

Clarifying the properties/features of nutrient loss from farmland surface runoff is essential for the mitigation of nutrient losses. Plough pan formation underneath topsoil is a common feature of long-term paddy soils that significantly affects water movement and nutrient runoff loss, especially during the upland season of paddy-upland rotation. To characterize the nutrients that are lost from wheat fields of paddy-wheat rotation with runoff, a field experiment was conducted in a wheat field using a simulated rainfall system from November 2019 to May 2020 in Nanjing, China. The aim of this study was to investigate the temporal characteristics of nitrogen (N) and phosphorus (P) loss under different rainfall intensities (low, 30 mm h-1; middle, 60 mm h-1; high, 90 mm h-1). The results showed that the time interval from the beginning of rain to the occurrence of runoff (time to runoff, Tr) was negatively correlated with "rainfall intensity" (Ri) (P＜0.01) but unaffected by soil moisture. Different rainfall intensities had no effect on the runoff coefficient (the ratio of the runoff volume over the precipitation, 0.14-0.17). The N and P loss concentrations in the nutrient discharge followed a power-function relationship that decreased over time (P＜0.01), and the peak nutrient concentration appeared during the initial runoff period (0-5 min). The N and P loss rates were the highest during the middle-to-late discharge period (15-30 min) for all intensities. In terms of cumulative nutrient losses, the amounts of TN lost were similar for all rainfall intensities, while TP significantly increased with intensity. The results revealed that nitrate-nitrogen (NOX--N) and particulate phosphorus (PP) were the predominant forms of N and P losses. Overall, during the initial runoff period, nutrient concentration peaks, whereas the nutrient loss rate is the highest during the middle-late phase of the phenomenon.

[Relationship Between Diversity of Aquatic Plant Communities and Water Environmental Factors in Lhalu Wetland].

Plant diversity plays an important role in the integrity and stability of wetland ecosystems. Lhalu Wetland is the highest wetland in the world and is the largest urban natural swamp in China. It plays an important role in ecological balance, increasing air humidity, improving the urban climate, and purifying the water environment in Lhasa. The changes in plant diversity in different areas of the Lhalu Wetland and its relationship with water environmental factors were analyzed via field investigation, field monitoring, and indoor analysis. Results showed that 18 species of aquatic plants were found in the Lhalu Wetland. The Margalef species richness index was in the order M (Middle west) > W (West) > E (East) > N (North) > S (South). Index of species richness ranked of W (11), M (11) > N (8) > E (7) > S (6). Index of ShannonWiener followed that of M (1.9) > W (1.89) > S (1.63) > E (1.26) > N(1.18). Index of Simpson ranked of N (0.44) > E (0.34) > M (0.24) > S (0.21) > W (0.18). The order of Pielou index was that of S (0.91) > M(0.79) > W(0.78) > E(0.65) > N(0.56). Redundancy analysis showed that the diversity of aquatic plants in the Lhalu Wetland was affected by dissolved oxygen, pH, water temperature, total nitrogen, and turbidity. The dominant species in the Lhalu Wetland are CeratopHyllum demersum L., Hippuris vulgaris, Polygonum hydropiper, Softstem bulrush, Acorus calamus, and Juncus effusus, which show a trend of non-pollution-resistant species succession to pollution-resistant species.

Responses of nitrogen transformation and dissolved oxygen in constructed wetland to biochar and earthworm amendment.

Many constructed wetland systems are facing the problem of low dissolved oxygen (DO) and reduced nitrogen removal efficiency. In this study, an experimental constructed wetland system is designed and used to investigate the effect of biochar (rice husk biochar (RHB), coconut shell biochar (CSB), and wood biochar (WB) and earthworm on DO concentration, nitrogen transformation, and ammonia nitrogen removal. Specifically, effects of different biochar and earthworm on NH4+-N in wastewater, N content of Phragmites australis, NH4+-N and NO3--N content in substrates, microbial nitrification and denitrification potentials, and the DO concentration were investigated. Results show that the addition of biochar and earthworm increased the removal efficiency of NH4+-N from wastewater. The addition of RHB and WB significantly increased the concentration of DO by 21.4% and 25.7% (P < 0.05) respectively in the constructed wetland. The addition of earthworm significantly increased the DO concentration in the constructed wetland system by an average of 30.35% (P < 0.05).The N content of P. australis increased when biochar and earthworm were introduced into the constructed wetland system, with higher relative N content observed in the above-ground biomass. NO3--N content increased, but NH4+-N decreased in the substrate. Addition of both biochar and earthworm increased nitrification and denitrification potentials. However, no significant increase in denitrification potential was observed when only biochar was added. The removal efficiency of NH4+-N from wastewater is significantly positively correlated with the DO, nitrification, and denitrification potential, and nitrogen content of above-ground part of P. australis (P < 0.05). Results suggest that the DO concentration in constructed wetland systems could be improved by the addition of biochar and earthworm. These findings imply that both biochar and earthworm could be added into constructed wetlands to solve the low DO concentration and improve the removal efficiency of nitrogen.

Effect of pyrolysis temperature on characteristics of biochars derived from different feedstocks: A case study on ammonium adsorption capacity.

Physiochemical properties of biochars derived from different feedstock materials (rice straw, Phragmites communis, sawdust and egg shell) at different pyrolysis temperatures were analyzed, and adsorption capacities of ammonium (NH4+) on the biochars were investigated. The results show a clear effect of pyrolysis temperature on physicochemical properties of the biochars, including specific surface area, pH, and zeta potential. Consequently, biochars derived from the studied feedstocks at the selected temperatures exhibited different capacities to absorb NH4+. Highest NH4+ adsorption capacities were associated with biochars of rice straw (4.2 mg/g) and sawdust (3.3 mg/g) produced at 500 °C; at 300 °C observed NH4+ adsorption capacity was lower and highest figures were derived from the biochars of Phragmites communis (3.2 mg/g) and egg shell (2.2 mg/g). For all feedstocks, biochars produced at 700 °C showed the lowest NH4+ adsorption capacity. Our results suggest that zeta potential and C/H ratio, rather than surface area, are the most important factors in determining NH4+ sorption potential of biochars.

Phosphorus sorption capacity of biochars from different waste woods and bamboo.

Four biochars were made via pyrolysis at 500 °C using different waste plant materials, including tree branches from Cinnamonum campora (L.) Pres (CCP), Eriobotrya japonica (Thunb.) Lindl (EJL), Rohdea roth (RR) and bamboo shoots (Phyllostachys sulphurea) (PS). Phosphorus sorption capacities of the biochars were studied by isothermal experiments on their sorption kinetics. Results show that P sorption to the three wood biochars (CCP, EJL, and RR) fitted well with Lagergren pseudo second order model. However, P release was found in the PS biochar and sand amended with the PS biochar treatments during the isothermal sorption experiment. Phosphorus sorption capacity of the CCP biochar, EJL biochar and RR biochar was 4,762.0, 2, 439.0 and 1, 639.3 mg/kg, respectively. The CCP biochar showed the highest P sorption capacity due to its higher pH, lower dissolved P content, larger surface area (23.067 m2/g) and pore volume (0.058 cm3/g). The PS biochar showed the lowest P sorption due to its higher dissolved P content, more carboxyl groups, and smaller surface area (2.982 m2/g) and pore volume (0.017 cm3/g). Results suggest that the CCP biochar could be a potential alternative adsorbent for P sorption, such as removing P in wastewater treatment by constructed wetlands.

Tuning density of Si nanoparticles on graphene sheets in graphene-Si aerogels for stable lithium ion batteries.

Silicon is one of the most promising candidates for anodes of lithium ion batteries attributed to the highest theoretical specific capacity (4200 mAh/g). However, the conductivity and structural integrity during the lithiation-delithiation process are very poor, which seriously affect the actual electrochemical performance. To address these issues, we introduce graphene framework as both structural skeletons and conductive networks for silicon in this work. Through a facile freeze-drying approach, Si nanoparticles are successfully anchored on graphene sheets uniformly, and graphene form strong and conductive framework, which serves as mechanical support, electrical network, and buffer layer for Si, highly improving the structural integrity and conductivity. The electrochemical examinations indicate that the synthesized graphene-Si aerogels can deliver 104% specific capacity retention after cycled for 195 times at 0.8 A/g. Multi-walled carbon nanotubes are utilized to improve the rate property, and the resulting anode exhibits average specific capacities of 1415, 1209, 1057, 888, 781, and 646 mAh/g at charge/discharge rates of 0.05 C, 0.18 C, 0.2 C, 0.5 C, 1 C, and 2 C, respectively. Benefit from the facile synthesis and excellent cycling stability, it is expected that graphene-Si aerogels may play an important role in lithium ion battery.

[Effect of Biochar on Root Morphological Characteristics of Wetland Plants and Purification Capacity of Constructed Wetland].

A constructed wetland with Acorus calamus L. was built. Straw biochar, reed biochar, and sawdust biochar was added into the constructed wetland individually to study the effect of different biochars on the root morphology, dissolved oxygen, and purification ability of the constructed wetland. The results show that the total root length, total projection area, total volume, total surface area, root number, branch number, and root dry weight of Acorus calamus L. significantly increased when all three kinds of biochar were added into the constructed wetland (P<0.05). Similarly, adding the biochars into the constructed wetland also significantly increased dissolved oxygen content in the wetland (P<0.05). Addition of sawdust biochar into the constructed wetland increased the root length, projection area, surface area, total volume, number of root tips, number of branches, and root dry weight of Acorus calamus L. by 96.1%, 106.2%, 185.6%, 172.5%, 75.3%, 121.6%, and 84.9%, respectively. After adding biochars into the constructed wetland, the root morphology of Acorus calamus L. and dissolved oxygen content was significantly correlated with removal rate of TN, TP, and COD, respectively. Addition of sawdust biochar into the constructed wetland significantly increased the removal rates of total nitrogen, total phosphorus, and COD when the hydraulic load was 0.022 m3·(m2·d)-1 (P<0.05). These results suggested that the addition of sawdust biochar to the constructed wetland increased the root growth of Acorus calamus L. and enhanced dissolved oxygen content, resulting in purification capacity of the constructed wetland.

Contamination and Risk Assessment of Estrogens in Livestock Manure: A Case Study in Jiangsu Province, China.

This study investigated the occurrence and contamination risk of estrogens in livestock manure in Jiangsu Province, China. Four estrogens-estriol (E3), 17ß-estradiol (17ß-E2), bisphenol A (BPA), and 17α-ethinyloestradiol (EE2)-were detected in livestock manure from hens, ducks, swine, and cows. The respective mean concentrations of each estrogen found in these manures were 289.8, 334.1, 330.3, and 33.7 µg/kg for E3; 38.6, 10.9, 52.9, and 38.8 µg/kg for 17ß-E2; 63.6, 48.7, 51.9, and 11.7 µg/kg for BPA; and 14.3, 11.3, 25.1, and 21.8 µg/kg for EE2. Estrogens were most frequently detected at high concentrations in the manure of finishing pigs, followed by the manure of growing pigs and piglets. Estrogens can be partially degraded after banking up for seven days; yet, great quantities of estrogens remain in livestock manure. The total estradiol equivalent quantity (EEQt) estimated to be present in aquatic environments but originating from livestock waste was 10.5 ng/L, which was greater than the hazard baseline value (1 ng/L) and also higher than the proposed lowest observable effect concentration (10 ng/L) of E2 in aquatic environments. The results of our study demonstrate that livestock waste is an important source of estrogens, which may potentially affect the hormonal metabolism of aquatic organisms.

Using Fenton Oxidation to Simultaneously Remove Different Estrogens from Cow Manure.

The presence of estrogens in livestock excrement has raised concerns about their potential negative influence on animals and the overall food cycle. This is the first investigation to simultaneously remove estrogens, including estriol (E3), bisphenol A (BPA), diethylstilbestrol (DES), estradiol (E2), and ethinyl estradiol (EE2), from cow manure using a Fenton oxidation technique. Based on the residual concentrations and removal efficiency of estrogens, the Fenton oxidation reaction conditions were optimized as follows: a H2O2 dosage of 2.56 mmol/g, a Fe(II) to H2O2 molar ratio of 0.125 M/M, a solid to water mass ratio of 2 g/mL, an initial pH of 3, and a reaction time of 24 h. Under these conditions, the simultaneous removal efficiencies of E3, BPA, DES, E2, and EE2, with initial concentrations in cow manure of 97.40, 96.54, 100.22, 95.01, and 72.49 mg/kg, were 84.9%, 99.5%, 99.1%, 97.8%, and 84.5%, respectively. We clarified the possible Fenton oxidation reaction mechanisms that governed the degradation of estrogens. We concluded that Fenton oxidation technique could be effective for efficient removal of estrogens in livestock excrement. Results are of great importance for cow manure reuse in agricultural management, and can be used to reduce the threat of environmental estrogens to human health and ecological safety.

Physicochemical properties and ecotoxicological effects of yttrium oxide nanoparticles in aquatic media: Role of low molecular weight natural organic acids.

Understanding how engineered nanoparticles (ENPs) interact with natural organic acids is important to ecological risk assessment of ENPs, but this interaction remains poorly studied. Here, we investigate the dispersion stability, ion release, and toxicity of yttrium oxide nanoparticles (nY2O3) suspensions after exposure to two low molecular weight natural organic acids (LOAs), namely benzoic acid and gallic acid. We find that in the presence of LOAs the nY2O3 suspensions become more stable with surface zeta potential more positive or negative, accompanied by small agglomerated size. LOA interaction with nY2O3 is shown to promote the release of dissolved yttrium from the nanoparticles, depending on the concentrations of LOAs. Toxic effects of the nY2O3 suspensions incubated with LOAs on Scenedesmus obliquus as a function of their mixture levels show three types of signs: stimulation, inhibition, and alleviation. The mechanism of the effects of LOAs on the nY2O3 toxicity may be mainly associated with the degree of agglomeration, particle-induced oxidative stress, and dissolved yttrium. Our results stressed the importance of LOA impacts on the fate and toxicity of ENPs in the aquatic environment.

Impacts of low-molecular-weight organic acids on aquatic behavior of graphene nanoplatelets and their induced algal toxicity and antioxidant capacity.

Knowledge of the interaction between graphene-based materials and low-molecular-weight organic acids (LOAs) is essential to understand fate and effects of graphene-based materials in the aquatic environment, but this interaction remains poorly elucidated. In this study, the effects of LOAs on the physicochemical properties of graphene nanoplatelets (GNPs) in an aqueous medium and on the GNP toxicity to algae were studied. The unicellular green alga Scenedesmus obliquus was exposed to GNP suspensions in the presence of benzoic acid or gallic acid at various concentrations. The GNPs had smaller hydrodynamic sizes and the GNP suspensions were more stable and had higher or lower surface zeta potentials in the presence of LOAs than when LOAs were not present. The toxic effects in S. obliquus cultures incubated with GNP suspensions containing LOAs were related to the LOA concentration, and the presence of LOAs caused three effects: stimulation, alleviation, and synergistic inhibition. The intensities of the effects mainly correlated with the LOA concentration, the extent of agglomeration, and particle-induced oxidative stress. The results indicate that the environmental fates and toxicities of GNPs are strongly affected by the binding of GNPs to LOAs.

Purifying capability, enzyme activity, and nitrification potentials in December in integrated vertical flow constructed wetland with earthworms and different substrates.

The response of purifying capability, enzyme activity, nitrification potentials, and total number of bacteria in the rhizosphere in December to wetland plants, substrates, and earthworms was investigated in integrated vertical flow constructed wetlands (IVFCW). The removal efficiency of total nitrogen (TN), NH4-N, chemical oxygen demand (COD), and total phosphorus (TP) was increased when earthworms were added into IVFCW. A significantly average removal efficiency of N in IVFCW that employed river sand as substrate and in IVFCW that employed a mixture of river sand and Qing sand as substrate was not found. However, the average removal efficiency of P was higher in IVFCW with a mixture of river sand and Qing sand as substrate than in IVFCW with river sand as substrate. Invertase activity in December was higher in IVFCW that used a mixture of river sand and Qing sand as substrate than in IVFCW which used only river sand as substrate. However, urease activity, nitrification potential, and total number of bacteria in December was higher in IVFCW that employed river sand as substrate than in IVFCW with a mixture of river sand and Qing sand as substrate. The addition of earthworms into the integrated vertical flow constructed wetland increased the above-ground biomass, enzyme activity (catalase, urease, and invertase), nitrification potentials, and total number of bacteria in December. The above-ground biomass of wetland plants was significantly positively correlated with urease and nitrification potentials (p < 0.01). The addition of earthworms into IVFCW increased enzyme activity and nitrification potentials in December, which resulted in improving purifying capability.

The forms and bioavailability of phosphorus in integrated vertical flow constructed wetland with earthworms and different substrates.

A sequential extraction method was utilized to analyze seven forms of P in an integrated vertical-flow constructed wetland (IVFCW) containing earthworms and different substrates. The aluminum-bound P (Al-P) content was found to be lower, and the occluded P (Oc-P) content was higher in the IVFCW. The addition of earthworms into the influent chamber of IVFCW increased the exchange P (Ex-P), iron-bound P (Fe-P), calcium bound P (Ca-P), Oc-P, detritus-bound (De-P) and organic P (Org-P) content in the influent chamber, and also enhanced P content uptake by wetland plants. A significantly positive correlation between P content of above-ground wetland plants and the Ex-P, Fe-P, Oc-P and Org-P content in the rhizosphere was found (P<0.05), which indicated that the Ex-P, Fe-P, Oc-P and Org-P could be bio-available P. The Ex-P, Fe-P, De-P, Oc-P and Ca-P content of the influent chamber was higher where the substrate contained a mixture of Qing sand and river sand rather than only river sand. Also the IVFCW with earthworms and both Qing sand and river sand had a higher removal efficiency of P, which was related to higher P content uptake by wetland plants and P retained in IVFCW. These findings suggest that addition of earthworms in IVFCW increases the bioavailable P content, resulting in enhanced P content uptake by wetland plants.