Natural mineral and industrial solid waste-based adsorbent for perfluorooctanoic acid and perfluorooctane sulfonate removal from surface water: Advances and prospects.

PER: and polyfluorinated alkyl substances, especially perfluorooctanoic acid and perfluorooctane sulfonic acid (PFOX), have attracted considerable attention lately because of their widespread occurrence in aquatic environment and potential biological toxicity to animals and human beings. The development of economical, efficient, and engineerable adsorbents for removing PFOX in water has become one of the research focuses. This review summarized the recent progress on natural mineral and industrial solid based adsorbent (NM&ISW-A) and removal mechanisms concerning PFOX onto NM&ISW-A, as well as proposed the current challenges and future perspectives of using NM&ISW-A for PFOX removal in water. Kaolinite and montmorillonite are usually used as model clay minerals for PFOX removal, and have been proved to adsorb PFOX by ligand exchange and electrostatic attraction. Fe-based minerals, such as goethite, magnetite, and hematite, have better PFOX adsorption capacity than clay minerals. The adsorbent prepared from industrial solid waste by high temperature roasting has great potential application prospects. Fabricating nanomaterials, amination modification, surfactant modification, fluorination modification, developing versatile composites, and designing special porous structure are beneficial to improve the adsorption performance of PFOX onto NM&ISW-A by enhancing the specific surface area, positive charge, and hydrophobicity. Electrostatic interaction, hydrophobic interaction, hydrogen bond, ligand and ion exchange, and self-aggregation (formation of micelle or hemimicelle) are the main adsorption mechanisms of PFOX by NM&ISW-A. Among them, electrostatic and hydrophobic interactions play a considerable role in the removal of PFOX by NM&ISW-A. Therefore, NM&ISW-A with electrostatic functionalities and considerable hydrophobic segments enables rapid, efficient, and high-capacity removal of PFOX. The future directions of NM&ISW-A for PFOX removal include the preparation and regeneration of engineerable NM&ISW-A, the development of coupling technology for PFOX removal based on NM&ISW-A, the in-depth research on adsorption mechanism of PFOX by NM&ISW-A, as well as the development of NM&ISW-A for PFOX alternatives removal. This review paper would be helpful the comprehensive understanding of NM&ISW-A potential for PFOX removal and the PFOX removal mechanisms, and identifies the gaps for future research and development.

Intertwined role of mechanism identification by DFT-XAFS and engineering considerations in the evolution of P adsorbents.

Adsorption method exhibits promising potential in effectively removal of phosphate from wastewater, yet it faces tremendous challenges in practical application. Limited comprehension of adsorption mechanisms and the lack of evaluation method for scaling up application are the two main obstacles. To fully realize the practical application of P adsorbents, we reviewed advanced tools, including density functional theory (DFT) and/or X-ray absorption fine structure (XAFS) to elucidate mechanisms, underscored the significance of thermodynamics and kinetics in engineering design, and proposed strategies for regenerating and reusing P adsorbents. Specifically, we delved into the utilization of DFT and XAFS to gain insights into adsorption mechanisms, focusing on active site verification and molecular interaction configurations. Additionally, we explored precise calculation methods for adsorption thermodynamics and adsorption kinetics, encompassing thermodynamic equilibrium constants, reactor selection, and the regeneration, recovery, and disposal of P adsorbents. Our comprehensive review aims to serve as a guiding light in advancing the development of highly efficient P adsorbents for engineering applications.

Modelling the dynamic gas/particle partitioning process of semi-volatile organic compounds emitted from point sources: Quantitative analysis and impact assessment.

The deleterious impact of pollution point sources on the surrounding environment and human has long been a focal point of environmental research. When considering the local atmospheric dispersion of semi-volatile organic compounds (SVOCs) around the emission sites, it is essential to account the dynamic process for the gas/particle (G/P) partitioning, which involves the transition from an initial state to a steady state. In this study, we have developed a model that enables the prediction of the dynamic process for G/P partitioning of SVOCs, particularly considering the influence from emission. It is important to note that the dynamic processes of the concentrations of SVOCs in particle phase (CP) and in gas phase (CG) differ significantly. These differences arise due to the influence of two critical factors: particulate proportion of SVOCs in the emissions (ϕ0) and octanol-air partitioning coefficient (KOA). The validity of our model was assessed by comparing its predictions of the extremum value of the G/P partitioning quotient (KP) with the results obtained from the steady-state model. Remarkably, the characteristic time (tC), used to evaluate the timescale required for SVOCs to reach steady state, demonstrated different variations with KOA for CP and CG. Additionally, the values of tC were quite different for CP and CG, which were markedly influenced by ϕ0. For some SVOCs with high KOA values, it took approximately 35 h to reach steady state. Furthermore, it was found that the time to achieve 95 % of steady state (t95 ≈ 3tC) could reach approximately 105 h. This duration is sufficient for chemicals to disperse from their emission site to the surrounding areas. Therefore, it is crucial to consider the dynamic process of G/P partitioning in local atmospheric transport studies. Moreover, the influence of ϕ0 should be incorporated into future investigations examining the dynamic process of G/P partitioning.

Efficient low-concentration phosphate removal from sub-healthy surface water by adsorbent prepared based on functional complementary strategy.

The remediation of low-concentration phosphorus polluted surface water (LP-SW) is one of most challenging environmental issues worldwide. Adsorption is more suitable for LP-SW remediation due to its low cost and operability. Based on the strategy of functional complementation among industrial solid wastes (ISWs), ISW-based phosphate absorbent material (PAM) was prepared from coal ash (CA, binder), rich­calcium (Ca) carbide slag (CS, active component) and iron salt (functional reagent) by optimizing materials ratios and roasting conditions. PAM prepared under optimal conditions (Fe/CC-2opt) had good phosphate adsorption efficiency. Notably, Fe/CC-2opt not only ensured that the effluent met Environmental Quality Standards for Surface Water (pH = 6.0-9.0), but also facilitated the formation of brushite instead of hydroxyapatite due to FeSO4 addition. Compared with hydroxyapatite, brushite had greater potential application value as fertilizer due to its solubility and high P/Ca ratio. The possible mechanisms of phosphate adsorption by PAM included surface precipitation, surface complexation, electrostatic adsorption and release of Ca2+/OH-. Preparation cost of PAM was 80 US$/ton, and treatment cost was 0.07 US$/g P. Regeneration efficiency of PAM was still above 80 % after five cycles. The design idea and result of this study provide theoretical basis and technical support for the preparation of PAM with low cost, commercial production and great adsorption capacity.

Environmental behaviors of emerging contaminants in freshwater ecosystem dominated by submerged plants: A review.

Persistent exposure of emerging contaminants (ECs) in freshwater ecosystem has initiated intense global concerns. Freshwater ecosystem dominated by submerged plants (SP-FES) has been widely constructed to control eutrophic water. However, the environmental behaviors (e.g. migration, transformation, and degradation) of ECs in SP-FES have rarely been concerned and summarized. This review briefly introduced the sources of ECs, the pathways of ECs entering into SP-FES, and the constituent elements of SP-FES. And then the environmental behaviors of dissolved ECs and refractory solid ECs in SP-FES were comprehensively summarized, and the feasibility of removing ECs from SP-FES was critically evaluated. Finally, the challenges and perspectives on the future development for ECs removal from SP-FES were prospected, giving possible research gaps and key directions. This review will provide theoretical and technical support for the effective removal of ECs in freshwater ecosystem, especially in SP-FES.

Ecotoxic side-effects of allelochemicals on submerged plant and its associated microfloras effectively relieved by sustained-release microspheres.

Harmful algae bloom caused by water eutrophication is a burning question worldwide. Allelochemicals sustained-release microspheres (ACs-SMs) exhibited remarkable inhibition effect on algae, however, few studies have focused on the ecotoxic side-effects of ACs-SMs on submerged plant and its associated microfloras. Herein the effects of different exposure situations including single high-concentration ACs (15 mg/L, SH-ACs), repeated low-concentration ACs (3 × 5 mg/L, RL-ACs) and ACs-SMs containing 15 mg/L ACs on morphological indexes, chlorophyll content, lipid peroxidation, enzymatic activity, and chlorophyll fluorescence indexes of submerged plant Vallisneria natans and the richness and diversity of its associated microfloras (epibiotic microbes and sediment microbes) were studied. The results showed that pure ACs (RL-ACs and SH-ACs groups) had negative effects on plant height, mean leaf number and area of V. natans, but promoted the increase of mean leaf length. In addition, pure ACs caused lipid peroxidation, activated the antioxidant defense system, decreased chlorophyll content, and damaged photosynthetic system in leaves. Interestingly, ACs-SMs not only had barely negative effects on above indexes of V. natans, but had certain positive effects at the later experiment stage (days 50-60). Pure ACs and ACs-SMs all reduced the richness and diversity of microfloras in each group, and promoted the increase of relative abundance of dominant bacteria Pseudomonas, leading to a simpler community structure. Significantly, V. natans leaves diminished the effects of pure ACs and ACs-SMs on epibiotic microbes, and the plant rhizosphere was beneficial to the increase of dominant bacteria that promoted plant growth. Thus, sustained-release microspherification technology can effectively relieve the ecotoxic side-effects of pure ACs on submerged plant and its associated microfloras. This study fills the gap on the ecological safety knowledge of ACs-SMs and provides primary data for evaluating the feasibility and commercialization prospects of ACs-SMs as algae inhibitor in aquatic ecosystem.

Effect of allelochemicals sustained-release microspheres on the ingestion, incorporation, and digestion abilities of Daphnia magna Straus.

Allelochemicals sustained-release microspheres (ACs-SMs) exhibited great inhibition effect on algae, however, few studies have focused on ACs-SMs toxicity on invertebrate. In this study, the effects of single high-concentration ACs (15 mg/L, SH-ACs), repeated low-concentration ACs (3 × 5 mg/L, RL-ACs) and ACs-SMs containing 15 mg/L ACs exposure on the ingestion, incorporation, and digestion of Daphnia magna Straus (DS) were investigated by stable isotope 15N labeling method. Meanwhile, the diversity and abundance of microflora in DS guts were determined by 16S rRNA genes and cloning methods. The results showed that SH-ACs exposure caused 50% and 33.3% death rates for newborn and adult DS, while RL-ACs exposure caused 10% death rate for newborn DS and no obvious effect on the activity of adult DS. And ACs-SMs exposure did not diminish the motility of both newborn and adult DS, indicating the lower acute toxicity of ACs-SMs. Furthermore, SH-ACs inhibited the ingestion (-6.45%), incorporation (-47.1%) and digestion (-53.8%) abilities of DS and reduced the microbial abundance (-27.7%) in DS guts. Compared with SH-ACs, RL-ACs showed relatively low impact on the ingestion (-3.23%), incorporation (-5.89%) and digestion (-23.9%) abilities of DS. Interestingly, ACs-SMs enhanced the ingestion (+9.68%), incorporation (+52.9%) and digestion (+51.3%) abilities of DS and increased the microbial abundance (+10.7%) in DS guts. Overall ACs and ACs-SMs reduced the diversity of microflora in DS guts. In conclusion, ACs-SMs can release ACs sustainably and prolong the sustained release time, which not only effectively reduce the toxicity of ACs, but also had positive effects on DS.

Effects and mechanisms of aged polystyrene microplastics on the photodegradation of sulfamethoxazole in water under simulated sunlight.

Pharmaceutical and microplastics (MPs) have been frequently detected in aquatic environment. In this study, the effects of polystyrene MPs (PS MPs) with different aging degrees on the photolysis of sulfamethoxazole (SMX) in simulated sunlit water were investigated. The results showed that the presence of PS MPs inhibited the photodegradation of SMX, and the photodegradation rate (kobs) of SMX was negatively correlated with the aging degree of PS MPs (R2 = 0.998). The aged PS MPs would cause light-screening effect, thereby reducing the photodegradation of SMX in sunlit water. Further, the free radical quenching experiment showed that the mechanism for inhibiting the photolysis of SMX was the reduction of the triplet excited state SMX (3SMX*). According to sample characterization, aging PS MPs formed more unsaturated chromophores and produced organic intermediates that enhanced photon absorption. Additionally, aged PS MPs also decreased the types and yields of degradation products of SMX via product analysis. This study provides an insight into the environmental behaviors of SMX and the photochemical roles of aged MPs in sunlit surface waters.

Reaction kinetics of dissolved black carbon with hydroxyl radical, sulfate radical and reactive chlorine radicals.

As an important component of dissolved organic matter (DOM), dissolved black carbon (DBC) which is characterized of abundant aromatic and oxygen-containing functional groups, is widely distributed in aquatic environments. Its presence may hinder the oxidation of organic micro-pollutants during advanced oxidation processes (AOPs) via free radicals scavenging effect. However, the second-order reaction rate constants of DBC with different free radicals including hydroxyl radical (OH•), sulfate radical (SO4•-), reactive chlorine radicals (RCR) are unknown and the relationship between the chemical composition of DBC and the second-order reaction rate constants during different AOPs (UV/H2O2, UV/PDS, UV/Chlorine) is also unclear. In this study, a plant-derived DBC was extracted from wheat biochar and fractionated according to molecular weight (i.e., <10 k, <3 k, and < 1 k Da). The second order rate constants of DBC reaction with different free radicals were determined by competitive kinetic method. Besides, the chemical composition of DBC was revealed by ultraviolet-visible (UV-Vis) spectroscopy, fluorescence excitation-emission-matrix (EEM) spectroscopy Fourier Transform Infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with statistical analysis. The results showed that the second-order rate constants decreased as the molecular weight increased. For the <1 k Da DBC, the kDBC-OH•, kDBC-SO4•--, kDBC-RCR were (1.83 ± 0.06) × 104, (7.60 ± 0.21) × 103, and (1.71 ± 0.13) × 104 L·mgC-1·s-1, which were 1.98, 2.19, 1.43 times of that for the <10 k Da fraction and 1.38, 1.36, 1.24 times of that for the <3 k Da fraction in UV/H2O2, UV/PDS and UV/Chlorine processes. In addition, the results of chemical composition analysis showed that DBC mainly contained humic substances and was rich in O-containing functional groups such as CO. The second order reaction rate constants of DBC with different free radicals decreased with increasing the molecular weight of DBC due to the more aggregated structure of the small molecules that the inner carbon of DBC was not easily exposed to free radicals.

Advances and prospects on the aquatic plant coupled with sediment microbial fuel cell system.

Energy resource scarcity and sediment pollution perniciousness have become enormous challenges, to which research has been focused on energy recovery and recycle technologies to solve both above problems. The organic matter stored in anoxic sediments of freshwater ecosystem represents a tremendous potential energy source. The system of aquatic plant coupled with sediment microbial fuel cell (AP-SMFC) has attracted much attention as a more feasible, economical and eco-friendly way to remediate sediment and surface water and generate electricity. However, the research on AP-SMFC has only been carried out in the last decade, and relevant studies have not been well summarized. In this review, the advances and prospects on AP-SMFC were systematically introduced. Firstly, the annual publication counts and keywords co-occurrence cluster of AP-SMFC were identified and visualized by resorting to the CiteSpace software, and the result showed that the research on AP-SMFC increased significantly in the last decade on the whole and will continue to increase. The bibliometric results provided valuable references and information on potential research directions for future studies. And then, the research progress and reaction mechanism of AP-SMFC were systematically described. Thirdly, the performance of AP-SMFC, including nutrients removal, organic contaminants removal, and electricity generation, was systematically summarized. AP-SMFC can enhance the removal of pollutants and electricity generation compared with SMFC without AP, and is considered to be an ideal technology for pollutants removal and resource recovery. Finally, the current challenges and future perspectives were summarized and prospected. Therefore, the review could serve as a guide for the new entrants to the field and further development of AP-SMFC application.

Recent advances and trends of trichloroethylene biodegradation: A critical review.

Trichloroethylene (TCE) is a ubiquitous chlorinated aliphatic hydrocarbon (CAH) in the environment, which is a Group 1 carcinogen with negative impacts on human health and ecosystems. Based on a series of recent advances, the environmental behavior and biodegradation process on TCE biodegradation need to be reviewed systematically. Four main biodegradation processes leading to TCE biodegradation by isolated bacteria and mixed cultures are anaerobic reductive dechlorination, anaerobic cometabolic reductive dichlorination, aerobic co-metabolism, and aerobic direct oxidation. More attention has been paid to the aerobic co-metabolism of TCE. Laboratory and field studies have demonstrated that bacterial isolates or mixed cultures containing Dehalococcoides or Dehalogenimonas can catalyze reductive dechlorination of TCE to ethene. The mechanisms, pathways, and enzymes of TCE biodegradation were reviewed, and the factors affecting the biodegradation process were discussed. Besides, the research progress on material-mediated enhanced biodegradation technologies of TCE through the combination of zero-valent iron (ZVI) or biochar with microorganisms was introduced. Furthermore, we reviewed the current research on TCE biodegradation in field applications, and finally provided the development prospects of TCE biodegradation based on the existing challenges. We hope that this review will provide guidance and specific recommendations for future studies on CAHs biodegradation in laboratory and field applications.

Enhanced photocatalytic performance of visible-light-driven CuOx/TiO2-x for degradation of gaseous formaldehyde: Roles of oxygen vacancies and nano copper oxides.

Photocatalysis is an effective method for the removal of formaldehyde (HCHO), and high-efficiency visible-light-driven photocatalysts were urgently required. Herein, oxygen vacancies (OVs) and nano copper oxides (CuOx) synergistically modified TiO2 (CuOx/TiO2-x) photocatalysts were synthesized by one-step hydrothermal followed by impregnation method. The photocatalytic decomposition of HCHO reached 100% at initial concentration of 180 ppm under relative humidity (RH) = 60% by 0.1g CuOx/TiO2-x in 150 min visible light irradiation. Characterization results explored the complementary effect of OVs and CuOx systematically. The OVs increased the separation efficiency of photogenerated charge carriers and act as adsorption/active sites in HCHO photocatalytic oxidation. The moisture and O2 were adsorbed and actived by OVs to generate reactive oxygen species (ROS). After doped CuOx on the surface of TiO2-x, the photoexcited electrons in Cu2O could transfer to the conduction band (CB) of TiO2-x and the photoexcited electrons of TiO2-x could be captured by Cu nanoparticles. Therefore, more ROS were generated due to the synergistic effect of OVs and CuOx. The In-situ Fourier transform infrared (in-situ FTIR) measurements show the hydroxyl radical (•OH) was the dominant radical in HCHO photocatalytic oxidation, while •O2- could also upgrade the photodegradation efficiency of HCHO. Furthermore, the stability tests showed the degradation efficiency of HCHO still reached 90% after five recycles, indicating that CuOx/TiO2-x nanocomposites displayed a stable and high photoactivity in volatile organic compounds (VOCs) decomposition.

Enhanced performance and mechanisms of sulfamethoxazole removal in vertical subsurface flow constructed wetland by filling manganese ore as the substrate.

Sulfamethoxazole (SMX), a typical sulfonamide antibiotic, is ubiquitous in secondary effluent and may pose undesirable effects on the aquatic ecosystem and human health. Constructed wetland (CW) is more and more applied in advanced sewage treatment, and the substrate plays an important role in removing pollutants. Manganese (Mn) ore has been widely concerned as a new type of substrate to remove pollutants in CW due to its high adsorption and redox properties. However, the removal mechanism of antibiotics by Mn ore CW is still unclear. In this study, Mn ore was selected as the substrate of a vertical flow constructed wetland (VFCW) while gravel substrate was selected as a control group, and the removal efficiencies of SMX in two VFCWs were investigated and compared. Experimental devices were layered as different regions, including anaerobic (0-32 cm), anoxic (32-64 cm) and aerobic (64-80 cm) zones, to examine the removal characteristics of SMX in different regions. And the removal mechanism of SMX was also explored by examining the adsorption and oxidation of Mn ore and the microbial degradation performance. The results showed that the final removal efficiency of SMX in CW filled with Mn ore substrate (M-CW) (48.4%) increased by 39.6%, compared with CW filled with gravel substrate (G-CW) (8.8%). According to the calculation of mass balance, the total loss of SMX caused by the oxidation of Mn ore and biodegradation accounted for 33.0% of the total SMX input in M-CW, the SMX loss caused by the biodegradation in G-CW accounted for 13.0%, and the substrate adsorption in M-CW and G-CW occupied 15.0% and 7.0% of the total SMX input, respectively. Mn(II) was formed during the oxidation of SMX by Mn(III, IV) and dissimilated Mn(III, IV) reduction by microorganisms in anaerobic environment (0-32 cm). Whereafter, the produced Mn(II) entered into the aerobic zone (64-80 cm) with the water flow and was re-oxidized into biogenic Mn oxides (BioMnOx) which had high adsorption and oxidation performance for SMX. Therefore, Mn ore could enhance SMX removal efficiency in anaerobic and aerobic zones by Mn redox process.

A review: Application of allelochemicals in water ecological restoration--algal inhibition.

Problems caused by harmful algal blooms have attracted worldwide attention due to their severe harm to aquatic ecosystems, prompting researchers to study applicable measures to inhibit the growth of algae. Allelochemicals, as secondary metabolites secreted by plants, have excellent biocompatibility, biodegradability, obvious algal inhibiting effect and little ecological harm, and have promising application prospect in the field of water ecological restoration. This review summarized the research progress of allelochemicals, including (i) definition, development, and classification, (ii) influencing factors and mechanism of algal inhibition, (iii) the preparation methods of algal inhibitors based on allelochemicals. The future research directions of allelochemicals sustained-released microspheres (SRMs) were also prospected. In the future, it is urgent to explore more efficient allelochemicals, to study the regulation mechanism of allelochemicals in natural water bodies, and to improve the preparation method of allelopathic algal suppressant. This paper proposed a feasible direction for the development of allelochemicals SRMs which exhibited certain guiding significance for their application in water ecological restoration.